United States
Environmental Protection
.gency
Office of Solid Waste
and Emergency Response
Washington, DC 20460
November 1986
SW846
Third Edition
Solid Waste
Test Methods
for Evaluating Solid Waste
Volume IB: Laboratory Manual
Physical/Chemical Methods
-------
ABSTRACT
4 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, 1gnitab1l1ty, and composition of the waste and the mobility of
toxic species present In the waste.
ABSTRACT - 1
Revision
Date September 1986
-------
VOLUME ONE,
SECTION B
Revision 0
Date September 1986
-------
For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402
-------
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
-------
CHAPTER THREE — METALLIC ANALYTES
3.1 Sampling Considerations
3.2 Sample Preparation Methods
Method 3005: Acid Digestion of Waters for Total Recoverable
or Dissolved Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy ,
Method 3010: Acid Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
Method 3020: ' Acid Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Furnace
Atomic Absorption Spectroscopy
Method 3040: Dissolution Procedure for Oils, Greases, or
Waxes
Method 3050: Acid Digestion of Sediments, Sludges, and Soils
3.3 Methods for Determination of Metals
Method 6010:
Inductively Coupled
Spectroscopy
Plasma Atomic Emission
Method 7000:
Method 7020:
Method 7040:
Method 7041:
Method 7060:
Method 7061:
Method 7080:
Method 7090:
Method 7091:
Method 7130:
Method 7131:
Method 7140:
Method 7190:
Method 7191:
Method 7195:
Method 7196:
Method 7197:
Method 7198:
Method 7200:
Method 7201:
Method 7210:
Method 7380:
Method 7420:
Method 7421:
Method 7450:
Method 7460:
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace 'Technique)
Arsenic (AA, Gaseous Hydride)
Barium (AA, Direct Aspiration)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Coprecipitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Chelation/Extraction)
Chromium, Hexavalent (Differential Pulse
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
-------
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 sol id 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)
Zinc (AA, Direct Aspiration)
APPENDIX — COMPANY REFERENCES
CONTENTS - 3
Revision 0
Date September 1986
-------
VOLUME ONE.
SECTION B
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 References
CHAPTER FOUR — ORGANIC ANALYTES
4.1 Sampling Considerations
4.2 Sample Preparation Methods
4.2.1 Extractions and Preparations
Method 3500: Organic Extraction And Sample Preparation
Method 3510: Separatory Funnel Liquid-Liquid Extraction
Method 3520: Continuous Liquid-Liquid Extraction
Method 3540: Soxhlet Extraction
Method 3550: Sonication Extraction
Method 3580: Waste Dilution
Method 5030: Purge-and-Trap
Method 5040: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train
4.2.2 Cleanup
Method 3600: Cleanup
Method 3610: Alumina Column Cleanup
Method 3611: Alumina Column Cleanup And Separation of
Petroleum Wastes
Method 3620: Florisil Column Cleanup
Method 3630: Silica Gel Cleanup
Method 3640: Gel-Permeation Cleanup
Method 3650: Acid-Base Partition Cleanup
Method 3660: Sulfur Cleanup
CONTENTS - 4
-------
4.3 Determination of Organic Analytes
4.3.1 Gas Chromatographic Methods
Method 8000: Gas Chromatography
Method 8010: Halogenated Volatile Organics
Method 8015: Nonhalogenated Volatile Organics
Method 8020: Aromatic Volatile Organics
Method 8030: Acrolein, Acrylonitrile, Acetonitrile
Method 8040: Phenols
Method 8060: Phthalate Esters
Method 8080: Organochlorine Pesticides and PCBs
Method 8090: Nitroaromatics and Cyclic Ketones
Method 8100: Polynuclear Aromatic Hydrocarbons
Method 8120: Chlorinated Hydrocarbons
Method 8140: Organophosphorus Pesticides
Method 8150: Chlorinated Herbicides
4.3.2 Gas Chromatographic/Mass Spectroscopic Methods
Method 8240: Gas Chromatography/Mass Spectrometry for
Volatile Organics
Method 8250: Gas Chromatography/Mass Spectrometry for
Semi volatile Organics: Packed Column
Technique
Method 8270: Gas Chromatography/Mass Spectrometry for
Semi volatile Organics: Capillary Column
Technique
Method 8280: The Analysis of Polychlorinated Dibenzo-P-
Dioxins and Polychlorinated Dibenzofurans
Appendix A: Signal-to-Noise Determination Methods
Appendix B: Recommended Safety and Handling Procedures
for PCDD's/PCDF's
4.3.3 High Performance Liquid Chromatographic Methods
Method 8310: Polynuclear Aromatic Hydrocarbons
4.4 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
APPENDIX — COMPANY REFERENCES
CONTENTS - 5
Revision
Date September 1986
-------
VOLUME ONE,
SECTION C
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 References
CHAPTER FIVE — MISCELLANEOUS TEST METHODS
Method 9010:
Method 9012:
Method 9020:
Method 9022:
Method 9030:
Method 9035:
Method 9036:
Method 9038:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071:
Total and Amenable Cyanide (Colorimetric,
Manual)
Total and Amenable Cyanide (Colorimetric,
Automated UV)
Total Organic Hal ides (TOX)
Total Organic Hal ides (TOX) by Neutron
Activation Analysis
Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methyl thymol
Blue, AA II)
Sulfate (Turbidimetric)
Total Organic Carbon
Phenolics (Spectrophotometric, Manual 4-AAP With
Distillation)
Phenolics (Colorimetric, Automated 4-AAP with
Distillation)
Phenolics (Spectrophotometric, MBTH with
Distillation)
Total Recoverable Oil & Grease (Gravimetric,
Separatory Funnel Extraction)
Oil & Grease Extraction Method for Sludge
Samples
CONTENTS - 6
Revision 0
Date September 1986
-------
Method 9131:
Method 9132:
Method 9200:
Method 9250:
Method 9251:
Method 9252:
Method 9320:
Total Coliform: Multiple Tube Fermentation
Technique
Total Coliform: Membrane Filter Technique
Nitrate
Chloride (Colorimetric, Automated Ferricyanide
AAI)
Chloride (Colorimetric, Automated Ferricyanide
AAI I)
Chloride (Titrimetric, Mercuric Nitrate)
Radium-228
CHAPTER SIX — PROPERTIES
Method 1320:
Method 1330:
Method 9040:
Method 9041:
Method 9045:
Method 9050:
Method 9080:
Method 9081:
Method 9090:
Method 9095:
Method 9100:
Method 9310:
Method 9315:
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil pH
Specific Conductance
Cation-Exchange Capacity of Soils (Ammonium
Acetate)
Cation-Exchange Capacity of Soils (Sodium
Acetate)
Compatibility Test for Wastes and Membrane
Liners
Paint Filter Liquids Test
Saturated Hydraulic Conductivity, Saturated
Leachate Conductivity, and Intrinsic
Permeability
Gross Alpha & Gross Beta
Alpha-Emitting Radium Isotopes
PART II CHARACTERISTICS
CHAPTER SEVEN — INTRODUCTION AND REGULATORY DEFINITIONS.
7.1 Ignitability
7.2 Corrositivity
7.3 Reactivity
Section 7.3.3.2: Test Method to Determine Hydrogen Cyanide
Released from Wastes
Section 7.3.4.1: Test Method to Determine Hydrogen Sulfide
Released from Wastes
7.4 Extraction Procedure Toxicity
CONTENTS - 7
Revision 0
Date September 1986
-------
CHAPTER EIGHT — METHODS FOR DETERMINING CHARACTERISTICS
8.1 Ignilability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Method 1020: Setaflash Closed-Cup Method for Determining
Ignitability
8.2 Corrosivity
Method 1110: Corrosivity Toward Steel
8.3 Reactivity
8.4 Toxicity
Method 1310: Extraction Procedure (EP) Toxicity Test Method
and Structural Integrity Test
APPENDIX — COMPANY REFERENCES
CONTENTS - 8
Revision 0
Date September 1986
-------
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 IIISAMPLING
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
-------
PART IV MONITORING
CHAPTER ELEVEN — GROUND WATER MONITORING
11.1 Background and Objectives
11.2 Relationship to the Regulations and to Other Documents
11.3 Revisions and Additions
11.4 Acceptable Designs and Practices
11.5 Unacceptable Designs and Practices
CHAPTER TWELVE — LAND TREATMENT MONITORING
12.1 Background
12.2 Treatment Zone
12.3 Regulatory Definition
12.4 Monitoring and Sampling Strategy
12.5 Analysis
12.6 References and Bibliography
CHAPTER THIRTEEN — INCINERATION
13.1 Introduction
13.2 Regulatory Definition
13.3 Waste Characterization Strategy .
13.4 Stack-Gas Effluent Characterization Strategy
13.5 Additional Effluent Characterization Strategy
13.6 Selection'of Specific Sampling and Analysis Methods
13.7 References
APPENDIX — COMPANY REFERENCES
CONTENTS - 10
Revision
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
Method Number,
Third Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
3500
3510
3520
3540
3550
3580
3600
3610
3611
3620
3630
3640
3650
3660
3810
3820
5030
5040
6010
7000
7020
Chapter Number,
Third Edition
Ten
Ten
Ten
Eight (8.1)
Eight (8.1)
Eight (8.2
Eight (8.4
Six
Six
Three
Three
Three
Three
Three
Four (4.2.1)
Four (4.2.1)
Four (4.2.1)
Four (4.2.1)
Four (4.2.1)
Four (4.2.1)
Four (4.2.2)
Four (4.2.2
Four (4.2.2
Four (4.2.2
Four (4.2.2
Four (4.2.2)
Four (4.2.2)
Four (4.2.2)
Four (4.4)
Four (4.4)
Method Number.
Current Revision
Four (4
Four (4
Three
Three
Three
(4.2.1)
(4.2.1)
Second Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
None (new method)
3510
3520
3540
3550
None (new method)
None (new method)
None (new method)
3570
None (new method)
None (new method)
None (new method)
None (new method)
None (new method)
5020
None (new method)
5030
3720
6010
7000
7020
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 1
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
Number
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 2
Revision Q
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
7840
7841
7870
7910
7911
7950
8000
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
8240
8250
8270
8280
8310
9010
9020
9022
9030
9035
9036
9038
9040
9041
9045
9050
Chapter Number,
Third Edition
Three
Three
Three
Three
Three
Three
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Method Number,
Current Revision
Four
Four
(4.
(4.
Four
Four
(4,
(4,
Four (4.3
1)
1)
Four (4.3.1)
Four (4.3.2)
.2)
,2)
.2)
Four (4.3.3)
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
Second Edition
7840
7841
7870
7910
7911
7950
None (new method)
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
8240
8250
8270
None (new method)
8310
9010
9020
9022
9030
9035
9036
9038
9040
9041
9045
9050
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 3
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
Number
9060 Five
9065 Five
9066 Five
9067 Five
9070 Five
9071 Five
9080 Six
9081 Six
9090 . Six
9095 Six
9100 . ' Six
9131 Five
9132 . Five
9200 Five
9250 Five
9251 Five
9252 Five
9310 Six
9315 Six
9320 Five
HCN Test Method Seven
Test Method ..Seven
9060
9065 .
9066
9067
9070
9071
9080
9081
9090
9095
9100
9131
9132
9200
9250
9251
9252
9310
9315
9320
HCN Test Method
H2S Test Method
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 4
Revision 0
Date September 1986
-------
PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
Test Methods for Evaluating Solid Waste (SW-846) is intended to provide a
unified, up-to-date source of information on sampling and analysis related to
compliance with RCRA regulations. It brings together into one reference all
sampling and testing methodology approved by the Office of Solid Waste for use
in implementing the RCRA regulatory program. The manual provides methodology
for collecting and testing representative samples of waste and other materials
to be monitored. Aspects of sampling and testing covered in SW-846 include
quality control, sampling plan development and implementation, analysis of
inorganic and organic constituents, the estimation of intrinsic physical
properties, and the appraisal of waste characteristics.
The procedures described in this manual are meant to be comprehensive and
detailed, coupled with the realization that the problems encountered in
sampling and analytical situations require a certain amount of flexibility.
The solutions to these problems will depend, in part, on the skill, training,
and experience of the analyst. For some situations, it is possible to use
this manual in rote fashion. In other situations, it will require a
combination of technical abilities, using the manual as guidance rather than
in a step-by-step, word-by-word fashion. Although this puts an extra burden
on the user, it is unavoidable because of the variety of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
This manual is divided into two volumes. Volume I focuses on laboratory
activities and is divided for convenience into three sections. Volume IA
deals with quality control, selection of appropriate test methods, and
analytical methods for metallic species. Volume IB consists of methods for
organic analytes. Volume 1C includes a variety of test methods for
miscellaneous analytes and properties for use in evaluating the waste
characteristics. Volume II deals with sample acquisition and includes quality
control, sampling plan design and implementation, and field sampling methods.
Included for the convenience of sampling personnel are discusssions of the
ground water, land treatment, and incineration monitoring regulations.
Volume I begins with an overview of the quality control precedures to be
Imposed upon the sampling and analytical methods. The quality control chapter
(Chapter One) and the methods chapters are interdependent. The analytical
procedures cannot be used without a thorough understanding of the quality
control requirements and the means to Implement them. This understanding can
be achieved only be reviewing Chapter One and the analytical methods together.
It is expected that individual laboratories, using SW-846 as the reference
PREFACE - 1
Revision 0
Date September 1986
-------
source, will select appropriate methods and develop a standard operating
procedure (SOP) to be followed by the laboratory. The SOP should incorporate
the pertinent information from this manual adopted to the specific needs and
circumstances of the individual laboratory as well as to the materials to be
evaluated.
The method selection chapter (Chapter Two) presents a comprehensive
discussion of the application of these methods to various matrices in the
determination of groups of analytes or specific analytes. It aids the chemist
in constructing the correct analytical method from the array of procedures
whigh may cover the matrix/analyte/concentration combination of interests.
The • section discusses the objective of the testing program and . its
relationship to the choice of an analytical method. Flow charts are presented
along with tables to guide in the selection of the correct analytical
procedures to form the appropriate method.
The analytical methods are separated into distinct procedures describing
specific, independent analytical operations. These include extraction,
digestion, cleanup, and determination. This format allows linking of the
various steps in the analysis according to: the type of sample (e.g., water,
soil, sludge, still bottom); analytes(s) of interest; needed sensitivity; and
available analytical instrumentation. The chapters describing Miscellaneous
Test Methods and Properties, however, give complete methods which are not
amenable to such segmentation to form discrete procedures.
The introductory material at the beginning of each section containing
analytical procedures presents information on sample handling and
preservation, safety, and sample preparation.
Part II of Volume I (Chapters Seven and Eight) describes the
characteristics of a waste. Sections following the regulatory descriptions
contain the methods used to determine if the waste is hazardous because it
exhibits a particular characteristic.
Volume II gives background Information on statistical and nonstatistical
aspects of sampling. It also presents practical sampling techniques
appropriate for situations presenting .a variety of physical conditions.
A discussion of the regulatory requirements with respect to several
monitoring categories is also given in this volume. These include ground
water monitoring, land treatment, and incineration. The purpose of this
guidance is 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 is 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
-------
CHAPTER ONE, REPRINTED
QUALITY CONTROL
1.1 INTRODUCTION
Appropriate use of data generated under the great range of analytical
conditions encountered in RCRA analyses requires reliance on the quality
control practices incorporated into the methods and procedures. The
Environmental Protection Agency generally requires using approved methods for
sampling and analysis operations fulfilling regulatory requirements, but the
mere approval of these methods does not guarantee adequate results.
Inaccuracies can result from many causes, including unanticipated matrix
effects, equipment malfunctions, and operator error. Therefore, the quality
control component of each method is indispensable.
The data acquired from quality control procedures are used to estimate
and evaluate the information content of analytical data and to determine the
necessity or the effect of corrective action procedures. The means used to
estimate information content include precision, accuracy, detection limit, and
other quantifiable and qualitative indicators.
1.1.1 Purpose of this Chapter
This chapter defines the quality control procedures and components that
are mandatory 1n the performance of analyses, and indicates the quality
control information which must be generated with the analytical data. Certain
activities in an integrated program to generate quality data can be classified
as management (QA) and other as functional (QC). The presentation given here
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 similarily 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.
ONE - 1
Revision 0
Date September 1986
-------
1.1.2 Program Design
The initial step for any sampling or analytical work should be strictly
to define the program goals. Once the goals have been defined, a program must
be designed to meet them. QA and QC measures will be used to monitor the
program and to ensure that all data generated are suitable for their intended
use. The responsibility of ensuring that the QA/QC measures are properly
employed must be assigned to a knowledgeable person who is not directly
involved in the sampling or analysis.
One approach that has been found to provide a useful structure for a
QA/QC program is 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,
it 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 in QAMS-004/80 (see References, Section
1.6).
Project-specific QA/QC plans differ from program plans in that specific
details of a particular sampling/analysis program are addressed. For example,
a program plan might state that all analyzers will be calibrated according to
a specific protocol given in written standard operating procedures for the
laboratory (SOP), while a project plan would state that a particular protocol
will be used to calibrate the analyzer for a specific set of analyses that
have been defined in the plan. The project plan draws on the program plan or
its basic structure and applies this management approach to specific
determinations. A given agency or laboratory would have only one quality
assurance program plan, but would have a quality assurance project plan for
each of its projects. The elements of a project plan and its preparation are
described in QAMS/005/80 (see References, Section 1.6) and are listed in
Figure 1-1.
Some organizations may find it 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, it is
especially important that adequate QA management structures exist and that any
procedures used exist as standard operating procedures (SOP), written
documents which detail an operation, analysis or action whose mechanisms are
thoroughly prescribed and which is commonly accepted as the method for
performing certain routine or repetitive tasks. Having copies of SW-846 and
all its referenced documents in one's laboratory is not a substitute for
having in-house versions of the methods written to conform to specific
instrumentation, data needs, and data quality requirements.
ONE - 2
Revision 0
Date September 1986
-------
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
ONE - 3
Revision 0
Date September 1986
-------
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 is 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 is responsible for ensuring that the data produced by the
data generator meet agreed-upon specifications.
Responsibility for data review is sometimes assigned to a "Quality
Assurance Officer" or "QA Manager." This individual has broad authority to
approve or disapprove project plans, specific analyses and final reports. The
QA Officer is independent from the data generation activities. In general,
the QA Officer is responsible for reviewing and advising on all aspects of
QA/QC, including:
Assisting the data requestor in specifying the QA/QC procedure to be used
during the program;
Making on-site evaluations and submitting audit samples to assist in
reviewing QA/QC procedures; and,
f problems are detected, making recommendations to the data requestor and
upper corporate/institutional management to ensure that appropriate
corrective actions are taken.
In programs where large and complex amounts of data are generated from
both field and laboratory activities, it is helpful to designate sampling
monitors, analysis monitors, and quality control/data monitors to assist in
carrying out the program or project.
The sampling monitor is 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) is 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;
ONE - 4
Revision
Date September 1986
-------
Receiving samples from the field and verifying that incoming samples
correspond to the packing list or chain-of-custody sheet; and
Verifying that laboratory QC and analytical procedures are being followed
as specified in the workplan, reviewing sample and QC data during the
course of analyses, and, if questionable data exist, determining which
repeat samples or analyses are needed.
The quality control and data monitor is responsible for QC activities and
data management. These include:
Maintaining records of all incoming samples, tracking those samples
through subsequent processing and analysis, and, ultimately,
appropriately disposing of those samples at the conclusion of the
program;
Preparing quality control samples for analysis prior to and during the
program;
Preparing QC and sample data for review by the analysis coordinator and
the program manager; and
Preparing QC and sample data for transmission and entry into a computer
data base, if appropriate.
1.1.4 Performance and Systems Audits
The QA Officer may carry out performance and/or systems audits to ensure
that data of known and defensible quality are produced during a program,.
Systems audits are qualitative evaluations of all components of field and
laboratory quality control measurement systems. They determine if 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 in the QA/QC plan with those actually scheduled or performed.
A special type of systems audit is the data management audit. This audit
addresses only data collection and management activities.
The performance audit is a quantitative evaluation of the measurement
systems of a program. It requires testing the measurement systems with
samples of known composition or behavior to evaluate precision and accuracy.
The performance audit is carried out by or under the auspices of the QA
Officer without the knowledge of the analysts. Since this is seldom
achievable, many variations are used that increase the awareness of the
analyst as to the nature of the audit material.
ONE - 5
Revision 0
Date September 1986
-------
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 is 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 1n 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.
ONE - 6
Revision
Date September 1986
-------
The individual responsible within the organization structure for
preparing the periodic reports should be identified in the organizational or
management plan. The final report for each project should also include a
separate QA section which summarizes data quality information contained in the
periodic reports.
Other guidance on quality assurance management and organizations is
available from the Agency and professional organizations such as ASTM, AOAC,
APHA and FDA.
1.1.7 Quality Control Program for the Analysis of RCRA Samples
An analytical quality control program develops information which can be
used to:
Evaluate the accuracy and precision of analytical data in order to
establish the quality of the data;
Provide an indication of the need for corrective actions, when comparison
with existing regulatory or program criteria or data trends shows that
activities must be changed or monitored to a different degree; and
To determine the effect of corrective actions.
1.1.8 Definitions
ACCURACY:
ANALYTICAL BATCH:
BLANK:
Accuracy means the nearness of a result or the mean (7) of
a set of results to the true value. Accuracy is assessed
by means of reference samples and percent recoveries.
The basic unit for analytical quality control is the
analytical batch. The analytical batch is defined as
samples which are analyzed together with the same method
sequence and the same lots of reagents and with the
manipulations common to each sample within the same time
period or in continuous sequential time periods. Samples
in each batch should be of similar composition.
A blank is an artificial sample designed to monitor the
introduction of artifacts into the process. For aqueous
samples, reagent water is used as a blank matrix; however,
a universal blank matrix does not exist for solid samples,
and therefore, no matrix is used. The blank is taken
through the appropriate steps of the process.
A reagent blank is an aliquot of analyte-free water or
solvent analyzed with the analytical batch. Field blanks
are aliquots of analyte-free water or solvents brought to
the field in sealed containers and transported back to the
ONE - 7
Revision 0
Date September 1986
-------
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 in the field and the contents are poured
appropriately over or through the sample collection device,
collected in a sample container, and returned to the
laboratory as a sample. Equipment blanks are a check on
sampling device cleanliness.
Verification of the ratio of instrument response to analyte
amount, a calibration check, is done by analyzing for
analyte standards in an appropriate solvent. Calibration
check solutions are made from a stock solution which is
different from the stock used to prepare standards.
A blank which has been spiked with the analyte(s) from an
independent source in 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. The matrix used
shall be phase matched with the samples and well
characterized: for an example, reagent grade water is
appropriate for an aqueous sample.
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 is requested or required. For
the purposes of this manual, environmental samples shall be
classified as follows:
Surface Water and Ground Water;
.Drinking Water -- delivered (treated or untreated) water
designated as potable water;
Water/Wastewater — raw source waters for public drinking
water supplies, ground waters, municipal influents/
effluents, and industrial Influents/effluents;
Sludge — municipal sludges and Industrial sludges;
Waste -- aqueous and nonaqueous liquid wastes, chemical
solids, contaminated soils, and industrial liquid and solid
wastes.
ONE - 8
Revision 0
Date September 1986
-------
MATRIX/SPIKE-
DUPLICATE
ANALYSIS:
MQL:
PRECISION:
PQL:
RCRA:
REAGENT GRADE:
REPLICATE SAMPLE:
STANDARD CURVE:
SURROGATE:
In matrix/spike duplicate analysis, predetermined quantl-
stock solutions of certain analytes are added to a
ties 01
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 1n the sample 1s greater than
0.1%, no spike of the analyte is 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 is
replicate results among
any prior information as to
assessed by means of duplicate/replicate sample analysis.
The practical quantitation 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 is a sample prepared by dividing a
sample into two or more separate aliquots. Duplicate
samples are considered to be two replicates.
A standard curve is 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.
ONE - 9
Revision 0
Date September 1986
-------
WATER: Reagent, analyte-free, or laboratory pure water means
distilled or deionized water or Type II reagent water which
is free of contaminants that may interfere with the
analytical test in question.
1.2 QUALITY CONTROL
The procedures indicated below are to be performed for all analyses.
Specific instructions relevant to particular analyses are given in the
pertinent analytical procedures.
1.2.1 Field Quality Control
The sampling component of the Quality Assurance Project Plan (QAPP) shall
include: . •
Reference to or incorporation of accepted .sampling techniques in the
sampling plan; ,
Procedures for documenting and justifying any field actions contrary to
the QAPP;
Documentation of all pre-field activities such as equipment check-out,
calibrations, and container storage and preparation;
Documentation of field measurement quality control data (quality control
procedures for such measurements shall be equivalent to corresponding
laboratory QC procedures); -
Documentation of field activities;
Documentation of post-field activities including sample shipment and
receipt, field team de-briefing and equipment check-in;
Generation of quality control samples including duplicate samples, field
blanks, equipment blanks, and trip blanks; and
The use of these samples in the context of data evaluation, with details
of the methods employed (including statistical methods) and of the
criteria upon which the information generated will be judged.
1.2.2 Analytical Quality Control
A quality control operation or component is only useful if it can be
measured or documented. The following components of analytical quality
control are related to the analytical batch. The procedures described are
intended to be applied to chemical analytical procedures; although the
principles are applicable to radio-chemical or biological analysis, the
procedures may not be directly applicable to such techniques.
ONE - 10
Revision
Date September 1986
-------
All quality control data and records required by this section shall be
retained by the laboratory and shall be made available to the data requestor
as appropriate. The frequencies of these procedures shall be as stated below
or at least once with each analytical batch.
1.2.2.1 Spikes, Blanks and Duplicates
General Requirements
These procedures shall be performed at least once with each analytical
batch with a minimum of once per twenty samples.
1.2.2.1.1 Duplicate Spike
A split/spiked field sample shall be analyzed with every analytical batch
or once in twenty samples, whichever is the greater frequency. Analytes
stipulated by the analytical method, by applicable regulations, or by other
specific requirements must be spiked into the sample. Selection of the sample
to be spiked and/or split depends on the information required and the variety
of conditions within a typical matrix. In some situations, requirements of
the site being sampled may dictate that the sampling team select a sample to
be spiked and split based on a pre-visit evaluation or the on-site inspection.
This does not preclude the laboratory's spiking a sample of its own selection
as well. In other situations the laboratory may select the appropriate
sample. The laboratory's selection should be guided by the objective of
spiking, which is to determine the extent of matrix bias or interference on
analyte recovery and sample-to-sample precision. For soil/sediment samples,
spiking is performed at approximately 3 ppm and, therefore, compounds in
excess of this concentration in the sample may cause interferences for the
determination of the spiked analytes.
1.2.2.1.2 Blanks
Each batch shall be accompanied by a reagent blank. The reagent blank
shall be carried through the entire analytical procedure.
1.2.2.1.3 Field Samples/Surrogate Compounds
Every blank, standard, and environmental sample (including matrix
spike/matrix duplicate samples) shall be spiked with surrogate compounds prior
to purging or extraction. Surrogates shall be spiked into samples according
to the appropriate analytical methods. Surrogate spike recoveries shall fall
within the control limits set by the laboratory (in accordance with procedures
specified in the method or within +20%) for samples falling within the
quantification limits without dilution. Dilution of samples to bring the
analyte concentration into the linear range of calibration may dilute the
surrogates below the quantification limit; evaluation of analytical quality
then will rely on the quality control embodied in the check, spiked and
duplicate spiked samples.
ONE - 11
Revision 0
Date September 1986
-------
1.2.2.1.4 Check Sample
Each analytical batch shall contain a check sample. The analytes
employed shall be a representative subset of the analytes to be determined.
The concentrations of these analytes shall approach the estimated
quantification limit in the matrix of the check sample. In particular, check
samples for metallic analytes shall be matched to field samples in phase and
in generaT~matrix composition.
1.2.2.2 Clean-Ups
Quality control procedures described here are intended for adsorbent
chromatography and back extractions applied to organic extracts. All batches
of adsorbents (Florisil, alumina, silica gel, etc.) prepared for use shall be
checked for analyte recovery by running the elution pattern with standards as
a column check. The elution pattern shall be optimized for maximum recovery
of analytes and maximum rejection of contaminants.
1.2.2.2.1 Column Check Sample
The elution pattern shall be reconfirmed with a column check of standard
compounds after activating or deactivating a batch of adsorbent. These
compounds shall be representative of each elution fraction. Recovery as
specified in the methods is considered an acceptable column check. A result
lower than specified indicates that the procedure is not acceptable or has
been misapplied.
1.2.2.2.2 Column Check Sample Blank
The check blank shall be run after activating or deactivating a batch of
adsorbent.
1.2.2.3 Determinations
1.2.2.3.1 Instrument Adjustment: Tuning, Alignment, etc.
Requirements and procedures are instrument- and method-specific.
Analytical instrumentation shall be tuned and aligned in accordance with
requirements which are specific to the instrumentation procedures employed.
Individual determinative procedures shall be consulted. Criteria for initial
conditions and for continuing confirmation conditions for methods within this
manual are found in the appropriate procedures.
1.2.2.3.2 Calibration
Analytical instrumentation shall be calibrated in 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.
ONE - 12
Revision 0
Date September 1986
-------
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 is verified by using at least one
reagent blank and one standard at a level normally encountered or expected 1n
such samples. The response for each standard shall be based upon the average
of three replicate readings of the standard. If the results of the
verification are not within +10% of the original curve, a new standard shall
be prepared and analyzed. If the results of the second verification are not
within +10% of the original standard curve, a reference standard should be
employee! to determine if the discrepancy is with the standard or with the
instrument. New standards should also be prepared on a quarterly basis at a
minimum. All data used in drawing or describing the curve shall be so
indicated on the curve or its description. A record shall be made of the
verification.
Standard deviations and relative standard deviations shall be calculated
for the percent recovery of analytes from the spiked sample duplicates and
from the check samples. These values shall be established for the twenty most
recent determinations in each category.
1.2.2.3.4 Additional Quality Control Requirements for
Organic Analysis
The following requirements shall be applied to the analysis of samples by
gas chromatography, liquid chromatography and gas chromatography/mass
spectrometry.
The calibration of each instrument shall be verified at frequencies
specified in 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-bromofluorobenzene (BFB) for determinations
of volatiles and with decafluorotriphenylphosphine (DFTPP) for determinations
of semi-volatiles. The required ion abundance criteria shall be met before
determination of any analytes. If the system does not meet the required
specification for one or more of the required ions, the instrument must be
retuned and rechecked before proceeding with sample analysis. The tune
performance check criteria must be achieved daily or for each 12 hour
operating period, whichever is more frequent.
Background subtraction should be straightforward and designed only to
eliminate column bleed or instrument background ions. Background subtraction
ONE - 13
Revision 0
Date September 1986
-------
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 in the
appropriate general procedures (7000, 8000) and the specific analytical
methods.
In some situations in the course of determining metal analytes, matrix-
..matched calibration standards may be required. These standards shall be
composed of the pure reagent, approximation of the matrix, and reagent
addition of major interferents in the samples. This will be stipulated in the
procedures.
Estimation of the concentration of an organic compound not contained
within the calibration standard may be accomplished by comparing mass spectral
response of the compound with that of an internal standard. The procedure is
specified in the methods.
ONE - 14
Revision 0
Date September 1986
-------
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 in the
batch. If analyte is present, the noise level adjacent in retention time to
the analyte peak may be used. For wave-length dispersive instrumentation,
multiple determinations of digestates with no detectable analyte may be used
to establish the noise level. The method of standard additions should then be
used to determine the calibration curve using one digestate or extracted
sample in which the analyte was not detected. The slope of the calibration
curve, m, should be calculated using the following relations:
m = slope of calibration line
SB = standard deviation of the average noise level
MDL = KSB/m
For K = 3; MDL = method detection limit.
For K = 5; MQL = method quantisation limit.
1.4 DATA REPORTING
The requirement of reporting analytical results on a wet-weight or a dry-
weight basis is dictated by factors such as: sample matrix; program or
regulatory requirement; and objectives of the analysis.
Analytical results shall be reported with the percent moisture or percent
solid content of the sample.
1.5 QUALITY CONTROL DOCUMENTATION
The following sections list the QC documentation which comprises the
complete analytical package. This package should be obtained from the data
generator upon request. These forms, or adaptations of these forms, shall be
used by the data generator/reporter for inorganics (I), or for organics (0) or
both (I/O) types of determinations.
1.5.1 Analytical Results (I/O: Form I)
Analyte concentration.
Sample weight.
Percent water (for non-aqueous samples when specified).
Final volume of extract or diluted sample.
Holding times (I: Form X).
ONE - 15
Revision 0 '
Date September 1986
-------
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 in 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.
ONE - 16
Revision
Date September 1986
-------
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 K
Date
COVER PACE
INORGANIC ANALYSES DATA PACKAGE
Case No.
Q.C. Report No.
Sample Num
EPA No.
Comments:
Lab ID No.
EPA No.
Lab ID No.
ONE - 18
Revision 0
Date September 1986
-------
LAB NAME
LAb SAMPLE ID. NO.
Form I
Sarsple
No.
Date
INORGANIC ANALYSIS DATA SHLET
CASE NO.
Lab Receipt Date
QC REPORT NO.
Elements Identified and Measured
Matrix: Water
Soil
Sludge uther
ug/L or ra^/kg dry weight (Circle One)
1. Aluminum 13. Magnesiuc
2. Antimony
3. Arsenic
A. bariurc
5. Beryllium
6. Cadmium
7. Calciuir,
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
14.
13.
16.
17.
Ib.
19.
2u.
21.
22.
23.
Manganese
Mercury
Nickel
Potassium
Seleniur?
Silver
Sodiuc
Thallium
Vanadiura
Zinc
Precent Solids (:=)
Cyanide
Comnrnts:
Lab Manager
ONE - 19
Revision 0
Date September 1986
-------
LAB NAMt
Form II
Q. C. Report No.
INITIAL AND CONTINUING CALIBRATION VERIFICATION
CASK NO.
DATE
Compound Initial Calib
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
b. Cadmium
7. Calcium
b. Chromium
y. Cobalt
10. Copper
1 1 . Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
True Value
Ib. Nickel
17. Potassium
16. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Found
UNITS: ug/L
.* Continuing Calibration2
ZR
True Value
Found
ZR
i
i
i
Found
/.k
i i
i
i
Method4,1
1
1 Initial Calibration Source
(,'otit inuioK Calibration Source
Indicate Analytical Method Used: F - 1CH; A - Flame AA; F - Furnace AA
ONE - 20
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form III
CJ. C. Report No.
BLANKS
CASE NO.
UMTb
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. beryllium
6. Cadcium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
Ib. Nickel
17. Potassium
IB. Selenium
ly. Silver
2(J. Sodium
2.1. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Initial
Calibration
Blank Value
Continuing Calibration
1
Blank Value
2 3
U
Preparation Blar-'r-
Matrix: Matrix:
1 2
Reporting Units:aqueous, u&/L;solid
ONE - 21
0
Revision
Date September 1986
-------
Form IV
Q. C. Report No.
LAB NAME
1CP INTERFERENCE CHECK SAMPLE
CASL NO.
DATE
Check Sample l.D.
Check Sample Source
Units: ug/L
Compound
Metals:
1 . Aluminum
2. Antimony
3. Arsenic
fc. 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
2J. Zinc
Other:
Control
Mean
Limits1
Std. Dev.
True^
Initial
Observed
7.R
Final
Observed
%R
Moan value based on n =
True value of EHA 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. Antimony
3. Arsenic
4. Barium
5. Beryllium
6. Cadmiuc
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
IR
Spiked Sample
Result (SSR)
Sample
Result (SR)
Spiked
Added (SA)
ZR1
1 *R = USSR - SK)/SAj x 100
"N"- out of control
NR1- 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. Chromiuc
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
la. Selenium
ly. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Control Limit1
Sample(S)
t
Duplicate^)
*
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
-------
Form VII
Q.C. Report No.
LAB NAME
INSTRUMENT DETECTION LIMITS AND
LABORATORY CONTROL SAMPLE
CASE NO.
DATL
LCS NO.
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
fe. Cadmium
7 . Ca 1 c i UQ
8. Chromium
2. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Required Detection
Limits (CRDL)-uK/!
Instrument Detection
Limits (IDL)-ug/!'
ICP/AA Furnace
IDf ID*
NR
I:K
Lab Control Sample
ug/L mfi/kp
(circle one)
True Found ZR
1
Mi - Not required
ONE - 25
Revision 0
Date September 1986
-------
Form VIII
Q.C. Report No.
STANDARD ADDITION RESULTS
LAB NAME
UATt
tPA
Sample V
CASE NO.
tlement
Matrix
0 ADD
ABS.
1 ADD
CON .
ABS-
UMTS .' ug/L
2 ADD
CON.
ABS.Z
3 ADD
CON.
AfcS.^
FINAL
CON.3
r*
(
i
^ CON is the concentration added, ABS. is the instrument readout in absorbance or
concentration.
•* Concentration as_ determined by ."•iSA
*"r" is the correlation coefficient.
+ - correlation coefficient is outsidu ot control window of
ONE - 26
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form IX
Q« C. Report No.
ICP SERIAL DILUTIONS
CASE NO.
Sample No.
Lab Sample ID Mo,
Units'. ug/L
Matrix
Compound
Metals:
1 . Aluninun
2. Antimony
3. Arsenic
4. barium
5. Bervlliuc
6. Cadmium
7. Calcium
t>. Chromium
V. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Nickel
16. Potassiur.
17. Seleniur
lb. Silver
1^. Sodium
20. Thallium
/I . Vanadium
2.2. Zinc
OLhc-r :
Initial Sample
Concentration( I)
Serial Dilution1
Result(S)
A Difference2
, i
^
' Diluted sample concentration corrected for 1:4 dilution (see Exhibit D)
2 Percent Difference U ~ sl x luu
1
Nk - Not Required, initial sample concentration less than 10 times IUL
NA - Not Applicable, analyte not determined by 1CP
ONE - 27
Revision 0
Date September 1986
-------
Form X
QC Report No.
HOLDING TIKES
LAb NAME
DATE
CASE Nu.
EPA
Sample No.
Matrix
Date
Received
Mercury
Prep Date
Mercury
Holding Time1
(Days)
CN Prep
Date
CN
Holding Time1
(Davs)
t
'holding time is defined as number of days between the date received and the
sample preparation date.
ONE - 28
Revision 0
Date September 1986
-------
LAK NAME
Form XI
INSTRUMENT DETECTION LIMITS
DATE
ICP/Flame AA (Circle One)
Element
1 • Aluminum
2. Antimony
3. Arsenic
A. Barium
b. Beryllium
0. Cadciun
7. Calcium
6. Chromium
9. Cobalt
1U. Copper
11. Iron
12. Lead
Wavelength
(nm)
Model Number Furnace AA Number
IDL
(ug/L)
Element
13. Magnesium
14. Manganese
Wavelength
(no)
15. Mercury
16. Nickel
17. Potassium
IB. Selenium
19. Silver
20. Sodium
21. Thalliun
22. Vanadium
23. Zinc
IDL
(UE/L)
Footnotes: • Indicate the instrument for which the IDL applies with a "f" (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.
CUMMLNTb:
Lab Manager
ONE - 29
Revision 0
Date September 1986
-------
Forn XII
ICP Interelement Correction Factors
LABORATORY
DATE
ICP Model Number
Analyte
1. Antimonv
2. Arsenic
3. Bariuc
4. Bervllius
5. Cadcius
6. ChroEiur.
7. Cobalt
8. Copper
9. Lead
10. Manganese
11. Mercurv
12. Nickel
13. Potassiur:
14. Seleniuc
15. Silver
16. Sodium
17. Thallium
IB. Vanadium
r>. Zinc
Analyte
Wavelength
(no)
Intereleraent. Correction Factors
for
Al
i
Ca
Fe
Mg
i
•
COMMENTS:
Lab Manager
ONE - 30
Revision 0
Date September 1986
-------
Form XII
1CP Interelement Correction Factors
LABORATOKY_
DATE
ICP Model Nunber
Analyte
1. Antimony
2. Arsenic
3. bariutr.
4. BerylliuE
5. Cadmiuir.
6. Chromium
7. Cobalt
6. Copper
9. Lead
10. Manganese
11. Mercury
12. Nickel
13. Potassium
14. Selenium
15. Silver
16. Sodium
17. Thallium
18. Vanadium
iy. Zinc
Analyte
Wavelength
(nn)
Interelement Correction Factors
for
1
1
1
:
COMMENTS:
Lab Manager
ONE - 31
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form XIII
ICP Linear Ranges
TCP Model Number
Analyte
1. Aluminum
2. Antimony
3. Arsenic
4 . Bariur
5. Beryllium
6. Cadmium
7. Calcium
b. Chroniuni
9. Cobalt
10. Copper
1 1 . Iron
12. Lead |
Integration
Time
(Seconds )
.
Concen-
tration
(ug/L)
1
Ana 1 y t e
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodiur.
21. Thalliun:
22. Vanadiuir
23. Zinc
Integrat ion
Time
(Seconds )
Concen-
tration
(ug/L)
Footnotes:
Indicate elements not analyzed by ICP with the notation "NA".
COMMENTS:
Lab Manager
ONE - 32
Revision 0
Date September 1986
-------
Organics Analysis Data Sheet
(Pagel)
Sample Number
Laboratory Name:
Case No:
Lab Sample ID No
Sample Matrix
QC Report No:
Data Release Authorized By
Date Sample Received:
Volatile Compounds
Date Extracted/Prepared:
Date Analyzed: __
Conc/Di! 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
Bromoniethane
Vinyl Cnio'ide
Chloroethane
Metnylene Chloride
Acetone
Carbon Oisulfide
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
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-Oichloropropene
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-Tetrachloroeihane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
Data Reporting Qualifiers
For reporting remits to EPA. the following results qualifiers are used.
Additional flags or footnotes e«plainmg results are encouraged However, the
definition of each flag must be anplicit
Value
If the resuli is a value greater than or equal to the detection limit.
report me value
Indicates compound was analyzed for but not detected Report the
minimum detection limit for the (ample with the U (e.g.. 100) based
on necessary concentration 'dilution action (This is not necessarily
the instrument detection limn | The footnote should read U-
Compound was analyied lor but not detected The number is the
minimum attainable detection limit lor the sample
Indicates an estimated value Tms flag is used either when
estimating a concentration for tentatively identified compounds
where a 1 1 response is assumed or when me mass spectral data
indicated the pretence of a compound that meets the identification
criteria but me result is less than the rpecified detection limit but
greater tnan tero le g . 10JI If limit o' detection is 10 ug 'I and a
concentration of 3 pg *l is calculated, report as 3J.
Other
This flag applies to pesticide parameters where me identification nas
been confirmed by CC/MS Single component pesncides^tO
ng 'ul in the final attract should be confirmed by GC MS
This flag is used when the analyte is found m me blank as wen as a
sample It indicates possible• probable blank contamination and
warns the data user to lake appropriate action
Other specific flags and footnotes may be required to properly define
the results If used, they must be lully described and sucn description
attached to me data summary report
Form I
ONE - 33
Revision 0_
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 QYes
Continuous Liquid - Liquid Extraction DYes
Cone/Oil Factor:
Percent Moisture (Decanted).
CAS
Number
ug/lorug/Kg
(Circle One)
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
Oibenzofuran
2, 4-Dinitrotoluene
2, 6-Dinitrotoluene
Oiethylphthalate
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
Benzo(k)Fluoranthene
Benzo(a)Pyrene
Indenod . 2, 3-cd)Pyrene
Dibenz(a, h)Anthracene
Benzo(g. h, i)Perylene
(1)-Cannot be separated Irom diphenylamine
Form I
ONE - 34
Revision 0
Date September 1986
-------
Laboratory Name
Case No
Sample Number
Date Extracted/Prepared:
Date Analyzed:
Conc/Dil Factor:
Organics Analysis Data Sheet
(Page 3)
Pesticide/PCBs
GPC Cleanup DYes DNo
Separatory Funnel Extraction DYes
Continuous Liquid - Liquid Extraction DYes
Percent Moisture (decanted).
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 (Lindane)
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan I
Dieldrm
4,4'-DDE
Endrin
Endosulfan II
4. 4--DDD
Endosulfan Sulfate
4,4'-DDT
Methoxychlor
Endrin Ketone
Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Vj = Volume of extract injected (ul)
V$ = Volume of water extracted (ml)
Ws = Weight of sample extracted (g)
V, = Volume of total extract (ul)
orW.
Form 1
ONE - 35
Revision 0
Date September 1986
-------
Laboratory Name:.
Case No:
Organics Analysis Data Sheet
Sample Number
CAS
Number
V
•2.
a
A
6
fi
7
R
9
10
11
13
13
14
IS
IS
17
1fl
19
3f>
21
22
33
3d
3K
3fi
27
3B
3<>
30
Compound Name
Fraction
RT or Scan
Number
Estimated
Concentration
(ug/lorug/kg)
Form 1, Pan B
ONE - 36
Revision 0
Date September 1986
-------
Case No..
WATER SURROGATE PERCENT RECOVERY SUMMARY
Laboratory Name
•AMPlt
NO.
tOLUCNC-M
IH-110)
•ft
(••-IIS)
l.t OICHLOHO-
ETHANC-04
(M-1141
NIIHO-
•CIIZCN009
(It- 114)
t-'LUOKO-
eiPHtXri
(43- lie)
UOPHENltL-
OI4
(13-141)
EMI-VOLATIL
r
mCNOL-05
(10-14)
t-riuOM>-
mCNOL
(11-100)
2.4.6 TRIKROHO-
PHENOL
(10-113)
-PESTICIOE--
oiaurtL-
CHIOHCHOATC
U4-1B4)
I
00
O 70
(U O
ft <
(0 -••
(/>
C/) O
n> 3
o
rt-
O>
vO
CD
C7>
VALUES ARE OUTSIDE OF REQUIRED QC LIMITS
Volatiles:
Semi-Volatiles:
Pesticides:
. out of.
out of.
out of.
.; outside of QC limits
.; outside of OC limits
.; outside of QC limits
Comments:
FORM II
-------
SOIL SURROGATE PERCENT RECOVERY SUMMARY
Date September 1986
o
m
1
GJ
00
n>
<
J2.
o
0
MMM.B
NO.
TOLUCNC-0*
ui-iir)
»
U OICm.000-
CTHXIC-D4
NITKO -
(CNZCNC-OS
j-riuono-
(90-tK)
(ie-iif)
Volat
VALUES ARE OUTSIDE OF REQUIRED OC LIMITS e .
oeitw-
Pestk
EMI-VOLATIL
7.7T
,
IPS: ., nut of •
Vnlatilps* . out 0
idea: out o
f .
f .
f-rioono-
l.4.« TUtgHOHO-
•-PE3TICIOE--
OttUtTL-
outside of OC limits
outside of OC limits
outside of QC limits
FORM II
-------
WATER MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Case No.
Laboratory Name.
OJ
IO
FRACTION
VOA
SAMPLE NO.
B/N
SAMPLE NO.
API n
SAMPLE NO
PEST
bAMPLE NO.
COMPOUND
1 ,1 -Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
1 ,2.4.TrichlorobefUene
Acenaphth,:ne
2.4 Dinitrotoluene
Oi-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
Endrin
4 4'-DOT
CONC. SPIKE
ADDED (uq/L)
SAMPLE
RESULT
CONC.
MS
%
REC
CONC.
MSD
%
REC
ppn
t 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
76-1^5 __.
76-1?7
39-98
46-118
24-96
11-117
26-127
41-116
36 97
9 103
12 89
27-123
23 97
10 80
56 123
40 131
40 120
52-126
56-121
38-1 27
O
tu
ADVISORY LIMITS
oo o
n> 3
o
r1-
O)
CT
fD
-i
00
CTv
RPD:
Conwr
VOAs
R/N
Ann
PFST
4»nt«f
out of
out nf
nut nf
nut nf
outside
outside
outside
outside
OC limits
QC limits
OC limits
QC limits
RECOVERY: VOAs out of :
B/N , Out "'
ACID _ "»' "' , - - ;
PPST out nf - ;
outside
outside
outside
outside
OC
OC
OC
OC
limits
limits
limits
limits
FORM III
-------
SOIL MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Case No.
Laboratory Name.
I
o
O
fu
n> -^
co o
(D =J
CT
ft)
CO
cn
FRACTION
VGA
SAMPLE NO.
B/N
SAMPLE NO.
ACID '
SAMPLE NO.
PEST
SAMPLE NO.
COMPOUND
1 ,1 -Dicholorethene
Trichlorocthene
Chlorobenzene
Toluene .
Benzene
CONC. SPIKE
ADDED (iig/Kq)
1,2,4-Trichlorobenzene }
AcenapKthene
2,4 Dinitrotoluene
Dj-n-Butylphthalate
Pyrene
N-Nitrosodi-n-Propylamine
1 ,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
Lindane
Heptachlor
Aldrin
Oieldrin
Endrin
4.4'DDT
SA'MPLE
RESULT
CONC.
MS
%
REC
CONC.
MSD
%
REC
RPD
O.C LIMITS
RPD
22
24
21
21
21
23
19
47
47
36
38
27
47
35
50
33
50
50
31
43
38
45
50
RECOVERY
59172
62-137
60133
59-139
66142
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
35130
34132
31-134
42-139
23134
ADVISORY LIMITS
RPD: VOAs
R/N
Arm
PFST
Conwnents:
nut of nntsidp OC limits
nut nf . Qiit*iHp OO limit*
«M1 of OH'*'dP Or limit*
_ out of outsiHp OC linriit*
RFrOVFRY- VOA* out of out*idp Of! limits
R/N ...out of. . . OMt*irlp Or limit*
Arm out nf nnKiHp DP limit*
PfST nut of niit*iHp OC limits
FORM III
-------
METHOD BLANK SUMMARY
Case No.
Laboratory .Name.
O 73
a> n
ft>
a
a-
o
m
1
i— «
FLEIO
OATC OF
ANALYSIS
TRACTION
MATRIX
CONC.
LEVEL
INST.IO
CAS NUMBER
COMPOUND (MSL.TIC OR UNKNOWN)
CONC.
UNITS
CROL
Comments:
to
00
FORM IV
-------
GC/MS TUNING AND MASS CALIBRATION
Bromofluorobenzene (BFB)
Case No..
Instrument ID
Laboratory Name.
Date
Time.
Data Release Authorized By:
.m/e
ION ABUNDANCE CRITERIA
^RELATIVE ABUNDANCE
50
75
95
96
173
174
175
176
177
15.0 - 40.0% of the base p«ak
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% of mass 174
5.0 - 9.0% of mass 176
( )'
( r
c )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING
SAMPLES, BLANKS AND STANDARDS.
Value in .parenthesis ii % mass 174.
Value in parenthesis is % mass 175.
SAMPLE ID
LAB ID
DATE OF ANALYSIS
TIME OF ANALYSIS
FORM V
ONE - 42
Revision 0
Date September 1986
-------
Case No..
Instrument ID
GC/MS TUNING AND MASS CALIBRATION
Decafluorotriphenylphosphine (DFTPP)
Laboratory Name
Date Time
Data Release Authorized By:
m/e
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 man 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 ' 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 Q
Date September 1986
-------
Initial Calibration Data
Volatile HSL Compounds
Case No:
Laboratory Name
Instrument I D: .
Calibration Date-
Minimum RFfor SPCCis 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-Bichloroethene
1, 1-Dichloroethane
Trans-1. 2-Dichioroethene
Chloroform
1. 2-Dichloroeihane
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-Pentanone
2-Hexanone
Tetrachloroethene
1.1.2. 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
RF20
,
RF50
RF100
RF150
.
RF200
RF
%RSD
CCC*
SPCC"
* *
•
*
» •
*
*
» *
» *
*
* *
•
RF -Response Factor (subscript is the amount of ug/L)
757 -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 IO
Compound
RF20
RF
50
RF
100
RF150
RF
200
RT
%RSD
CCC-
SPCC«
RF -Response Factor (subscript is the amount of ug/L)
fiT -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-Dichlorobenzene
2-Methylphenol
bis(2-Chloroisopropyl)Ether
4-Methylphenol
N-Nitroso-Di-n-Propylamme
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2. 4-Dimethylphenol
Benzoic Acid
bis(-2-Chloroethoxy)Metriane
2. 4-Oichlorophenol
1 . 2, 4-Trichlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2, 4. 6-Trichlorophenol
2, 4. 5-Trichloropheno!
2-Chloronaphthalene
2-Nitroaniline
Dimethy! Phthalate
Acenaphthylene
3-Nitroanilme
Acenaphthene
2, 4-Dmitrophenol
4-Nitrophenol
Dibenzofuran
RF20
T
T
T
t
t
T
"50
"BO
> •
RF120
x
"160
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 j.)
SPCC -System Performance Check Compounds (••)
t -Not detectable at 20 ng
Form VI
ONE - 46
Revision 0
Date September 1986
-------
Case No:
Laboratory Name
Initial Calibration Data
Semivolatile HSL Compounds
(Page 2)
Instrument ID: _
Calibration Date:
Minimum RF for SPCC is 0.050 Maximum % RSD for CCC is 30%
Laboratory ID
Compound
2, 4-Dinitrotoluene
2, 6-Dmitrotoluene
Diethylphthalate
4-Chlorophenyl-Dhenylether
Fluorene
4-Nitroaniline
4. 6-Dinitro-2-Methylpheno!
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachloropheno!
Pnenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3. 3'-Dichlorobenzidme
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalaie
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
IndenoO. 2. 3-cd)Pyrene
Dib€nz(a, h)Anthracene
Benzo(g. h. i)Perylene
RF20
t
t
t
«F50
RF80
RF120
RF160
IP
VcRSD
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
(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
(Page!)
Instrument ID: _
, Calibration Date:
Minimum RF for SPCC is 0.050 Maximum % RSD for CCC is 30%
Laboratory ID
Compound
RF
20
RF80
RF120
RF
160
RF
%RSD
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
Meihylene Chloride
Acetone
Carbon Disulfide
1. 1-Dichloroethene
1. 1-Oichloroethane
Trans-1. 2-Dichloroethene
Chloroform
1, 2-Dichloroe:hane
2-Butanone
1,1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1, 2-Dichloropropane
Trans-1. 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1. 2-Tnchloroethane
Benzene
cis-1, 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1. 1.2, 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenrene
Styrene
Total Xylenes
RF
RF50
•
%D
CCC
»
*
*
•
*
*
SPCC
» *
* •
'
* *
• *
* *
RFgg -Response Factor from daily standard die 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 o
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
RF
RF
50
%D
CCC
SPCC
"F50 -Response Factor from daily standard file at 50 ug I
RF -Average Response Factor from initial calibration Form VI
°oD -Percent Difference
CCC -Calibration Cneck Compounds (•)
SPCC System Performance Check 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 JD:
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-Dichlorobenzene
1 . 4-Dichlorobenzene
Benzyl Alcohol
1. 2-Oichlorobenzene
2-Melliylphenol
bis(2-chloroisopropyl)Ether
4-Methylphenol
N-Nitroso-Di-n-Propylamine
Hexachloroeihane
Nitrobenzene
Isophorone
2-Nitrophenol
2, 4-Dimeihylphenol
Benzoic Acid "f
biS(-2-Chloroethoxy)Meihane
2, 4-Dichlorophenol
1. 2. 4-Trichlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2. 4. 6-Tnchlorophenol
2. 4. 5-Tnchloiophenol |
2-Chloronaphihalene
2-Nitroanilme f
Dimethyl Phthalate
Acenaphthylene
3-Nitroanilme f
Acenaphthene
2, 4-Dmitrophenol
4-Nitrophenol
Oibenzofuran
FT*
R^BO
%D
CCC
*
*
*
*
*
*
*
«
SPCC
* *
• »
» *
* *
RFjQ -Response Factor from daily standard die at concentration
indicated (50 total n»nognms)
RT -Average Response Factor from initial calibration Form VI
+ >Due to low response, analyze
•t 80 total nanograms
S>D -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-phenylether
Fluorene
4-Nitroaniline t
4, 6-Dmitro-2-Methylphenol J
N-Nitrosodiphenylamine (1 )
4-Bromophenyl-phenyle!her
Hexachlorobenzene
Pemachlorophenol f
Phenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3, 3'-Dichlorobenzidme
Benzofa (Anthracene
bis(2-Ethylhexvl)Phthalate
Chrysene
Di-n-Octyl Phthalaie
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
IndenoO. 2. 3-cd)Pyrene
Oibenz(a, hJAnthracene
Benzo(g. h, i)Perylene
RF
RF50
%D
CCC
-
»
*
*
»
*
SPCC
RF^Q Response F.u-lur (ruin Oiiily Sl.inil.iul lilu .il njocenii.il
indicated (50 total nanograms)
RT -AvufiiyL- Ri;s|)oi)ie F.iclor (ruin iinli.il t.ilibi.iliuii Form VI
"oD Peiceni Dil(uruiii;i/
t-Due to low response, analyze
at 80 total nanograms
CCC -Ciilibr.Miuii Check Cumyuumlb (•)
SPCC Sybloin Perlurni;ince Check Cuinuuumlb (. -I
11) -Crinnul l)c sepiirjtuJ (ruin Uiphenyl.unine
Form VII
ONE - 52
Revision Q
Date September 1986
-------
Continuing Calibration Check
Semivolatile HSL Compounds
(Page1)
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
RFgg -Response Factor from daily suml.iril file .11 concentration
indicated (50 total nanograms)
RT -Average Response F.itlor lron> niitml c.ilitji.inon Form VI
•^•Oue to low response, analyze
•t 80 total nanograms
%D -Percent Difference
CCC -Calibration Check Compuund:, (•)
SPCC System Performance Check Compounds I • • I
Form VII
ONE - 53
Revision o
Date September 1986
-------
Pesticide Evaluation Standards Summary
(Page 1)
Case No:
Date o' Analysis;
Laboratory Name:.
GC Column:.
Instrument ID..
Evaluation Check for Linearity
Laboratory
ID
Pesticide
Aldnn
Endrin
4.4'. DDT(''
Dibutyl
Cnlorendate
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)
Eva! Mix B
72 Hour
Eval Mix B
Eval MixB
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval MixB
Eval Mix B
Eval Mix B
Eval MixB
Eval Mix B
Laboratory
I.D.
Time of
Analysis
Endrin
r
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 Q
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
Oiff.
SMO
Sample No.
Lab
I.D.
Time of
Analysis
Percent
Diff.
RCRA
Form VIM (Continued) 4/86
ONE - 55
Revision Q
Date September 1986
-------
PESTICIDE/PCB STANDARDS SUMMARY
Case No..
Laboratory Name.
QC Column
GC Instrument ID
o
•z.
m
I
CJ1
en
O 70
01 n>
(0 -*
_j.
> O
3
o
r*
n
vo
oo
COMPOUND
alpha -BHC
beta-BHC
delta-BHC
gamma -BHC
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan I
Dieldrin
4,4'-DDE
Endrin
Endosulfan I
4,4'-DDD
Endrin Aldehyde
Endosulfan Sulfate
4. 4'- DDT
Methoxychlor
Endrin Ketone
Tech. Chlordane
alpha-Chlordane
gamma-Chlordane
Toxaphene
Aroclor - 1 0 1 6
Aroclor - 1 22 1
Aroclor - 1 232
Aroclor - 1 24 .
Aroclor - 1 248
Aroclor - 1 254
Aroclor - 1260
DATE OF AN
TIME OF AN/
LABORATORY
RT
A| YRIfi
!>l Y«IS
t in
RETENTION
TIME
WINDOW
CALIBRATION
FACTOR
CONF.
OR
QUANT.
\
DATE OF ANJ
TIME OF AN/I
LABORATOR'
RT
M YRIR
1 YRIR
nn
CALIBRATION
FACTOR
CONF.
OR
QUANT.
PERCENT
DIFF. **
** CONF. = CONFIRMATION (*2O% DIFFERENCE)
O'JANT.— OUANTITATIOM
FORM IX
-------
Case No.
P«stlcide/PCB Identification
Laboratory Name.
en
•vj
O 73
cu n
n — >•
(/> O
CO =3
O
ft)
n>
oo
SAMPLE
ID
PRIMARY
COLUMN
PESTICIDE/
PCB
RT OF
TENTATIVE
ID
RT WINDOW
OF APPROPRIATE
STANDARD
-
CONFIRMATION
COLUMN
RT ON
CONFIRMATORY
COLUMN
RT WINDOW OF
APPROPRIATE
STANDARD
GC/MS
CONFIRMED
-------
CHAPTER FOUR
ORGANIC ANALYTES
4.1 SAMPLING CONSIDERATIONS
4.1.1 Introduction
Following the initial and critical step of designing a sampling plan
(Chapter Nine) is the implementation of that plan such that a representative
sample of the solid waste is collected. Once the sample has been collected it
must be stored and preserved to maintain the chemical and physical properties
that it possessed at the time of collection. The sample type, type of
containers and their preparation, possible forms of contamination, and
preservation methods are all items which must be thoroughly examined in order
to maintain the integrity of the samples. This section highlights
considerations which must be addressed in order to maintain a sample's
integrity and representativeness.
4.1.2 Sample Handling and Preservation
This section deals separately with volatile and semivolatile organics.
Refer to Chapter Two (Table 2-16) and Table 4-1 of this Section for
recommended sample containers, sample preservation, and sample holding times.
Volatile Organics
Standard 40-mL glass screw-cap VOA vials with Teflon-faced silicone
septum may be used for both liquid and solid matrices. The vials and septum
should be soap and water washed and rinsed with distilled deionized water.
After thoroughly cleaning the vials and septum, they should be placed in a
muffle furnace and dried at 105*C for approximately one hour. (Note: Do not
heat the septum for extended periods of time, i.e., more than one hr, because
the silicone begins to slowly degrade at 105*C).
When collecting the samples, liquids and solids should be introduced into
the vials gently to reduce agitation which might drive off volatile compounds.
Liquid samples should be poured into the vial without introducing any air
bubbles within the vial as it is being filled. Should bubbling occur as a
result of violent pouring, the sample must be poured out and the vial
refilled. Each VOA vial should be filled until there is a meniscus over the
lip of the vial. The screw-top lid with the septum (Teflon side toward the
sample) should then be tightened onto the vial. After tightening the lid, the
vial should be inverted and tapped to check for air bubbles. If there are any
air bubbles present the sample must be retaken. Two VOA vials should be
filled per sample location.
VOA vials for samples with solid or semi-solid (sludges) matrices should
be completely filled as best as possible. The vials should be tapped slightly
as they are filled to try and eliminate as much free air space as possible.
Two vials should also be filled per sample location.
FOUR - 1
Revision 0
Date September 1986
-------
VGA vials should be filled and labeled immediately at the point at which
the sample is collected. They should NOT be filled near a running motor or
any type of exhaust system because discharged fumes and vapors may contaminate
the samples. The two vials from each sampling locations should then be sealed
in separate plastic bags to prevent cross-contamination between samples
particularly if the sampled waste is suspected of containing high levels of
volatile organics. (Activated carbon may also be included in the bags to
prevent cross-contamination from highly contaminated samples). VGA samples
may also be contaminated by diffusion of volatile organics through the septum
during shipment and storage. To monitor possible contamination, a trip blank
prepared from distilled deionized water should be carried throughout the
sampling, storage, and shipping process.
Semi volatile Organics (This includes Pesticides and Herbicides.)
Containers used to collect samples for the determination of semi volatile
organic compounds should be soap and water washed followed by methanol (or
isopropanol) rinsing (see Section 4.1.4 for specific instructions on glassware
cleaning). The sample containers should be of glass or Teflon and have screw-
top covers with Teflon liners. In situations where Teflon is not available,
solvent-rinsed aluminum foil may be used as a liner. Highly acidic or basic
samples may react with the aluminum foil, causing eventual contamination of
the sample. Plastic containers or lids may NOT be used for the storage of
samples due to the possibility of sample contamination from the phthalate
esters and other hydrocarbons within the plastic. Sample containers should be
filled with care so as to prevent any portion of the collected sample coming
in contact with the sampler's gloves, thus causing contamination. Samples
should not be collected or stored in the presence of exhaust fumes. If the
sample comes in contact with the sampler (e.g., if an automatic sampler is
used), run reagent water through the sampler and use as a field blank.
4.1.3 Safety
Safety should always be the primary consideration in the collection of
samples. A thorough understanding of the waste production process as well as
all of the potential hazards making up the waste should be investigated
whenever possible. The site should be visually evaluated just prior to
sampling to determine additional safety measures. Minimum protection of
gloves and safety glasses should be worn to prevent sample contact with the
skin and eyes. A respirator should be worn even when working outdoors if
organic vapors are present. More hazardous sampling missions may require the
use of supplied air and special clothing.
4.1.4 Cleaning of Glassware
In the analysis of samples containing components in the parts per billion
range, the preparation of scrupulously clean glassware is mandatory. Failure
to do so can lead to a myriad of problems in the interpretation of the final
chromatograms due to the presence of extraneous peaks resulting from
contamination. Particular care must be taken with glassware such as Soxhlet
extractors, Kuderna-Danish evaporative concentrators, sampling-train
FOUR - 2
Revision 0
Date September 1986
-------
components, or any other glassware coming 1n contact with an extract that will
be evaporated to a lesser volume. The process of concentrating the compounds
of Interest 1n this operation may similarly concentrate the contamination
substance, which may seriously distort the results.
The basic cleaning steps are:
1. Removal of surface residuals Immediately after use;
2. Hot soak to loosen and flotate most particulate material;
3. Hot-water rinse to flush away flotated particulates;
4. Soak with an oxidizing agent to destroy traces of organic compounds;
5. Hot-water rinse to flush away materials loosened by the deep penetrant
soak;
6. Distllled-water rinse to remove metallic deposits from the tap water;
7. Methanol rinse to flush off any final traces of organic materials and
remove the water; and
8. Flushing the Item immediately before use with some of the same solvent
that will be used in the analysis.
Each of these eight fundamental steps will be discussed in the order in
which they appear above.
1. As soon possible after glassware (I.e., beakers, pipets, flasks, or
bottles) has come in contact with sample or standards, the glassware
should be methanol-flushed before 1t is placed in the hot detergent
soak. If this Is not done, the soak bath may serve to contaminate all
other glassware placed therein.
2. The hot soak consists of a bath of a suitable detergent in water of
50*C or higher. The detergent ~ powder or liquid — should be
entirely synthetic and not a fatty add base. There are very few
areas of the country where the water hardness is sufficiently low to
avoid the formation of some hard-water scum resulting from the
reaction between calcium and magnesium salts with a fatty acid soap.
This hard-water scum or curd would have an affinity particularly for
many chlorinated compounds and, being almost wholly water-insoluble,
would deposit on all glassware in the bath in a thin film.
There are many suitable detergents on the wholesale and retail market.
Most of the common liquid dishwashing detergents sold at retail are
satisfactory but are more expensive than other comparable products
sold Industrially. Alconox, in powder or tablet form, is manufactured
by Alconox, Inc., New York, and is marketed by a number of laboratory
supply firms. Sparkleen, another powdered product, is distributed by
Fisher Scientific Company.
FOUR - 3
Revision 0
Date September 1986
-------
3. No comments required.
4. The most common and highly effective oxidizing agent for removal of
traces^ of organic compounds is the traditional chromic acid solution
made up of ^$04 and potassium or sodium dichromate. For maximum
efficiency, the soak solution should be hot (40-50°C). Safety
precautions must be rigidly observed in the handling of this solution.
Prescribed safety gear should include safety goggles, rubber gloves,
and apron. The bench area where this operation is conducted should be
covered with fluorocarbon sheeting because spattering will
disintegrate any unprotected surfaces.
The potential hazards of using chromic sulfuric acid mixture are great
and have been well publicized. There are now commercially available
substitutes that possess the advantage of safety in handling. These
are biodegradable concentrates with a claimed cleaning strength equal
to the chromic acid solution. They are alkaline, equivalent to
ca. 0.1 N NaOH upon dilution, and are claimed to remove dried blood,
silicone greases, distillation residues, insoluble organic residues,
etc. They are further claimed to remove radioactive traces and will
not attack glass or exert a corrosive effect on skin or clothing. One
such product is "Chem Solv 2157," manufactured by Mallinckrodt and
available through laboratory supply firms. Another comparable product
is "Detex," a product of Borer-Chemie, Solothurn, Switzerland.
5, 6, and 7. No comments required.
'8. There is always a possibility that between the time of washing and the
next use, the glassware could pick up some contamination from either
the air or direct contact. To ensure against this, it is good
practice to flush the item immediately before use with some of the
same solvent that will be used in the analysis.
The drying and storage of the cleaned glassware is of critical importance
to prevent the beneficial effects of the scrupulous cleaning from being
nullified. Pegboard drying is not recommended because contaminants can be
introduced -to the interior of the cleaned vessels. Neoprene-coated metal
racks are suitable for such items as beakers, flasks, chromatographic tubes,
and any glassware then can be inverted and suspended to dry. , Small articles
such as stirring rods, glass stoppers, and bottle caps can be wrapped in
aluminum foil and oven-dried a short time if oven space is available. Under
no circumstances should such small : items be left in the open without
protective covering. The dust cloud raised by( the daily sweeping of the
laboratory floor can most effectively recontaminatie the clean glassware.
As an alternative to air drying, the glassware can be heated to a minimum
of 300*C to vaporize any organics.
FOUR - 4
Revision 0
Date September 1986
-------
TABLE 4-1. RECOMMENDED SAMPLE CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES
Parameter
Container
Preservative
Holding Time
Volatile Organics
Concentrated Haste Samples 8-oz. wideraouth
glass with Teflon
liner
Liquid Samples
No Residual Chlorine
Present
Residual Chlorine
Present
Acrolein and
Acrylonitrile
2 40-mL vials with
Teflon lined septum
caps
2 40-mL vials with
Teflon lined septum
caps
2 40-mL vials with
Teflon lined septum
caps
Soil/Sediments and Sludges 4-oz (120-mL) widemouth
glass with Teflon liner
None
4 drops cone. HC1, Cool, 4°C
Collect sample in a 4 oz. soil
VOA container which has been
pre-preserved with 4 drops of
10% sodium thiosulfate. Gently
mix sample and transfer to a
40-mL VOA vial that has been
pre-preserved with 4 drops
cone. HC1, Cool to 4°C
Adjust to pH4-5, Cool, 4°C
Cool, 4°C
14 days
14 days
14 days
14 days
14 days
FOUR - 5
Revision 0
Date September 1986
-------
TABLE 4-1. Continued
Parameter
Container
Preservative
Balding Time
Semivolatile Organics
Concentrated Waste Samples 8-oz. widemouth
glass with Teflon
liner
liquid Samples
None
No Residual Chlorine
Present
1-gal. or 2 1/2-gal.
amber glass with Teflon
liner
Cool, 4°C
Residual Chlorine
Present
1-gal. or 2 1/2-gal.
amber glass with Teflon
liner
Add 3 raL 10% sodiun
thiosulfate per
gallon, Cool, 4°C
Soil/Sediments and Sludges 8-oz. widemouth glass
with Teflon liner
Cool, 4°C
14 days
Samples must be
extracted with-
in 7 days and
extracts ana-
lyzed within
40 days
Samples must be
extracted with-
in 7 days and
extracts ana-
lyzed within
40 days
14 days
FOUR - 6
Revision 0
Date September 1986
-------
4.2 SAMPLE PREPARATION METHODS
4.2.1 EXTRACTIONS AND PREPARATIONS
FOUR - 7
Revision
Date September 1986
-------
METHOD 3500
ORGANIC EXTRACTION AND SAMPLE PREPARATION
1.0 SCOPE AND APPLICATION
1.1 The 3500 Methods are procedures for quantitatively extracting
nonvolatile and semi volatile organic compounds from various sample matrices.
Cleanup and/or analysis of the resultant extracts are described in Chapter
Four, Sections 4.2.2 and 4.3, respectively.
1.2 Method 3580 describes a solvent dilution technique that may be used
on non-aqueous nonvolatile and semi volatile organic samples prior to cleanup
and/or analysis.
1.3 The 5000 Methods are procedures for preparing samples containing
volatile organic compounds for quantitative analysis.
1.4 Refer to the specific method of interest for further details.
2.0 SUMMARY OF METHOD
2.1 3500 Methods; A sample of a known volume or weight is solvent
extracted. The resultant extract is dried and then concentrated in a Kuderna-
Danish apparatus. Other concentration devices or techniques may be used in
place of the Kuderna-Danish concentrator if the quality control requirements
of the determinative methods are met (Method 8000, Section 8.0).
2.2 5000 Methods; Refer to the specific method of interest.
3.0 INTERFERENCES
3.1 Samples requiring analysis for volatile organic compounds, can be
contaminated by diffusion of volatile organics (particularly chlorofluoro-
carbons and methylene chloride) through the sample container septum during
shipment and storage. A field blank prepared from reagent water and carried
through sampling and subsequent storage and handling can serve as a check on
such contamination.
3.2 Solvents, reagent, glassware, and other sample processing hardware
may yield artifacts and/or interferences to sample analysis. All these
materials must be demonstrated to be free from interferences under the
conditions of the analysis by analyzing method blanks. Specific selection of
reagents and purification of solvents by distillation in all-glass systems may
be required. Refer to Chapter One for specific guidance on quality control
procedures.
3.3 Interferences coextracted from the samples will vary considerably
from source to source. If analysis of an extracted sample is prevented due to
interferences, further cleanup of the sample extract may be necessary. Refer
to Method 3600 for guidance on cleanup procedures.
3500 - 1
Revision 0
Date September 1986
-------
3.4 Phthalate esters contaminate many types of products commonly found
in the laboratory. Plastics, in particular, must be avoided because
phthalates are commonly used as plasticizers and are easily extracted from
plastic materials. Serious phthalate contamination may result at any time if
consistent quality control is not practiced.
3.5 Glassware contamination resulting in analyte degradation; Soap
residue on glassware may cause degradation of certain analytes. Specifically,
aldrin, heptachlor, and most organophosphorous pesticides will degrade in this
situation. This problem is especially pronounced with glassware that may be
difficult to rinse (e.g., 500-mL K-D flask). These items should be hand-
rinsed very carefully to avoid this problem.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific method of interest for a description of the
apparatus and materials needed.
5.0 REAGENTS
5.1 Refer to the specific method of interest for a description of the
solvents needed.
5.2 Stock standards; Stock solutions may be prepared from pure standard
materials or purchased as certified solutions..
5.2.1 Purgeable stock standards: Prepare stock standards in
methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these
materials should be prepared in a hood.
5.2.1.1 Place about 9.8 ml of methanol in a 10-mL tared
ground-glass-stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 min or until all alcohol-wetted surfaces
have dried. Weigh the flask to the nearest 0.1 mg.
5.2.1.2 Using a 100-uL syringe,! immediately add two or more
drops of assayed reference material to the flask, then reweigh. The
liquid must fall directly into the 'alcohol without contacting the
neck of the flask.
5.2.1.3 Reweigh, dilute to volume, stopper, then mix by
inverting the flask several times. Calculate the concentration 1n
micrograms per microliter (ug/uL) from the net gain in weight. When
compound purity is assayed to be 96% or greater, the weight may be
used without correction to calculate the concentration of the stock
standard. Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
3500 - 2
Revision
Date September 1986
-------
5.2.1.4 Transfer the stock standard solution into a Teflon-
sealed screw-cap bottle. Store, with minimal headspace, at -10*C to
-20°C and protect from light.
5.2.1.5 All standards must be replaced after 1 month, or
sooner if comparison with check standards indicates a problem.
5.2.2 Semi volatile stock standards: Base/neutral and acid stock
standards are prepared in methanol. Organochlorine pesticide standards
are prepared in acetone.
5.2.2.1 Stock standard solutions should be stored in Teflon-
sealed containers at 4'C. The solutions should be checked
frequently for stability. These solutions must be replaced after
six months, or sooner if comparison with quality control check
samples indicate a problem.
5.3 Surrogate standards: A surrogate standard (i.e., a chemically inert
compound not expected to occur in an environmental sample) should be added to
each sample, blank, and matrix spike sample just prior to extraction or
processing. The recovery of the surrogate standard is used to monitor for
unusual matrix effects, gross sample processing errors, etc. Surrogate
recovery is evaluated for acceptance by determining whether the measured
concentration falls within the acceptance limits. Recommended surrogates for
different analyte groups follow; however, these compounds, or others that
better correspond to the analyte group, may be used for other analyte groups
as well. Normally three or more standards are added for each analyte group.
5.3.1 Base/neutral and acid surrogate spiking solutions: The
following are recommended surrogate standards.
Base/neutral Acid
2-Fluorobiphenyl 2-Fluorophenol
Nitrobenzene-ds 2,4,6-Tribromophenol
Terphenyl-di4 Phenol-ds
5.3.1.1 Prepare a surrogate standard spiking solution in
methanol that contains the base/neutral compounds at a concentration
of 100 ug/mL, and the acid compounds at 200 ug/mL for water and
sediment/soil samples (low- and medium-level). For waste samples,
the concentration should be 500 ug/mL for base/neutrals and 1000
ug/mL for acids.
5.3.2 Organochlorine pesticide surrogate spiking solution: The
following are recommended surrogate standards for Organochlorine
pesticides.
Organochlorine pesticides
Dibutylchlorendate (DBC)
2,4,5,6-Tetrachloro-meta-xylene (TCMX)
3500 - 3
Revision 0
Date September 1986
-------
5.3.2.1 Prepare a surrogate standard spiking solution at a
concentration of 1 ug/mL in acetone for water and sediment/soil
samples. For waste samples, the concentration should be 5 ug/mL.
5.3.3 Purgeable surrogate spiking solution: The following are
recommended surrogate standards for volatile organics.
Purgeable organics
p-Bromof1uorobenzene
l,2-Dichloroethane-d4
Toluene-ds
5.3.3.1 Prepare a surrogate spiking solution (as described in
Paragraph 5.2.1 or through secondary.dilution of the stock standard)
.in methanol containing the .surrogate standards at a concentration of
25 ug/mL.
5.4 Matrix spike standards: Select five or more analytes from each
analyte group for use in a spiking solution. The following are
recommended matrix spike standard mixtures for a few analyte groups.
These compounds, or .others that better correspond to the analyte
group, may be used for.other analyte groups as well.
>.••.• ' '
5.4.1 Base/neutral and acid matrix spiking solution: Prepare a
spiking solution in methanol that contains each of the following
base/neutral compounds at 100 ug/mL and the acid compounds at 200 ug/mL
for water and sediment/soil samples. The concentration of these
compounds should be five times.higher for waste samples.
Base/neutrals Acids
1,2,4-Trichlorobenzene . Pentachlorophenol
Acenaphthene t Phenol
2,4-Dinitrotoluene 2-Chlorophenol
.Pyrene 4-Chloro-3-methylphenol
N-Nitroso-di-n-propylamine . . 4-Nitrophenol
1,4-Dichlorobenzene .
5.4.2 Organochlorlne pesticide matrix spiking solution: Prepare a
spiking solution in acetone or methanol that contains the following
pesticides in the concentrations specified for water and sediment/soil.
The concentration should be five times higher for waste samples.
. Pesticide ' Concentration (ug/mL)
Lindane 0.2 ..
Heptachlor 0.2
Aldrin 0.2'
Dieldrin 0.5
Endrin 0.5
4,4'-DDT 0.5
3500 - 4
Revision
Date September 1986
-------
5.4.3 Purgeable matrix spiking solution: Prepare a spiking
solution 1n methanol that contains the following compounds at a
concentration of 25 ug/mL.
Purgeable organlcs
1,1-Dichloroethene
Trlchloroethene
Chlorobenzene
Toluene
Benzene
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to the Organic Analyte Chapter,
Section 4.1.
7.0 PROCEDURE
7.1 Semi volatile organic sample extraction; Water, soil/sediment,
sludge, and waste samples requiring analysis for base/neutral and add
extractables and/or organochlorlne pesticides must undergo solvent extraction
prior to analysis. This manual contains four methods that may be used for
this purpose: Method 3510; Method 3520; Method 3540; and Method 3550. The
method that should be used on a particular sample, 1s highly dependent upon
the physical characteristics of that sample. Therefore, review these four
methods prior to choosing one 1n particular. Appropriate surrogate standards
and, 1f necessary, matrix spiking solutions are added to the sample prior to
extraction for all four methods.
7.1.1 Method 3510: Applicable to the extraction and concentration
of water-Insoluble and slightly water-soluble organlcs from aqueous
samples. A measured volume of sample 1s solvent extracted using a
separatory funnel. The extract 1s dried, concentrated and, 1f necessary,
exchanged Into a solvent compatible with further analysis. Method 3520
should be used 1f an emulsion forms between the solvent-sample phases,
which can not be broken up by mechanical techniques.
7.1.2 Method 3520: Applicable to the extraction and concentration
of water-insoluble and slightly water-soluble organics from aqueous
samples. A measured volume of sample is extracted with an organic
solvent in a continuous liquid-liquid extractor. The solvent must have a
density greater than that of the sample. The extract is dried,
concentrated and, if necessary, exchanged into a solvent compatible with
further analysis. The limitations of Method 3510 concerning solvent-
sample phase separation do not interfere with this procedure.
3500 - 5
Revision
Date September 1986
-------
7.1.3 Method 3540: This is a procedure for extracting nonvolatile
and semi volatile organic compounds- from solids such as soils, sludges,
and wastes. A solid sample is mixed with anhydrous sodium sulfate,
placed into an extraction thimble or between two plugs of glass wool, and
extracted using an appropriate solvent in a Sbxhlet extractor. The
extract is dried, concentrated and, if necessary, exchanged into a
solvent compatible with further analysis.
7.1.4 Method 3550: This method is applicable to the extraction of
nonvolatile and semi volatile organic compounds from solids such as soils,
sludges, and wastes using the technique of sonication. Two procedures
are detailed depending upon the expected concentration of organics in the
sample; a low concentration and a high concentration method. In both, a
known weight of sample is mixed with anhydrous sodium sulfate and solvent
extracted using sonication. The extract is dried, concentrated and, if
necessary, exchanged into a solvent compatible with further analysis.
7.1.5 Method 3580: This method describes the technique of solvent
dilution of non-aqueous waste samples. It is designed for wastes that
may contain organic chemicals at a level greater than 20,000 mg/kg and
that are soluble in the dilution solvent.
;
7.2 Volatile organic sample preparation; There are three methods for
volatile sample preparation: Method 5030; Method 5040; and direct injection.
Method 5030 is the most widely applicable procedure for analysis of volatile
organics, while the direct injection technique may have limited applicability
to aqueous matrices.
7.2.1 Method 5030: This method .describes the technique of purge-
and-trap for the introduction of purgeable organics into a gas^
chromatograph. This procedure is applicable for use with aqueous samples
directly and to solids, wastes, soils/sediments, and water-miscible
liquids following appropriate preparation. An inert gas is bubbled
through the sample, which will efficiently transfer the purgeable
organics from the aqueous phase to the vapor phase. The vapor phase is
swept through a sorbent trap where the purgeables are trapped. After
purging is completed, the trap is heated and backflushed with the inert
gas to desorb the purgeables onto a gas chromatographic column. Prior to
application of the purge-and-trap procedure, all samples (including
blanks, spikes, and duplicates) should be spiked with surrogate standards
and, if required, with matrix spiking compounds.
7.2.2 Method 5040: This method is applicable to the investigation
of sorbent cartridges from volatile organic sampling train (VOST).
7.3 Sample analysis; Following preparation of a sample by one of the
methods described above, the sample is ready for further analysis. For
samples requiring volatile organic analysis, application of one of the three
methods described above is followed directly by gas chromatographic analysis
(Methods 8010, 8015, 8020, or 8030). Samples prepared for semi volatile
analysis may, if necessary, undergo cleanup (See Method 3600) prior to
application of a specific determinative method.
3500 - 6
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific guidance on quality control
procedures.
8.2 Before processing any samples, the analyst should demonstrate
through the analysis of a reagent water blank that all glassware and reagents
are interference free. Each time a set of samples are processed, a method
blank(s) should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample-preparation and measurement.
8.3 Surrogate standards should be added to all samples when specified in
the appropriate determinative method 1n Chapter Four, Section 4.3.
8.4 A reagent blank, a matrix spike, and a duplicate or matrix spike
duplicate must be performed for each analytical batch (up to a maximum of 20
samples) analyzed.
8.5 For GC or GC/MS analysis, the analytical system performance must be
verified by analyzing quality control (QC) check samples. Method 8000,
Section 8.0 discusses in detail the process of verification; however,
preparation of the QC check sample concentrate is dependent upon the method
being evaluated.
8.5.1 Volatile organic QC check samples: QC check sample
concentrates containing each analyte of Interest are spiked into reagent
water (defined as the QC check sample) and analyzed by purge-and-trap
(Method 5030). The concentration of each analyte 1n the QC check sample
1s 20 ug/L. The evaluation of system performance is discussed in detail
in Method 8000, beginning with Paragraph 8.6.
8.5.2 Semivolatile organic QC check samples: To evaluate the
performance of the analytical method, the QC check samples must be
handled 1n exactly the same manner as actual samples. Therefore, 1.0 mL
of the QC check sample concentrate is spiked into each of four 1-L
aliquots of reagent water (now called the QC check sample), extracted,
and then analyzed by GC. The variety of semi volatile analytes which may
be analyzed by GC 1s such that the concentration of the QC check sample
concentrate 1s different for the different analytical techniques
presented in the manual. Method 8000 discusses in detail the procedure
of verifying the detection system once the QC check sample has been
prepared. The concentrations of the QC check sample concentrate for the
various methods are as follows:
8.5.2.1 Method 8040 - Phenols; The QC check sample
concentrate should contain each analyte at a concentration of
100 ug/mL in 2-propanol.
8.5.2.2 Method 8060 - Phthalate esters; The QC check sample
concentrate should contain thefollowinganalytes at the following
concentrations in acetone: butyl benzyl phthalate, 10 ug/mL; bis(2-
ethylhexyl)phthalate, 50 ug/mL; d1-n-octylphthalate, 50 ug/mL; and
any other phthalate at 25 ug/mL.
3500 - 7
Revision 0
Date September 1986
-------
8.5.2.3 Method 8080 - Organochlorine pesticides and PCBs; The
QC check sampleconcentrate shouldcontain each single-component
analyte at the following concentrations in acetone: 4,4'-DDD, 10
ug/mL; 4,4'-DDT, 10 ug/mL; endosulfan II, 10 ug/mL; endosulfan
sulfate, 10 ug/mL; and any other single-component pesticide at 2
ug/mL. If the method is only to be used to analyze PCBs, chlordane,
or toxaphene, the QC check sample concentrate should contain the
most representative multicomponent parameter at a concentration of
50 ug/mL in acetone.
8.5.2.4 Method 8090 - Nitroaromatics and Cyclic Ketones: The
QC check sample concentrate should contain each analyte at the
following concentrations in acetone: each dinitrotoluene at
20 ug/mL; and isophorone and nitrobenzene at 100 ug/mL.
8.5.2.5 Method 8100 - Polynuclear aromatic hydrocarbons: The
QC check sample concentrate should contain each analyte at the
following concentrations in acetonitrile: naphthalene, 100 ug/mL;
acenaphthylene, 100 ug/mL; acenaphthene, 100 ug/mL; fluorene,
100 ug/mL; phenanthrene, 100 ug/mL; anthracene, 100 ug/mL;
benzo(k)fluoranthene 5 ug/mL; and any other PAH at 10 ug/mL.
8.5.2.6 Method 8120 - Chlorinated hydrocarbons; The QC check
sample concentrate should contain each analyte at the following
concentrations in acetone: hexachloro-substituted hydrocarbons,
10 ug/mL; and any other chlorinated hydrocarbon, 100 ug/mL.
9.0 METHOD PERFORMANCE
9.1 The recovery of surrogate standards is used to monitor unusual
matrix effects, sample processing problems, etc. The recovery of
matrix spiking compounds indicates the presence or absence of
unusual matrix effects.
9.2 The performance of this method will be dictated by the overall
performance of the sample preparation in combination with the
analytical determinative method.
10.0 REFERENCES
10.1 None required.
3500 - 8
Revision
Date September 1986
-------
METHOD 3500
ORGANIC EXTRACTION AND SAMPLE PREPARATION
U>
o
o
O 73
v>
_j.
c/> o
3
a
l-h
a>
a-
oo
cr>
-------
METHOD 3510
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for Isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described 1n Section 4.3 of Chapter Four.
1.2 This method Is applicable to the Isolation and concentration of
water-Insoluble and slightly water-soluble organlcs 1n preparation for a
variety of chromatographlc procedures.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), 1s serially extracted with methylene chloride using a separatory
funnel. The extract 1s dried, concentrated, and, as necessary, exchanged into
a solvent compatible with the cleanup or determinative step to be used.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel; 2-l1ter, with Teflon stopcock.
4.2 Drying column; 20-mm I.D. Pyrex chromatographlc column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone followed by
50 mL of elutlon solvent prior to packing the column with adsorbent.
4.3 Kuderna-Danlsh (K-D) apparatus;
4.3.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper 1s used to prevent evaporation of
extracts.
4.3.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
3510 - 1
Revision
Date September 1986
-------
TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8080
8090
8100
8120
8140,
8250*
8270b
8310
Initial
extraction
pH
< 2
as received
5-9
5-9
as received
as received
6-8
Ml
>11
as received
Secondary
extraction
pH
none
none
none
none
none
none
none
<2
<2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
^
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
•»
Final
extract
volune
for
analysis (mL)
1.0, 10 .Oa
10.0
10.0
1.0
1.0
1.0
10.0
10)
1.0
1.0
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by GC/FID. Method 8040 also
contains an optional derivatization procedure for phenols which results in a 10 mL hexane extract to be
analyzed by GC/ECD.
The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on
the cleanup procedures available if required.
3510 - 2
Revision 0
Date September 1986
-------
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.6 Vials: Glass, 2-mL capacity with Teflon-lined screw cap.
4.7 pH indicator paper; pH range including the desired extraction pH.
4.8 Erlenmeyer flask; 250-mL.
4.9 Syringe; 5-mL.
4.10 Graduated cylinder; 1-liter.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.2 Sodium hydroxide solution, 10 N: (ACS) Dissolve 40 g NaOH in
reagent water and dilute to 100 ml.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
5.4 Sulfuric acid solution (1:1): Slowly add 50 ml of ^04 (sp. gr.
1.84) to 50 ml of reagent water.
5.5 Extraction/exchange solvent; Methylene chloride, hexane,
2-propanol, cyclohexane, acetonitrile (pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3510 - 3
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Using a 1-liter graduated cylinder, measure 1 liter of sample and
transfer it to the separatory funnel. Add 1.0 ml of the surrogate standards
to all samples, spikes, and blanks (see Method 3500 for details on the
surrogate standard solution and the matrix spike solution). For the sample in
each analytical batch selected for spiking, add 1.0 ml of the matrix spiking
standard. For base/neutral-acid analysis, the amount added of the surrogates
and matrix spiking compounds should result in a final concentration of
100 ng/uL of each base/neutral analyte and 200 ng/uL of each acid analyte in
the extract to be analyzed (assuming a 1 uL injection). If Method 3640, Gel-
permeation cleanup, is to be used, add twice the volume of surrogates and
matrix spiking compounds since half the extract is -lost due to loading of the
GPC column.
7.2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.3 Add 60 ml of methylene chloride to the separatory funnel.
7.4 Seal and shake the separatory funnel vigorously for 1-2 min with
periodic venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 min. If the emulsion interface between layers is more than one-
third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. ; The optimum technique depends
upon the sample and may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods. Collect the solvent
extract in an Erlenmeyer flask. If the emulsion cannot be broken (recovery of
<80% of the methylene chloride, corrected for the water solubility of
methylene chloride), transfer the sample, solvent, and emulsion into the
extraction chamber of a continuous extractor and proceed as described in
Method 3520.
7.6 Repeat the extraction two more times using fresh portions of solvent
(steps 7.3 through 7.5). Combine the three solvent extracts.
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1. Serially extract
three times with 60 ml of methylene chloride, as outlined in Paragraphs 7.3
through 7.5. Collect and combine the extracts and label the combined extract
appropriately.
7.8 If performing GC/MS analysis (Method 8250 or 8270), the acid and
base/neutral extracts may be combined prior to concentration. However, in
some situations, separate concentration and analysis of the acid and
3510 - 4
Revision 0
Date September 1986
-------
base/neutral extracts may be preferable (e.g., if for regulatory purposes the
presence or absence of specific acid or base/neutral compounds at low
concentrations must be determined, separate extract analyses may be
warranted).
7.9 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporation flask.
7.10 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the Erlenmeyer flask, which contained the solvent
extract, with 20-30 ml of methylene chloride and add it to the column to
complete the quantitative transfer.
7.11 Add one or two clean boiling chips to the flask and attach a three-
ball Snyder column. Prewet the Synder column by adding about 1 mL of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
water bath (80-90*C) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 10-20 min. At the
proper rate of distillation, the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid reaches
1 mL, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 min.
7.12 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent, a new
boiling chip, and re-attach the Snyder column. Concentrate the extract, as
described in Paragraph 7.11, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.13 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange
solvent. If sulfur crystals are a problem, proceed to Method 3660 for
cleanup. The extract may be further concentrated by using the technique
outlined in Paragraph 7.14 or adjusted to 10.0 ml with the solvent last used.
7.14 If further concentration is indicated in Table 1, add another clean
boiling chip to the concentrator tube and attach a two-ball micro Snyder
column. Prewet the column by adding 0.5 mL of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot water bath
so that the concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as required,
to complete the concentration in 5-10 min. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will not
flood. When the apparent volume of liquid reaches 0.5 ml, remove the K-D
apparatus from the water bath and allow it to drain and cool for at least 10
min. Remove the Synder column and rinse the flask and its lower joints into
the concentrator tube with 0.2 mL of extraction solvent. Adjust the final
volume to 1.0-2.0 mL, as indicated in Table 1, with solvent.
3510 - 5
Revision 0
Date September 1986
-------
7.15 The extract obtained (from either Paragraph 7.13 or 7.14) may now
be analyzed for analyte content using a variety of organic techniques. If
analysis of the extract will not be performed Immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, 1t should be transferred to a Teflon-sealed screw-cap vial
and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3510 - 6
Revision
Date September 1986
-------
METHOD 3510
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
7.1 I Aad
'surrogate
standards to
•11 samples.
•Pikes, and
blanks
7.Z
Check end
adjust pH
7.3-7.6
Extract 3 tines
Yes
7.7
Collect
•no combine
extract* ana
label
O
7.6
I Combine
baae/neutral
extracts
prior to
concentratIon
I* CC/MS analy-
-------
METHOD 3520
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative steps
described in Section 4.3 of Chapter Four.
1.2 This method is applicable to the
water-Insoluble and slightly soluble organics
chromatographlc procedures.
Isolation and concentration of
1n preparation for a variety of
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate
the effectiveness of any such automatic extraction device before employing it
1n sample extraction.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, Is placed Into a
continuous liquid-liquid extractor, adjusted, 1f necessary, to a specific pH
(see Table 1), and extracted with organic solvent for 18-24 hr. The extract
1s dried, concentrated, and, as necessary, exchanged Into a solvent compatible
with the determinative step being employed.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Continuous liquid-liquid extractor; Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Hershberg-Wolf
Extractor -- Ace Glass Company, Vlneland, New Jersey, P/N 6841-10, or
equivalent).
4.2 Drying column; 20-mm I.D. Pyrex chromatographlc column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone followed by
50 mL of elutlon solvent prior to packing the column with adsorbent.
3520 - 1
Revision 0
Date September 1986
-------
TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8080
8090
8100
8120
8140,
8250*
8270b
8310
.
' . (
Initial
extraction
pH .
<2
as received
5-9
5-9
as received
as received
6-8
Ml
Ml
as received
Secondary
extraction
pH
none.
none
none
none
none
none
none
< 2
< 2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane .
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
• -
, —
Volume
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
—
—
—
Final
extract
volune
for
analysis (mL)
1.0, 10.08
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by GC/FID. Method 8040 also
contains an optional derivatization procedure for phenols which results in a 10 mL hexane extract to be
analyzed by OC/ECD. .• • • . - • •
The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on
the cleanup procedures available if. required.
3520 - 2
0
Revision
Date September 1986
-------
4.3 Kuderna-Danish (K-D) apparatus;
4.3.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.6 Vials: Glass, 2-mL capacity, with Teflon-lined screw cap.
4.7 pH indicator paper: pH range including the desired extraction pH.
4.8 Heating mantle; Rheostat controlled.
4.9 Syringe; 5-mL.
4.10 Graduated cylinder: 1-liter.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.2 Sodium hydroxide solution. 10 N: (ACS) Dissolve 40 g NaOH in
reagent water and dilute to 100 ml.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400'C for 4 hr in a shallow tray).
5.4 Sulfuric acid solution (1:1): Slowly add 50 mL of ^04 (sp. gr.
1.84) to 50 ml of reagent water.
5.5 Extraction/exchange solvent; Methylene chloride, hexane, 2-
propanol, cyclohexane, acetonitrile (pesticide quality or equivalent).
3520 - 3
Revision
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Using a graduated cylinder, measure out 1 liter (nominal) of sample
and transfer it to the continuous extractor. Check the pH of the sample with
wide-range pH paper and adjust the pH, if necessary, to the pH indicated in
Table 1. Pi pet 1.0 mL of the surrogate standard spiking solution into each
sample into the extractor and mix well. (See Method 3500 for details on the
surrogate standard solution and the matrix spike solution.) For the sample in
each analytical batch selected for spiking, add 1.0 mL of the matrix spiking
standard. For base/neutral-acid analysis, the amount of the surrogates and
matrix spiking compounds added to the sample should result in a final
concentration of 100 ng/uL of each base/neutral analyte and 200 ng/uL of each
acid analyte in the extract to be analyzed (assuming a 1 uL injection). If
Method 3640, Gel-permeation cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.2 Add 300-500 mL of methylene chloride to the distilling flask. Add
several boiling chips to the flask.
7.3 Add sufficient reagent water to the extractor to .ensure proper
operation and extract for 18-24 hr.
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and
concentrated as described in Section 7.7 through 7.11.
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to <2
with sulfuric acid (1:1). Attach a clean distilling flask containing 500 mL
of methylene chloride to the continuous extractor. Extract for 18-24 hr,
allow to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8250 or 8270), the acid and
base/neutral extracts may be combined prior to concentration. However, in
some situations, separate concentration and analysis of the acid and
base/neutral extracts may be preferable (e.g., if for regulatory purposes the
presence or absence of specific acid or base/neutral compounds at low
concentrations must be determined, separate extract analyses may be
warranted).
7.7 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporation flask.
7.8 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
3520 - 4
Revision 0
Date September 1986
-------
concentrator. Rinse the flask which contained the solvent extract with 20-30
ml of methylene chloride and add it to the column to complete the quantitative
transfer.
7.9 Add one or two clean boiling chips to the flask and attach a three-
ball Snyder column. Prewet the Snyder column by adding about 1 ml of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
water bath (80-90*C) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete the concentration in 10-20 min. At the
proper rate of distillation, the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 min. Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 ml of extraction solvent.
7.10 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent, a new
boiling chip, and re-attach the Snyder column. Concentrate the extract, as
described in Paragraph 7.9, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.11 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 mL of methylene chloride or exchange
solvent. If sulfur crystals are a problem, proceed to Method 3660 for
cleanup. The extract may be further concentrated by using the technique
outlined in Paragraph 7.12 or adjusted to 10.0 ml with the solvent last used.
7.12 Add another one or two clean boiling chips to the concentrator tube
and attach a two-ball micro Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column. Place the
K-D apparatus in a hot water bath so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete the concentration in 5-10 min.
At the proper rate of distillation, the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 min. Remove the Synder column, rinse the flask
and its lower joints into the concentrator tube with 0.2 ml of methylene
chloride or exchange solvent, and adjust the final volume to 1.0-2.0 ml, as
indicated in Table 1, with solvent.
7.13 The extracts obtained may now be analyzed for analyte content using
a variety of organic techniques (see Section 4.3 of this chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, it should be transferred to a Teflon-sealed screw-cap vial
and labeled appropriately.
3520 - 5
Revision 0
September 1986
-------
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample-preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES ,
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.-
3520 - 6
Revision
Date September 1986
-------
METHOD 3320
CONTINUOUS LIQUID-LIQUID EXTRACTION
7.1
1 Add
appropriate
surrogate ana
matrix •piking
solutions
7.2
Add
methylene
chloride to
distilling
flask
7. 13
Analyze using
organic
technique*
Dry
extract:
collect dried
extract in K-0
concentrator
7.3 I
1 Add
reagent water
to extractor;
extract for
16-24 hrs
-LLJ
Concentrate
using Snyder
column and K-O
apparatus
7.S
aquec
e>
18-Z'
Clt
Adjust
PH Of
us phase:
tract for
I Mrs with
an flask
Is solvent
exchange
required?
7.6 I Combine
I acid end
base/neutral
extracts
prior to
concentration
7.12
tret
if r
ad]
Further
concen-
.e extract
lecassary;
ust final
volume
3520 - 7
Revision 0
Date September 1986
-------
METHOD 3540
SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3540 is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes.
The Soxhlet extraction process ensures intimate contact of the sample matrix
with the extraction solvent.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water-soluble organics in preparation for a
variety of chromatographic procedures.
2.0 SUMMARY OF METHOD
2.1 The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using
an appropriate solvent in a Soxhlet extractor. The extract is then dried,
concentrated, and, as necessary, exchanged into a solvent compatible with the
cleanup or determinative step being employed.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extractor: 40-mm I.D., with 500-mL round-bottom flask.
4.2 Drying column; 20-mm I.D. Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone followed by
50 mL of elution solvent prior to packing the column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus;
4.3.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
3540 - 1
Revision 0
Date September 1986
-------
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath: Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.6 Vials: Glass, 2-mL capacity, with Teflon-lined screw cap.
4.7 Glass or paper thimble or glass wool: Contaminant free.
4.8 Heating mantle: Rheostat controlled.
4.9 Syringe: 5-mL.
4.10 Apparatus for determining percent moisture;
4.10.1 Oven: Drying.
4.10.2 Desiccator.
4.10.3 Crucibles: Porcelain.
4.11 Apparatus for grinding: If the sample will not pass through a 1-mm
standard sieve or cannot be extruded through a 1-mm opening, it should be
processed into a homogeneous sample that meets these requirements. Fisher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand and model, is recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
5.0 REAGENTS
5.1 Reagent water: Reagent water is defined as water in which an
ihterferent is not observed at the method detection limit of the compounds of
interest.
5.2 Sodium sulfate: (ACS) Granular anhydrous (purified by washing with
methylene chloride followed by heating at 400*C for 4 hr in a shallow tray).
5.3 Extraction solvents;
5.3.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems.
3540 - 2
Revision 0
Date September 1986
-------
5.3.1.1 Toluene/Methanol: 10:1 (v/v), pesticide quality or
equivalent.
5.3.1.2 Acetone/Hexane: 1:1 (v/v), pesticide quality or
equivalent.
5.3.2 Other samples shall be extracted using the following:
5.3.2.1 Methylene chloride: pesticide quality or equivalent.
5.4 Exchange solvents; Hexane, 2-propanol, cyclohexane, acetonitrile
(pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Sample handling;
7.1.1 Sediment/soil samples: Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.1.2 Waste samples: Samples consisting of multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding: Grind or otherwise
subdivide the waste so that it either passes through a 1-mm sieve or can
be extruded through a 1-mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.2 Determination of percent moisture; In certain cases, sample results
are desired based on a dry-weight basis. When such data is desired, a portion
of sample for moisture determination should be weighed out at the same time as
the portion used for analytical determination.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the percent
moisture by drying overnight at 105*C. Allow to cool in a desiccator
before weighing:
q of sample - q of dry sample x 100 _ % moisture
g of sample x 10U " * moisture
3540 - 3
Revision
Date September 1986
-------
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely
for the duration of the extraction period. A glass wool plug above and below
the sample in the Soxhlet extractor is an acceptable alternative for the
thimble. Add 1.0 ml of the surrogate standard spiking solution onto the
sample (See Method 3500 for details on the surrogate standard and matrix
spiking solutions.) For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng/uL of each base/neutral
analyte and 200 ng/uL of each acid analyte in the extract to be analyzed
(assuming a 1 uL injection). If Method 3640, Gel-permeation cleanup, is to be
used, add twice the volume of surrogates and matrix spiking compounds since
half the extract is lost due to loading of the GPC column.
7.4 Place 300 ml of the extraction solvent (Section 5.3) into a 500-mL
round-bottom flask containing one or two clean boiling chips. Attach the
flask to the extractor and extract the sample for 16-24 hrn
7.5 Allow the extract to cool after the extraction is complete.
7.6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporation flask.
7.7 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Wash the extractor flask and sodium sulfate column with
100-125 ml of extraction solvent to complete the quantitative transfer.
7.8 Add one or two clean boiling chips to the flask and attach a three-
ball Snyder column. Prewet the Snyder column by adding about 1 ml of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
water bath (15-20*C above the boiling point of the solvent) so that the
concentrator tube is partially immersed in the hot water and the entire lower
rounded surface of the flask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to complete
the concentration in 10-20 min. At the proper rate of distillation, the balls
of the column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 1 ml, remove the K-D apparatus from the
water bath and allow it to drain and cool for at least 10 min.
7.9 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent and a
new boiling chip, and re-attach the Snyder column. Concentrate the extract as
described in Paragraph 7.6, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.10 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange
solvent. If sulfur crystals are a problem, proceed to Method 3660 for
cleanup. The extract may be further concentrated by using the technique
outlined in Paragraph 7.9 or adjusted to 10.0 ml with the solvent last used.
3540 - 4
Revision 0
Date September 1986
-------
TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
80403
8060
8080
8090
8100
8120
8140
8250Y
8270a,C
8310
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
"
Volume
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
-
"
Final
extract
volune
for
analysis (mL)
1.0, 10 .Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by OC/FID. Method 8040
also contains an optional derivatization procedure for phenols which results in a 10 mL hexane
extract to be analyzed by GC/ECD.
The specificity of OC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
guidance on the cleanup procedures available if required.
3540 - 5
Revision 0
Date September 1986
-------
7.11 If further concentration 1s Indicated 1n Table 1, add another one
or two clean boiling chips to the concentrator tube and attach a two-ball
micro Snyder column. Prewet the column by adding 0.5 ml of methylene chloride
or exchange solvent to the top of the column. Place the K-D apparatus 1n a
hot water bath so that the concentrator tube is partially immersed in the hot
water. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete the concentration 1n 5-10 min. At the
proper rate of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid reaches
0.5 mL, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 min. Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 0.2 ml of solvent. Adjust
the final volume to 1.0-2.0 ml, as Indicated in Table 1, with solvent.
7.12 The extracts obtained may now be analyzed for analyte content using
a variety of organic techniques (see Section 4.3 of this chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, it should be transferred to a Teflon-sealed screw-cap vial
and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3540 - 6
Revision 0
Date September 1986
-------
METHOD 3540
SOXHLET EXTRACTION
7. 1
Use
appropriate
cample Dandling
technique
7 .Z
Determine
percent
moisture
7.7
Dry and collect
extract In K-D
concentrator
7.3
I Add
appropriate
surrogate and
matrix spiking
standards
4.6
Concentrate
using Snyder
column and K-O
apparatus
4.8 I
Reconccntrate
using Snyder
column and K-O
apparatus
7.4
I Place
Imethylene
cnloride:
acetone In
flask; extract
for 16-24 hrs
Analyze using
organic
techniques
3540 - 7
Revision p
Date September 1986
-------
METHOD 3550
SONICATION EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3550 Is a procedure for extracting nonvolatile and semi-
volatlle organic compounds from sol Ids such as soils, sludges, and wastes.
The sonlcatlon process ensures Intimate contact of the sample matrix with the
extraction solvent.
1.2 The method 1s divided Into two sections, based on the expected
concentration of organlcs 1n the sample. The low concentration method
(Individual organic components of <£20 mg/kg) uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract). The high concentration method (Individual organic components of
>20 mg/kg) 1s much simpler and therefore faster.
1.3 It 1s highly recommended that the extracts be cleaned up prior to
analysis. See Cleanup, Section 4.2.2 of Chapter Four, for applicable methods.
2.0 SUMMARY OF METHOD
2.1 Low concentration method; A 30-g sample 1s mixed with anhydrous
sodium sulfate to form a free-flowing powder. This 1s solvent extracted three
times using sonlcatlon. The extract 1s separated from the sample by vacuum
filtration or centrlfugatlon. The extract 1s ready for cleanup and/or
analysis following concentration.
2.2 High concentration method; A 2-g sample 1s mixed with anhydrous
sodium sulfate to form a free-flowing powder. This 1s solvent extracted once
using sonlcatlon. A portion of the extract 1s removed for cleanup and/or
analysis.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for grinding; If the sample will not pass through a 1-mm
standard sieve or cannot beextruded through a 1-mm opening, 1t should be
processed Into a homogeneous sample that meets these requirements. Fisher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand and model, 1s recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
3550 - 1
Revision 0
Date September 1986
-------
4.2 Sonication: A horn-type sonicator equipped with a titanium tip
should be used. The following sonicator, or an equivalent brand and model, 1s
recommended: .
Ultrasonic cell disrupter: Heat Systems - Ultrasonics, Inc., Model
W-385 (475 watt) sonicator or equivalent (Power wattage must be a
minimum of 375 with pulsing capability and No. 200 1/2" Tapped
Disrupter Horn) plus No. 207 3/4" Tapped Disrupter Horn, and No. 419
1/8" Standard Tapered microtip probe.
4.3 Sonabox; Recommended with above disrupters for decreasing
cavitation sound (Heat Systems - Ultrasonics, Inc., Model 432B or
equivalent).
4.4 Apparatus for determining percent moisture;
4.4.1 Oven: Drying.
4.4.2 Desiccator.
4.4.3 .Crucibles: Porcelain.
4.5 Pasteur glass pipets; Disposable, 1-mL.
4.6 Beakers; 400-mL.
4.7 Vacuum filtration: apparatus;
4.7.1 Buchner funnel.
4.7.2 Filter paper: Whatman No. 41 or equivalent.
4.8 Kuderna-Danish (K-D) apparatus;
4.8.1 Concentrator tube: 10-mL graduated (Kontes K-570050-1025 or
equivalent). '
4.8.2 Evaporator flask: 500-mL (Kontes K-570001-0500 or
equivalent).
4.8.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent). "
4.9 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent). ..-;••
4.10 Water bath: Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
3550 - 2
Revision
Date September 1986
-------
4.11 Balance; Top-loading, capable of accurately weighing 0.01 g.
4.12 Vials and caps; 2-mL for GC auto-sampler.
4.13 Glass scintillation vials; At least 20-mL, with screw-cap and
Teflon or aluminum foil liner.
4.14 Spatula; Stainless steel or Teflon.
4.15 Drying column: 20-mm I.D. Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 ml of elution solvent prior to packing the column with adsorbent.
4.16 Syringe; 5-mL.
5.0 REAGENTS
5.1 Sodium sulfate; Anhydrous and reagent grade, heated at 400*C for
4 hr, cooled in a desiccator, and stored in a glass bottle. Baker anhydrous
powder, catalog #73898, or equivalent.
5.2 Extraction solvents; Methylene chloride:acetone (1:1, v:v),
methylene chloride, hexane (pesticide quality or equivalent).
5.3 Exchange solvents; Hexane, 2-propano!, cyclohexane, acetonitrile
(pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Sample handling;
7.1.1 Sediment/sot! samples: Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.1.2 Waste samples: Samples consisting of multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
3550 - 3
Revision
Date September 1986
-------
7.1.3 Dry waste samples amenable to grinding: Grind or otherwise
subdivide the waste so that it either passes through a 1-mm sieve or can
be extruded through a 1-mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.2 Determination of percent moisture; In certain cases, sample results
are desired based on a dry-weight basis. When such data is desired, a portion
of sample for moisture determination should be weighed out at the same time as
the portion used for analytical determination.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the percent
moisture by drying overnight at 105'C. Allow to cool in a desiccator
before weighing:
q of sampT- qdry sample x 100 = % mo1sture
7.3 Determination of pH (if required): Transfer 50 g of sample to a
100-mL beaker. Add 50 ml of water and stir for 1 hr. Determine the pH of
sample with glass electrode and pH meter while stirring. Discard this portion
of sample.
7.4 Extraction method for samples expected to contain low concentrations
of organics and pesticides «20 mg/kg):
7.4.1 The following step should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of sample
into a 400-mL beaker. Record the weight to the nearest 0.1 g. Non-
porous or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with 60 g of anhydrous sodium sulfate
using a spatula. The sample should be free-flowing at this point. Add
1 mL of surrogate standards to all samples, spikes, and blanks (see
Method 3500 for details on the surrogate standard solution and the matrix
spike solution). For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-
acid analysis, the amount added of the surrogates and matrix spiking
compounds should result in a final concentration of 100 ng/uL of each
base/neutral analyte and 200 ng/uL of each acid analyte in the extract to
be analyzed (assuming a 1 uL injection). If Method 3640, Gel -permeation
cleanup, is to be used, add twice the volume of surrogates and matrix
spiking compounds since half of the extract is lost due to loading of the
GPC column. Immediately add 100 ml of 1:1 methylene chloride:acetone.
7.4.2 Place the bottom surface of the tip of the #207 3/4 in.
disrupter horn about 1/2 in. below the surface of the solvent, but above
the sediment layer.
7.4.3 Sonicate for 3 min, with output control knob set at 10 and
with mode switch on Pulse and percent-duty cycle knob set at 50%. Do NOT
use microtip probe.
3550 - 4
Revision 0
Date September 1986
-------
7.4.4 Decant and filter extracts through Whatman No. 41 filter
paper using vacuum filtration or centrifuge and decant extraction
solvent.
7.4.5 Repeat the extraction two or more times with two additional
100-mL portions of solvent. Decant off the extraction solvent after each
sonication. On the final sonication, pour the entire sample into the
Buchner funnel and rinse with extraction solvent.
7.4.6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a
10-mL concentrator tube to a 500-mL evaporative flask.
7.4.7 Dry the extract by passing it through a drying column
containing about 10 cm of anhydrous sodium sulfate. Collect the dried
extract in a K-D concentrator. Wash the extractor flask and sodium
sulfate column with 100-125 ml of extraction solvent to complete the
quantitative transfer.
7.4.8 Add one or two clean boiling chips to the evaporative flask
and attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1 ml methylene chloride to the top. Place the K-D apparatus
on a hot water bath (80-90'C) so that the concentrator tube is partially
immersed in the hot water and the entire lower rounded surface of the
flask is bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 10-15 min. At the proper rate of distillation the balls
of the column will actively chatter, but the chambers will not flood with
condensed solvent. When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus and allow it to drain and cool for at least
10 min.
7.4.9 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent
and a new boiling chip, and re-attach the Snyder column. Concentrate the
extract as described in Paragraph 7.4.8, raising the temperature of the
water bath, if necessary, to maintain proper distillation.
7.4.10 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 mL of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
technique outlined in Paragraph 7.4.11 or adjusted to 10.0 ml with the
solvent last used.
7.4.11 Add a clean boiling chip and attach a two-ball micro-Snyder
column to the concentrator tube. Prewet the column by adding approxi-
mately 0.5 ml of methylene chloride or exchange solvent through the top.
Place the apparatus in the hot water bath. Adjust the vertical position
and the water temperature, as required, to complete the concentration in
5-10 min. At the proper rate of distillation, the balls of the column
will actively chatter, but the chambers will not flood. When the liquid
3550 - 5
Revision 0
Date September 1986
-------
TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
80403
8060
8380
8090
8100
8120
8140
8250V
8270a,C
8310
Extraction
pH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
~
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
-
~
Final
extract
volune
for
analysis (mL)
1.0, 10. Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.
Phenols may be analyzed, by Method 8940, using a 1.0 mL 2-propanol extract by GC/FID. Method 8340
also contains an optional derivatization procedure for phenols which results in a 10 mL hexane
extract to be analyzed by GC/ECD.
The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
guidance on the cleanup procedures available if required.
3550 - 6
Revision 0
Date September 1986
-------
reaches an apparent volume of approximately 0.5 ml, remove the apparatus
from the water bath and allow to drain and cool for at least 10 min.
Remove the micro-Snyder column and rinse its lower joint into the
concentrator tube with approximately 0.2 ml of appropriate solvent.
Adjust the final volume to the volume required for cleanup or for the
determinative method (see Table 1).
7.4.12 Transfer the concentrated extract to a clean screw-cap vial.
Seal the vial with a Teflon-lined lid and mark the level on the vial.
Label with the sample number and fraction and store in the dark at 4*C
until ready for analysis or cleanup.
7.5 Extraction method for samples expected to contain high concen-
trations of organics (>20 mg/kg);
7.5.1 Transfer approximately 2 g (record weight to the nearest
0.1 g) of sample to a 20-mL vial. Wipe the mouth of the vial with a
tissue to remove any sample material. Record the exact weight of sample
taken. Cap the vial before proceeding with the next sample to avoid any
cross contamination.
7.5.2 Add 2 g of anhydrous sodium sulfate to sample in the 20-mL
vial and mix well.
7.5.3 Surrogate standards are added to all samples, spikes, and
blanks (see Method 3500 for details on the surrogate standard solution
and on the matrix spike solution). Add 2.0 mL of surrogate spiking
solution to sample mixture. For the sample in each analytical batch
selected for spiking, add 2.0 mL of the matrix spiking standard. For
base/neutral-acid analysis, the amount added of the surrogates and matrix
spiking compounds should result in a final concentration of 200 ng/uL of
each base/neutral analyte and 400 ng/uL of each acid analyte in the
extract to be analyzed (assuming a 1 uL injection). If Method 3640, Gel-
permeation cleanup, is to be used, add twice the volume of surrogates and
matrix spiking compounds since half the extract is lost due to loading of
the GPC column.
7.5.4 Immediately add whatever volume of solvent is necessary to
bring the final volume to 10.0 mL considering the added volume of
surrogates and matrix spikes. Disrupt the sample with the 1/8-in.
tapered microtip ultrasonic probe for 2 min at output control setting 5
and with mode switch on pulse and percent duty cycle of 50%. Extraction
solvents are:
1. Nonpolar compounds, i.e., organochlorine pesticides and
PCBs: hexane.
2. Extractable priority pollutants: methylene chloride. /
7.5.5 Loosely pack disposable Pasteur pipets with 2- to 3-cm Pyrex
glass-wool plugs. Filter the extract through the glass wool and collect
3550 - 7
Revision 0
Date September 1986
-------
5.0 ml in a concentrator tube if further concentration is required.
Follow Paragraphs 7.4.6 through 7.4.12 for details on concentration.
Normally, the 5.0 ml extract is concentrated to.1.0 ml.
7.5.6 The extract is ready for cleanup or analysis, depending on
the extent of interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subject to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
2. U.S. EPA, Interlaboratory Comparison Study: Methods for Volatile and Semi-
Volatile Compounds, Environmental Monitoring Systems Laboratory, Office of
Research and Development, Las Vegas, NV, EPA 600/4-84-027, 1984.
3550 - 8
Revision
Date September 1986
-------
METHOD 3550
SONICATION EXTRACTION
7. J I
I Prepare
samples using
appropriate
method for the
•taste matrix
7 .Z
7.5.2
Add anhydrous
sodium sulfate
to sample
Determine
the percent
of moisture in
the sample
7.5.3
Is organic
concentration
expected to
be
-------
METHOD 3550
SONICATION EXTRACTION
(Continued)
o
Oo sulfur
crystals form?
Use *•thod 3660
far cleanup
Further
concentrate
and/or adjust
volume
3550 - 10
Revision 0
Date September 1986
-------
METHOD 3580
WASTE DILUTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a solvent dilution of a non-aqueous waste
sample prior to cleanup and/or analysis. It is designed for wastes that may
contain organic chemicals at a level greater than 20,000 mg/kg and that are
soluble in the dilution solvent.
1.2 It is recommended that an aliquot of the diluted sample be cleaned
up. See the Cleanup section of this chapter for methods (Section 4.2.2).
2.0 SUMMARY OF METHOD
2.1 One gram of sample is weighed into a capped tube, and the sample is
diluted to 10.0 mL with an appropriate solvent.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Glass scintillation vials: At least 20-mL, with Teflon or aluminum-
foil-lined screw-cap.
4.2 Spatula: Stainless steel or Teflon.
4.3 Balance: Capable of weighing 100 g to the nearest 0.01 g.
4.4 Vials and caps; 2-mL for GC autosampler.
4.5 Disposable pi pets; Pasteur.
4.6 Test tube rack.
4.7 Pyrex glass wool.
4.8 Volumetric flasks; 10-mL (optional).
5.0 REAGENTS
5.1 Sodium sulfate; (ACS) Granular, anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
3580 - 1
Revision
Date September 1986
-------
5.2 Solvents; Methylene chloride and hexane (pesticide quality or
equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1-.
7.0 PROCEDURE
7.1 Samples consisting of multlphases must be prepared by the phase
separation method (Chapter Two) before extraction.
7.2 The sample dilution may be performed in a 10-mL volumetric flask.
If disposable glassware 1s preferred, the 20-mL scintillation vial may be
calibrated for use. Simply pipet 10.0 mL of extraction solvent into the
scintillation vial and mark the bottom of the meniscus. Discard this solvent.
7.3 Transfer approximately 1 g of each phase (record weight to the
nearest 0.1 g) of the sample to separate 20-mL vials or 10-mL volumetric
flasks. Wipe the mouth of the vial with a tissue to remove any sample
material. Cap the vial before proceeding with the next sample to avoid any
cross-contamination.
7.4 Add 2.0 mL surrogate spiking solution to all samples and blanks.
For the sample in each analytical batch selected for spiking, add 2.0 mL of
the matrix spiking standard. For base/neutral-acid analysis, the amount added
of the surrogates and matrix spiking compounds should result 1n a final
concentration of 200 ng/uL of each base/neutral analyte and 400 ng/uL of each
acid analyte in the extract to be analyzed (assuming a 1 uL injection). If
Method 3640, Gel-permeation cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column. See Method 3500 for details on the surrogate
standard and matrix spiking solutions.
7.5 Immediately dilute to 10 mL with the appropriate solvent. For
compounds to be analyzed by GC/ECD, e.g., organochlorine pesticides and PCBs,
the dilution solvent should be hexane. For base/neutral and acid semivolatile
priority pollutants, use methylene chloride. If dilution is to be cleaned up
by gel permeation chromatography (Method 3640), use methylene chloride as the
dilution solvent for all compounds.
7.6 Add 2.0 g of anhydrous sodium sulfate to the sample.
7.7 Cap and shake the sample for 2 min.
7.8 Loosely pack disposable Pasteur pipets with 2-3 cm glass wool plugs.
Filter the extract through the glass wool and collect 5 mL of the extract 1n a
tube or vial.
3580-2
Revision 0
Date September 1986
-------
7.9 The extract 1s ready for cleanup or analysis, depending on the
extent of Interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks and matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
10.1 None applicable.
3580 - 3
Revision
Date September 1986
-------
METHOD 3580
WASTE DILUTION
Does sample
contain more than
one phase?
o
Use phase
separat Ion
method
(chapter 2)
7.5
Dilute with
appropriate
•olvent
7.31
Transfer 1 g
of aach phase
to separate
vials or flasks
7.4
7.6
Add anhydrous
ammonium
sulfate
Add
surrogate
spiking
solution to
all samples
and blanks
7 .A
7.7
Cap and shake
Add
matrix spiking
standard to
sample selected
for spiking
7.6
Filter through
glass wool
Q
Cleanup
or
analyze
3580 - 4
Revision 0
Date September 1986
-------
METHOD 5030
PURGE-AND-TRAP
1.0 SCOPE AND APPLICATION
1.1 This method describes sample preparation and extraction for the
analysis of volatile organics by a purge-and-trap procedure. The gas
chromatographic determinative steps are found in Methods 8010, 8015, 8020, and
8030. Although applicable to Method 8240, the purge-and-trap procedure is
already incorporated into Method 8240.
1.2 Method 5030 can be used for most volatile organic compounds that
have boiling points below 200*C (vapor pressure is approximately equal to
mm Hg @ 25*C) and are insoluble or slightly soluble in water. Volatile water-
soluble compounds can be included in this analytical technique; however,
quantisation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds
that elute as sharp peaks from a GC column packed with graphitized carbon
lightly coated with a carbowax. Such compounds include low-molecular-weight
halogenated hydrocarbons, aromatics, ketones, nitriles, acetates, acrylates,
ethers, and sulfides.
1.3 Water samples can be analyzed directly for volatile organic
compounds by purge-and-trap extraction and gas chromatography. Higher
concentrations of these analytes in water can be determined by direct
injection of the sample into the chromatographic system.
1.4 This method also describes the preparation of water-misdble
liquids, solids, wastes, and soil/sediments for analysis by the purge-and-trap
procedure.
2.0 SUMMARY OF METHOD
2.1 The purge-and-trap process; An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are adsorbed. After
purging is completed, the sorbent column is heated and backflushed with inert
gas to desorb the components onto a gas chromatographic column.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in methanol to dissolve the volatile
organic constituents. A portion of the methanolic solution is combined with
water in a specially designed purging chamber. It is then analyzed by purge-
and-trap GC following the normal water method.
5030 - 1
Revision
Date September 1986
-------
3.0 INTERFERENCES
3.1 Impurities In the purge .gas and from organic compounds out-gassing
from the plumbing ahead of the .trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from contami-
nation under the conditions of the analysis by running laboratory reagent
blanks. The use of non-TFE plastic coating, non-TFE thread sealants, or flow
controllers with rubber components in the purging,device-should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A field reagent blank prepared
from reagent water and. carried through sampling and handling protocols serves
as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-level and low-
level samples are analyzed sequentially. Whenever an unusually'concentrated
sample is analyzed, it should be followed by an analysis of reagent water to
check for cross-contamination.. The trap and other parts of the system are
subject to contamination; therefore, frequent bake-out and purging of the
entire system may be required.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes; 10-uL, 25-uL, 100-uL, 250-uL, 500-uL, and 1,000 uL:
These syringes shouldbe equipped with a 20-gauge (0.006-in I^D.) needle
having a length sufficient to extend from the sample inlet to within 1 cm of
the glass frit in the purging device. The needle length will depend upon the
dimensions of the purging device employed.'
4.2 Syringe valve; Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe; 5-mL, gas-tight with shutoff valve.
4.4 Balance; Analytical, capable of accurately weighing 0.0001 g, and a
top-loading balance capable of weighing 0.1 g.
4.5 Glass scintillation vials; 20-mL, with screw-caps and Teflon liners
or glass culture tubes with a screw-cap and Teflon Uner.
4.6 Volumetric flasks; 10-mL and. 100-mL, class A with ground-glass
stoppers.
4.7 Vials; 2-mL, for GC autosampler.
4.8 Spatula; Stainless steel.
5030 - 2
Revision 0
Date September 1986
-------
4.9 Disposable pi pets; Pasteur.
4.10 Purge-end-trap device; The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.10.1 The recommended purging chamber 1s designed to accept 5-mL
samples with a water column at least 3 cm deep. The gaseous headspace
between the water column and the trap must have a total volume of less
than 15 mL. The purge gas must pass through the water column as finely
divided bubbles with a diameter of less than 3-mm at the origin. The
purge gas must be introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be used, provided
equivalent performance is demonstrated.
4.10.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene
oxide polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is
recommended that 1.0 cm of methyl s111 cone-coated packing be inserted at
the inlet to extend the life of the trap (see Figures 2 and 3). If it is
not necessary to analyze for dichlorodifluoromethane or other fluoro-
carbons of similar volatility, the charcoal can be eliminated and the
polymer increased to fill 2/3 of the trap. If only compounds boiling
above 35*C are to be analyzed, both the silica gel and charcoal can be
eliminated and the polymer increased to fill the entire trap. Before
initial use, the trap should be conditioned overnight at 180°C by
backflushing with an inert gas flow of at least 20 mL/min. Vent the trap
effluent to the hood, not to the analytical column. J'rior to daily use,
the trap should be conditioned for 10 min at 180°C with backflushing.
The trap may be vented to the analytical column during daily
conditioning; however, the column must be run through the temperature
program prior to analysis of samples.
4.10.3 The desorber should be capable of rapidly heating the trap
to 180°C for desorption. The polymer section of the trap should not be
heated higher than 180*C, and the remaining sections should not exceed
220*C during bake-out mode. The desorber design illustrated in Figures 2
and 3 meet these criteria.
4.10.4 The purge-and-trap device may be assembled as a separate
unit or may be coupled to a gas chromatograph, as shown in Figures 4 and
5.
4.10.5 Trap Packing Materials
4.10.5.1 2,6-Diphenylene oxide polymer: 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.10.5.2 Methyl silicone packing: OV-1 (3%) on Chromosorb-W,
60/80 mesh or equivalent.
5030 - 3
Revision 0
Date September 1986
-------
OPTIONAL
FOAM TRAP
Exit 14 Inch 0. 0.
14 mm 0. D.
Inlet 14 Inch 0. D.
Inch 0. D. Exit
10 mm Glass Frit
Medium Porosity
Simple Inlet
2-Way Syringe Valve
17 cm, 20 Gauge Syringe Needle
6 mm 0. D. Rubber Septum
"•10mm 0. D.
Inlet
* Inch 0. 0.
V16 Inch 0. D.
Stainless Stee.'
13x Molecular
Sieve Purge
Gas Filter
Purge Gas
Flow Control
Figure 1. Purging chamber.
5030 - 4
Revision 0
Date September 1986
-------
Packing Procedure
Construction
_ Compression
Glass Wool 5 mm
I
Activated |
Charcoal 7.7 cm
i
Grade 15
Silica Gel 7.7 cm
•
Tenax 7.7cr
•
3% OV-1 1 cm ;
Glass Wool 5 mm
n
=
^*
1
y?
^
#
\
N^
^
^
^;
S
,>'•
'•'*•
^
7n/Foot
Resistance
Wire Wrapped •<
Solid
(Double Layer)
T
^
-~C
~*^^
^v
I
c
15cm ^
7S7/Foot •
Resistance
Wire Wrapped
Solid
(Single Layer)
c
C
>
<
' V
C
c
Bern *~
d
"" )^— Fining Nut
^ ^ and Ferrules
^
^M
**
•^
^
^•1
i^
^V
— **
^^
JWM
|M«
^^
D
s
J
/
*»
^
• '
" >
^
^%
5
J
>
>
* /
>J
i+s
Thermocouple/
Controller
Sensor
*£"
y2
'/~
I
Tub
• o.ic
Electronic
Temperature
Control and
Pyrometer
ing 25 cm
)5 In. I.D.
0.125 In. O.D.
Stainless Steel
Trap Inlet
Figure 2. Trap packings and construction for Method 8010.
5030 - 5
Revision p
Date September 1986
-------
Packing Procedure
Construction
Glass Wool 5 mm
Tenax 23 cm
3% OV-1 1 cm ^ ;
Glass Wool 5 mm
1
f
* wrr
K
i
*
'£/.
Trap Inlet
Compression Fitting Nut
and Ferrules
14 Ft. ?n/Foot Resistance
Wire Wrapped Solid
Thermocouple/Controller Sensor
Electronic
Temperature
Control and,
Pyrometer
Tubing 25 cm
OV105 In. I.D.
•0:125 In. O.D.
Stainless Steel
Figure 3. Trap packing and construction for Methods 8020 and 8030.
5030 - 6
Revision p
Date September 1986
-------
en
o
CO
o
O 70
a> n
r* <
n ->.
CO O
0> 3
Carrier Gas Flow Control
Pressure Regulator
Liquid Infection Ports
Purge Gas
Flow Control
13X Molecular
Sieve Filter
^
Column Oven
D Confirmatory Column
elector
Analytical Column
Valve-3
Optional 4-Port Column
Selection Valve
Trap Inlet (Tenax End)
Resistance Wire
Heater Control
Note: All Lines Between Trap and GC
Should be Heated to 80°C.
Valve-2
VO
00
Figure 4. Purgc-and trap system, purge-sorb mode, for Methods 8010, 8020, and 8030.
-------
en
o
CO
o
oo
O 73
O> O>
n> -••
CO O
O> 3
a>
Carrier Gas Flow Control
Pressure Regulator
Liquid Injection Ports
Purge Gas
Flow Control
13X Molecular
Sieve Filter
Column Oven
Confirmatory Column
To Detector
Analytical Column
Valve-3
Optional 4-Port Column
Selection Valve
Trap Inlet (Tenax End)
Resistance Wire
Heater Control
Note: All Lines Between Trap and GC
Should be Heated to 80°C.
Valve- 2
Figure 5. Purge-and trap system, desorb mode, for Methods 8010,8020, and 8030.
-------
4.10.5.3 Silica gel: 35/60 mesh, Davison, grade 15 or
equivalent.
4.10.5.4 Coconut charcoal: Prepare from Barnebey Cheney,
CA-580-26 lot #M-2649, by crushing through 26 mesh screen.
4.11 Heater or heated oil bath; Should be capable of maintaining the
purging chamber to within 1*C over a temperature range from ambient to 100°C.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.1.1 Reagent water may be generated by passing trap water through
a carbon filter bed containing about 500 g of activated carbon (Calgon
Corp., Filtrasorb-300 or equivalent).
5.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
5.1.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the water temperature at 90*C,
bubble a contaminant-free inert gas through the water for 1 hr. While
still hot, transfer the water to a narrow-mouth screw-cap bottle and seal
with a Teflon-lined septum and cap.
5.2 Methanol; Pesticide quality or equivalent. Store away from other
solvents.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to the introductory material to this chapter, Organic
Analytes, Section 4.1.
7.0 PROCEDURE
7.1 Initial calibration; Prior to using this introduction technique for
any GC method, the system must be calibrated. General calibration procedures
are discussed 1n Method 8000, Section 7.4, while the specific determinative
methods and Method 3500 give details on preparation of standards.
7.1.1 Assemble a purge-and-trap device that meets the specification
in Section 4.10. Condition the trap overnight at 180*C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition
the trap daily for 10 min while backflushing at 180*C with the column at
220*C.
5030 - 9
Revision 0
Date September 1986
-------
7.1.2 Connect the purge-and-trap device to a gas. chromatograph.
7.1.3 Prepare the .final solutions containing the required
.concentrations of calibration standards, including surrogate standards,
directly in the purging device. Add 5.0 ml of reagent water to the
purging device. . The reagent water is added to the purging device using a
5-mL glass syringe fitted with a 15-cm 20-gauge needle. The needle is
.inserted through the sample inlet shown in Figure 1. The internal
f,,.diameter of the 14-gauge needle that forms the sample inlet will permit
insertion of the 20-gauge needle. Next, using a 10-uL or 25-uL micro-
syringe equipped with a long needle (Paragraph 4.1), take a volume of the
secondary dilution solution containing appropriate concentrations of the
calibration standards. Add the aliquot of calibration solution directly
.to the,reagent water in the purging device by inserting the needle
1 through the sample inlet. When discharging the contents of the micro-
: syringe, be;sure that the end of the syringe needle is well beneath the
surface of the reagent water. Similarly, add 10 uL of the internal
standard solution. Close the 2-way syringe valve at the sample inlet.
7.1.4 Carry out the purge-and-trap analysis procedure using the
specific conditions given in Table 1. ......
7.1.5 Calculate response factors or calibration factors for each
analyte of interest using the procedure described in Method 8000, Section
7;4. - • • • ' • • • •
7.1.6 The average RF must be calculated for each compound. A
system performance check should be made before this calibration curve is
used. If the purge-and-trap procedure is used with Method 8010, the
following five compounds are checked for a minimum average response
factor: chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-tetra-
chloroethane; and chlorobenzene. The minimum acceptable average RF for
these compounds should be 0.300 (0.250 for bromoform). These compounds
typically have RFs of 0.4-0.6 and are used to check compound instability
and check for degradation caused by contaminated lines or active sites in
the system. Examples of these occurrences are:
7.1.6.1 Chloromethane; This compound is the most likely
compound to be lost if the purge flow is too fast.
7.1.6.2 Bromoform; This compound is one of the compounds most
likely to be purged very poorly if the purge flow is too slow. Cold
spots and/or active sites in the transfer lines may adversely affect
response.
7.1.6.3 Tetrachloroethane and 1,1-dichloroethane; These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2 On-going calibration; Refer to Method 8000, Sections 7.4.2.3 and
7.4.3.4 for details on continuing calibration.
5030 - 10
Revision 0
Date September 1986
-------
TABLE 1. PURGE-AND-TRAP OPERATING PARAMETERS
Analysis Method
8010
8015
8020
8030
Purge gas
Purge gas flow rate
(mL/min)
Purge time (m1n)
Purge temperature (*C)
Desorb temperature (*C)
Backflush Inert gas flow
(ml/mln)
Desorb time (min)
Nitrogen or Nitrogen or
Helium
40
11.0 + 0.1
Ambient
180
20-60
4
Helium
20
15.0 + 0.1
85 + 2
180
20-60
1.5
Nitrogen or Nitrogen or
Helium Helium
40
12.0 + 0.1
Ambient
180
20-60
4
20
15.0 + 0.1
85 + 2
180
20-60
1.5
5030 - 11
Revision 0
Date September 1986
-------
7.3 Sample preparation:
7.3.1 Water samples:
7.3.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be utilized are: the use
of an automated headspace sampler (modified Method 3810), interfaced
to a- gas chromatograph (GC), equipped with a photo ionization
detector (PID), in series with an electrolytic conductivity detector
(ECD); and extraction of the sample with hexadecane (Method 3820)
and analysis of the extract on a GC with a FID and/or an ECD.
7.3.1.2 All samples and standard solutions must be allowed to
warm to ambient temperature before analysis.
7.3.1.3 Assemble the purge-and-trap device. The operating
conditions for the GC are given in Section 7.0 of the specific
determinative method to be employed.
7.3.1.4 Daily GC calibration criteria must be met (Method
8000, Section 7.4) before analyzing samples.
7.3.1.5 Adjust the purge gas flow rate (nitrogen or helium) to
that shown in Table 1, on the purge-and-trap device. Optimize the
flow rate to provide the best response for chloromethane and
bromoform, if these compounds are analytes. Excessive flow rate
reduces chloromethane response, whereas insufficient flow reduces
bromoform response.
7.3.1.6 Remove the plunger from a 5-mL syringe and attach a
closed syringe valve. Open the sample or standard bottle, which has
been allowed to come to ambient temperature, and carefully pour the
sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, if
there is only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20-mL syringe would allow the use of only one
syringe. If a second analysis is needed from a syringe, it must be
analyzed within 24 hr. Care must be taken to prevent air from
leaking into the syringe.
7.3.1.7 The following procedure is appropriate for diluting
purgeable samples. All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.
5030 - 12
Revision 0
Date September 1986
-------
7.3.1.7.1 Dilutions may be made 1n volumetric flasks (10-
mL to 100-mL). Select the volumetric flask that will allow for
the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
7.3.1.7.2 Calculate the approximate volume of reagent
water to be added to the volumetric flask selected and add
slightly less than this quantity of reagent water to the flask.
7.3.1.7.3 Inject the proper aliquot of samples from the
syringe prepared in Paragraph 7.3.1.5 into the flask. Aliquots
of less than 1-mL are not recommended. Dilute the sample to
the mark with reagent water. Cap the flask, invert, and shake
three times. Repeat the above procedure for additional
dilutions.
7.3.1.7.4 Fill a 5-mL syringe with the diluted sample as
in Paragraph 7.3.1.5.
7.3.1.8 Add 10.0 uL of surrogate spiking solution (found in
each determinative method, Section 5.0) and, if applicable, 10 uL of
internal standard spiking solution through the valve bore of the
syringe; then close the valve. The surrogate and internal standards
may be mixed and added as a single spiking solution. Matrix spiking
solutions, 1f indicated, should be added (10 uL) to the sample at
this time.
7.3.1.9 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.3.1.10 Close both valves and purge the sample for the time
and at the temperature specified in Table 1.
7.3.1.11 At the conclusion of the purge time, attach the trap
to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and GC data
acquisition. Concurrently, introduce the trapped materials to the
gas chromatographic column by rapidly heating the trap to 180*C
while backflushing the trap with inert gas between 20 and 60 mL/min
for the time specified in Table 1.
7.3.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5-mL flushes of reagent water (or methanol followed
by reagent water) to avoid carryover of pollutant compounds into
subsequent analyses.
7.3.1.13 After desorbing the sample, recondition the trap by
returning the purge-and-trap device to the purge mode. Wait 15 sec;
then close the syringe valve on the purging device to begin gas flow
5030 - 13
Revision 0
Date September 1986
-------
through the trap. The trap temperature should be maintained at
180*C for Methods 8010 and 8020, and 210*C for Methods 8015 and
8030. Trap temperatures up to 220'C may be employed; however, the
higher temperature will shorten the useful life of the trap. After
approximately 7 min, turn off the trap heater and open the syringe
valve to stop the gas flow through the trap. When cool, the trap is
ready for the next sample.
7.3.1.14 If the initial analysis of a sample or a dilution of
the sample has a concentration of analytes that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. When a sample is analyzed that has saturated response
from a compound, this analysis must be followed by a blank reagent
water analysis. If the blank analysis 1s not free of Interferences,
the system must be decontaminated. Sample analysis may not resume
until a blank can be analyzed that is free of interferences.
7.3.1.15 All dilutions should keep the response of the major
constituents (previously saturated peaks) in the upper half of the
linear range of the curve. Proceed to Method 8000 and the specific
determinative method for details on calculating analyte response.
7.3.2 Water-misdble liquids:
7.3.2.1 Water-miscible liquids are analyzed as water samples
after first diluting them at least 50-fold with reagent water.
7.3.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample to a 100-mL volumetric flask and
diluting to volume with reagent water. Transfer immediately to a
5-mL gas-tight syringe.
7.3.2.3 Alternatively, prepare dilutions directly in a 5-mL
syringe filled with reagent water by adding at least 20 uL, but not
more than 100-uL of liquid sample. The sample is ready for addition
of surrogate and, if applicable, internal and matrix spiking
standards.
7.3.3 Sediment/soil and waste samples: It is highly recommended
that all samples of this type be screened prior to the purge-and-trap GC
analysis. These samples may contain percent quantities of purgeable
organics that will contaminate the purge-and-trap system, and require
extensive cleanup and instrument downtime. See Paragraph 7.3.1.1 for
recommended screening techniques. Use the screening data to determine
whether to use the low-level method (0.005-1 mg/kg) or the high-level
method (>1 mg/kg).
7.3.3.1 Low-level method: This is designed for samples
containing individualpurgeable compounds of <1 mg/kg. It is
limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-level method is based on
5030 - 14
Revision 0
Date September 1986
-------
purging a heated sediment/soil sample mixed with reagent water
containing the surrogate and, 1f applicable, Internal and matrix
spiking standards. Analyze all reagent blanks and standards under
the same conditions as the samples.
7.3.3.1.1 Use a 5-g sample If the expected concentration
1s <0.1 mg/kg or a 1-g sample for expected concentrations
between 0.1 and 1 mg/kg.
7.3.3.1.2 The GC system should be set up as in Section
7.0 of the specific determinative method. This should be done
prior to the preparation of the sample to avoid loss of
volatiles from standards and samples. A heated purge
calibration curve must be prepared and used for the
quantisation of all samples analyzed with the low-level method.
Follow the initial and dally calibration instructions, except
for the addition of a 40*C purge temperature for Methods 8010
and 8020.
7.3.3.1.3 Remove the plunger from a 5-mL Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger and
compress the water to vent trapped air. Adjust the volume to
5.0 ml. Add 10 uL each of surrogate spiking solution and
Internal standard solution to the syringe through the valve.
(Surrogate spiking solution and internal standard solution may
be mixed together.) Matrix spiking solutions, if Indicated,
should be added (10 uL) to the sample at this time.
7.3.3.1.4 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard
any supernatant liquids. Mix the contents of the sample
container with a narrow metal spatula. Weigh the amount
determined 1n Paragraph 7.3.3.1.1 into a tared purge device.
Note and record the actual weight to the nearest 0.1 g.
7.3.3.1.5 In certain cases, sample results are desired
based on a dry-weight basis. When such data is desired, a
portion of sample for moisture determination should be weighed
out at the same time as the portion used for analytical
determination. Immediately after weighing the sample for
extraction, weigh 5-10 g of the sample into a tared crucible.
Determine the percent moisture by drying overnight at 105*C.
Allow to cool 1n a desiccator before weighing:
q of sa1-drY samP1e x 100 = % moisture
5030 - 15
Revision 0
Date September 1986
-------
7.3.3.1.6 Add the spiked reagent water to the purge
device, which contains the weighed amount of sample, and
connect the device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device, steps
7.3.3.1.4 and 7.3.3.1.6 must be performed rapidly and
without interruption to avoid loss of volatile organics.
These steps must be performed in a laboratory free of
solvent fumes.
7.3.3.1.7 Heat the sample to 40'C + 1°C (Methods 8010 and
8020) or to 85°C + 2*C (Methods 8015 and 8030) and purge the
sample for the time shown in Table 1.
7.3.3.1.8 Proceed with the , analysis as outlined in
Paragraphs 7.3.1.11-7.3.1.15. Use 5 ml of the same reagent
water as in the reagent blank. If saturated peaks occurred or
would occur if a 1-g sample were analyzed, the high-level
method must be followed.
7.3.3.2 High-level method; The method is based on extracting
the sediment/soil with methanol. A waste sample is either extracted
or diluted, depending on its solubility in methanol. An aliquot of
the extract is added to reagent water containing surrogate and, if
applicable, internal and matrix spiking standards. This is purged
at the temperatures indicated in Table 1. All samples with an
expected concentration of >1.0 mg/kg should be analyzed by this
method.
7.3.3.2.1 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard
any supernatant liquids. Mix the contents of the sample
container with a narrow metal spatula. For sediment/soil and
waste that are insoluble in methanol, weigh 4 g (wet weight) of
sample into a tared 20-mL vial. Use a top-loading balance.
Note and record the actual weight to 0.1 gram and determine the
percent moisture of the sample using the procedure in Paragraph
7.3.3.1.5. For waste that is soluble in methanol, weigh 1 g
(wet weight) into a tared scintillation vial or culture tube or
a 10-mL volumetric flask. (If a vial or tube is used, it must
be calibrated prior to use. Pi pet 10.0 ml of methanol into the
vial and mark the bottom of the meniscus. Discard this
solvent.)
7.3.3.2.2 Quickly add 9.0 ml of methanol; then add 1.0 ml
of the surrogate spiking solution to the vial. Cap and shake
for 2 min.
NOTE: Steps 7.3.3.2.1 and 7.3.3.2.2 must be performed
rapidly and without interruption to avoid loss of volatile
organics. These steps must be performed in a laboratory
free from solvent fumes.
5030 - 16
Revision 0
Date September 1986
-------
7.3.3.2.3 Pipet approximately 1 ml of the extract to a GC
vial for storage, using a disposable pipet. The remainder may
be disposed of. Transfer approximately 1 ml of reagent
methanol to a separate GC vial for use as the method blank for
each set of samples. These extracts may be stored at 4*C in
the dark, prior to analysis.
7.3.3.2.4 The GC system should be set up as in Section
7.0 of the specific determinative method. This should be done
prior to the addition of the methanol extract to reagent water.
7.3.3.2.5 Table 2 can be used to determine the volume of
methanol extract to add to the 5 ml of reagent water for
analysis. If a screening procedure was followed, use the
estimated concentration to determine the appropriate volume.
Otherwise, estimate the concentration range of the sample from
the low-level analysis to determine the appropriate volume. If
the sample was submitted as a high-level sample, start with 100
uL. All dilutions must keep the response of the major
constituents (previously saturated peaks) in the upper half of
the linear range of the curve.
7.3.3.2.6 Remove the plunger from a 5.0-mL Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger and
compress the water to vent trapped air. Adjust the volume to
4.9 ml. Pull the plunger back to 5.0 ml to allow volume for
the addition of the sample extract and of standards. Add
10 uL of internal standard solution. Also add the volume of
methanol extract determined in Paragraph 7.3.3.2.5 and a volume
of methanol solvent to total 100 uL (excluding methanol in
standards).
7.3.3.2.7 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valve and
inject the water/methanol sample into the purging chamber.
7.3.3.2.8 Proceed with the analysis as outlined in the
specific determinative method. Analyze all reagent blanks on the
same instrument as that used for the samples. The standards and
blanks should also contain 100 uL of methanol to simulate the
sample conditions.
7.3.3.2.9 For a matrix spike in the high-level
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution and 1.0 ml of matrix spike solution.
Add a 100-uL aliquot of this extract to 5 mL of water for purging
(as per Paragraph 7.3.3.2.6).
5030 - 17
Revision
Date September 1986
-------
TABLE 2. QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF HIGH-LEVEL
SOILS/SEDIMENTS
Approximate
Concentration Range
Volume of
Methanol Extract3
500-10,000 ug/kg
1,000-20,000 ug/kg
5,000-100,000 ug/kg
25,000-500,000 ug/kg
100 uL
50 uL
10 uL
100 uL of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this
table. .
aThe volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5-mL syringe whatever volume of methanol is
necessary to maintain a volume of 100 uL added to the syringe.
^Dilute an aliquot of the methanol extract and then take 100 uL for
analysis. •
5030 - 18
Revision 0
Date September 1986
-------
7.4 Sample analysis;
7.4.1 The samples prepared by this method may be analyzed by
Methods 8010, 8015, 8020, 8030, and 8240. Refer to these methods for
appropriate analysis conditions.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3500 for sample preparation procedures.
8.2 Before processing any samples, the analyst should demonstrate
through the analysis of a reagent water method blank that all glassware and
reagents are interference free. Each time a set of samples is extracted, or
there is a change in reagents, a method blank should be processed as a safe-
guard against chronic laboratory contamination. The blank samples should be
carried through all stages of the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of the
sampling technique. Laboratory replicates should be analyzed to validate the
precision of the analysis. Fortified samples should be carried through all
stages of sample preparation and measurement; they should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified
samples do not indicate sufficient sensitivity to detect <1 ug/g of the
analytes in the sample, then the sensitivity of the instrument should be
increased, or the sample should be subjected to additional cleanup.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
5030 - 19
Revision
Date September 1986
-------
METHOD 5030
PUHGE-ANO-TRAP METHOD
C •— )
7. 1
o
Calibrate
GC system
and prepare
standards
7.1.2
7.1.4
Carry out
purge-end-trap
analysis
Assemble
purge-and-trap
device and
condition trap
7.1.3
7.1.5
Calculate
response or
calibration factor*
for each analyte
(Method 8000,
Section 7.4)
Connect to gas
chromatograph
7.1.3
7. 1.6
Calculate
average RF for
each compound
Prepare final
solutions
O
0
5030 - 20
Revision 0
Date September 1986
-------
METHOD SO30
PURG6-ANO-TRAP METHOD
(Continued)
7.3.31
Prepare ••mples
•nd
-------
METHOD 5040
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES
FROM VOLATILE ORGANIC SAMPLING TRAIN
1.0 SCOPE AND APPLICATION
1.1 Method 5040 was formerly Method 3720 in the Second Edition of this
manual.
1.2 This method covers the determination of volatile principal organic
hazardous constituents (POHCs), collected on Tenax and Tenax/charcoal sorberit
cartridges using a volatile organic sampling train, . VOST (1). Much of the
description for purge-and-trap GC/MS analysis is described in Method. 8240 of
this chapter. Because the majority of gas streams sampled using VOST Will;
contain a high concentration of water, the analytical method is based on the
quantitative thermal desorption of volatile POHCs from the Tenax and
Tenax/charcoal traps and analysis by purge-and-trap GC/MS. For the purposes
of definition, volatile POHCs are those POHCs with boiling points less than
100'C. ~. -;
1.3 This method is applicable to the analysis of Tenax and Tenax/
charcoal cartridges used to collect volatile POHCs from wet stack'gas
effluents from hazardous waste incinerators.
1.4 The sensitivity of the analytical method for a particular volatile
POHC depends on the level of interferences and the presence of detectable
levels of volatile POHCs in blanks. The desired target detection limit of the
analytical method is 0.1 ng/L (20 ng on a single pair of traps),for a
particular volatile POHC desorbed from either a single pair of Tenax and
Tenax/charcoal cartridges or by thermal desorption of up to six pairs of traps
onto a single pair of Tenax and Tenax/charcoal traps. The resulting single
pair of traps is then thermally desorbed and analyzed by purge-and-trap GO/MS*
1.5 This method is recommended for use only by experienced,1 mass
spectroscopists or under the close supervision of such qualified persons. : ?
2.0 SUMMARY OF METHOD
2.1 A schematic diagram of the analytical system is shown in Figure 1.
The contents of the sorbent cartridges are spiked with an internal standard
and thermally desorbed for 10 min at 180'C with organic-free nitrogen or
helium gas (at a flow rate of 40 mL/min), bubbled through 5 mL of organic-free
water, and trapped on an analytical adsorbent trap. After the 10-min
desorption, the analytical adsorbent trap is rapidly heated to 180'C, with the
carrier gas flow reversed so that the effluent flow from the analytical trap
is directed into the GC/MS. The volatile POHCs are separated by temperature-
programmed gas chromatography and detected by low-resolution mass
spectrometry. The concentrations of volatile POHCs are calculated using the
internal standard technique.
5040 - 1
Revision 0
Date September 1986
-------
en
0
j^
o
i
ro
O 73
O> ft)
rt <
-••
CO
.4.
GO O
n> 3
O
r+
(b I
Flow
GC/
CH:
o-j;
A
N2 A ••:
, . ., , ,*,., ,.._.., k!/ M "
® p -.^
it. ji prit Ssj
*"TL"<- \ 1
^P Thermal t
/^"\ D^nrplion , ;_ )
Chamber
i
Heated
Line
( Flow During J
Desorption
to
MS Flow During
1 Adsorption 1
j-1 "A*-!-*-!"-! • i
i i><|>ci>q>q H
r» T • T • T» i •
Analytical Trap
with Heating Coil
_ (0.3cm diameter
by 25cm long)
1" H20
Purge (T) 3
* Column ^-^
c / » \ _
\y T
© s
0c
He or
3-0
Vent
3%OV-I (1cm)
Tenax (7.7cm)
Silica Gel (7.7cm)
Charcoal (7.7cm)
Figure 1. Schematic diagram of trap desorp lion/analysis system.
00
cr>
-------
3.0 INTERFERENCES
3.1 Refer to Methods 3500 and 8240.
4.0 APPARATUS AND MATERIALS
4.1 Thermal desorption unit;
4.1.1 The thermal desorption unit (for Inside/Inside VOST car-
tridges, use Supelco "clamshell" heater; for Inside/Outside VOST car-
tridges, user fabricated unit is required) should be capable of thermally
desorbing the sorbent resin tubes. It should also be capable of heating
the tubes to 180 + 10*C with flow of organic-free nitrogen or helium
through the tubes.
4.2 Purge-and-trap unit;
4.2.1 The purge-and-trap unit consists of three separate pieces of
equipment: the sample purger, trap, and the desorber. It should be
capable of meeting all requirements of Method 5030 for analysis of
purgeable organic compounds from water.
4.3 GC/MS system; As described in Method 8240.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the parameters of
interest.
5.1.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 450 g of activated carbon (Calgon
Corporation, Filtrasorb-300, or equivalent).
5.1.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
5.1.3 Reagent water may also be prepared by boiling distilled
water for 15 min. Subsequently, while maintaining the temperature
at 90*C, bubble a contaminant-free inert gas through the water for 1 hr.
Allow the water to cool to room temperature while continuing to bubble
the inert gas through the water. This water should be transferred
directly to the purge-and-trap apparatus for use.
5.1.4 Other methods that can be shown to produce organic-free water
can be used.
5040 - 3
Revision 0
Date September 1986
-------
5.2 Analytical trap reagents:
5.2.1 2,6-Diphenylene oxide polymer: Tenax (60/80 mesh), chromato-
graphic grade or equivalent.
5.2.2 Methyl silicone packing: 3% OV-1 on Chromosorb W (60/80
mesh) or equivalent.
5.2.3 Silica gel: Davison Chemical (35/00 mesh), Grade 15, or
equivalent.
5.2.4 Charcoal: Petroleum-based (SKC Lot 104 or equivalent).
5.3 Stock standard solution:
5.3.1 Stock standard solutions will be prepared from pure standard
materials or purchased as certified solutions. The stock standards
should be prepared in methanol using assayed liquids or gases, as
appropriate. Because of the toxicity of some of the organohalides,
primary dilutions of these materials should be prepared in a hood. A
NIOSH/MESA-approved toxic gas respirator should be used when the analyst
handles high concentrations of such materials.
5.3.2 Fresh stock standards should be prepared weekly for volatile
POHCs with boiling points of <35*C. All other standards must be replaced
monthly, or sooner if comparison with check standards indicates a
problem.
5.4 Secondary dilution standards;
5.4.1 Using stock standard solutions, prepare in methanol secondary
dilution standards that contain the compounds of interest, either singly
or mixed together. The secondary dilution standards should be prepared
at concentrations such that the desorbed calibration standards will
bracket the working range of the analytical system.
5.5 4-Bromofluorobenzene (BFB) standard;
5.5.1 Prepare a 25 ng/uL solution of BFB in methanol.
5.6 Deuterated benzene;
5.6.1 Prepare a 25 ng/uL solution of benzene-ds in methanol.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to Method 0030, Chapter Ten.
6.2 Sample trains obtained from the VOST should be analyzed within
2-6 weeks of sample collection.
5040 - 4
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Assembly of PTD device;
7.1.1 Assemble a purge-and-trap desorptlon device (PTD) that meets
all the requirements of Method 5030 (refer to Figure 1).
7.1.2 Connect the thermal desorption device to the PTD device.
Calibrate the PTD-GC/MS system using the internal standard technique.
7.2 Internal standard calibration procedure;
7.2.1 This approach requires the use of deuterated benzene as the
internal standard for these analyses. Other internal standards may be
proposed for use in certain situations. The important criteria for
choosing a particular compound as an internal standard are that 1t be
similar in analytical behavior to the compounds of Interest and that 1t
can be demonstrated that the measurement of the Internal standard be
unaffected by method or matrix interferences. Other Internal standards
that have been used are djo-ethylbenzene and d4-l,2-d1chloroethane. One
adds 50 ng of BFB to all sorbent cartridges (in addition to one or more
Internal standards) to provide continuous monitoring of the GC/MS
performance relative to BFB.
7.2.2 Prepare calibration standards at a minimum of three
concentration levels for each analyte of interest.
7.2.3 The calibration standards are prepared by spiking a blank
Tenax or Tenax/charcoal trap with a methanollc solution of the
calibration standards (including 50 ng of the internal standard, such as
deuterated benzene), using the flash evaporation technique. The flash
evaporation technique requires filling the needle of a 5.0-uL syringe
with clean methanol and drawing air into the syringe to the 1.0-uL mark.
This is followed by drawing a methanol1c solution of the calibration
standards (containing 25 ug/uL of the internal standard) to the 2.0-uL
mark. The glass traps should be attached to the injection port of a gas
chromatograph while maintaining the injector temperature at 160*C. The
carrier gas flow through the traps should be maintained at about
50 mL/min.
7.2.4 After directing the gas flow through the trap, the contents
of the syringe should be slowly expelled through the gas chromatograph
injection port over about 15 sec. After 25 sec have elapsed, the gas
flow through the trap should be shut off, the syringe removed, and the
trap analyzed by the PTD-GC/MS procedure outlined 1n Method 8240. The
total flow of gas through the traps during addition of calibration
standards to blank cartridges, or internal standards to sample
cartridges, should be 25 ml or less.
7.2.5 Analyze each calibration standard for both Tenax and Tenax/
charcoal cartridges according to Section 7.3. Tabulate the area response
5040 - 5
Revision 0
Date September 1986
-------
of the characteristic ions of each analyte against the concentration of
the internal standard and calculate response factor (RF) for each
compound, using Equation 1.
RF = AsCis/A1sCs
(1)
where:
As = Area of the characteristic ion for the analyte to
be measured.
Ais = Area of the characteristic ion for the internal
standard.
Cjs = Amount (ng) of the internal standard.
Cs = Amount (ng) of the volatile POHC in calibration
standard.
If the RF value over the working range 1s a constant «10% RSD), the RF
can be assumed to be invariant, and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ajs versus RF.
7.2.6 The working calibration curve or RF must be verified on each
working day by tfie measurement of one or more of the calibration
standards. If the response varies by more than +25% for any analyte, a
new calibration standard must be prepared and analyzed, for that analyte.
7.3 The schematic of the PTD-GC/MS system is shown in Figure 1. The
sample cartridge is placed in the thermal desorption apparatus (for Inside/
Inside VOST cartridges, use Supelco "clamshell" heater; for Inside/Outside
VOST cartridges, user fabricated unit is required) and desorbed 1n the purge-
and-trap system by heating to 180'C for 10 min at a flow rate of 40 mL/mln.
The desorbed components pass into the bottom of the water column, are purged
from the water, and collected on the analytical adsorbent trap. After the 10-
min desorption period, the compounds are desorbed from the analytical adsor-
bent trap into the GC/MS system according to the procedures described 1n
Method 8240.
7.4 Qualitative identification;
7.4.1 The procedure for qualitative identification of volatile
POHCs using this protocol is described in Method 8240.
7.5 Calculations;
7.5.1 When an analyte has been qualitatively Identified,
quantification should be based on the integrated abundance from the EICP
of the primary characteristic ion chosen for that analyte. If the sample
produces an interference for the primary characteristic 1on, a secondary
characteristic ion should be used.
5040 - 6
Revision 0
Date September 1986
-------
7.5.1.1 Using the Internal standard calibration procedure, the
amount of analyte 1n the sample cartridge Is calculated using the
response factor (RF) determined In Paragraph 7.2.5 and Equation 2.
Amount of POHC = ASC^S/A^SRF (2)
where:
As = Area of the characteristic 1on for the analyte to be
measured.
AJS = Area for the characteristic ion of the internal
standard.
C^s = Amount (ng) of Internal standard.
7.5.1.2 The choice of methods for evaluating data collected
using VOST for Incinerator trial burns is a regulatory decision.
The procedures used extensively by one user are outlined below.
7.5.1.3 The total amount of the POHCs of Interest collected on
a pair of traps should be summed. These values should then be blank
corrected. Guidelines for blank correction of sample cartridges are
outlined below.
7.5.1.3.1 After all blanks (field and trip) are analyzed,
a paired t-test should be used to determine whether trip blanks
are significantly different from field blanks. If no
difference 1s found, then the mean and standard deviation of
the combined field and trip blanks for each POHC of Interest is
calculated.
7.5.1.3.2 If, when using the paired t-test, the field and
trip blanks are determined to be different, then the field
blank (or the mean of multiple field blanks) associated with a
particular run should be used as the blank value for that
particular run.
7.5.1.4 Next, for each sample/POHC combination, a
determination must be made as to whether a particular sample 1s
significantly different from the associated blank. If the mean of
the trip and field blanks is used, then a sample is different from
the blank if:
measured mean
(sample value) - (blank value) > (3 x blank standard deviation)
(If an individual field blank is used as the blank value, the above
criteria do not apply.) If the sample Is determined to be different
from the blank according to the above criteria, then the emission
value of a particular POHC 1s blank-corrected by subtracting the
mean blank value from the measured sample value.
5040 - 7
Revision 0
Date September 1986
-------
7.5.1.5 If, according to the above procedures, the sample
cannot be distinguished from the blank (I.e., for a given POHC there
1s a high sample value and high blank value or there 1s a low sample
value and low blank value), the measured sample value 1s not blank-
corrected. In this case, the measured sample value 1s used to
calculate a maximum emission value (and therefore a minimum ORE
value) for that particular run.
7.5.1.6 The observation of high concentrations of POHCs of
Interest 1n blank cartridges Indicates possible residual
contamination of the sorbent cartridges prior to shipment to and use
at the site. Data that fall 1n this category (especially data
Indicating high concentrations of POHCs in blank sorbent cartridges)
should be qualified with regard to validity, and blank data should
be reported separately. The. applicability of data of this type to
the determination of ORE is a regulatory decision. Continued
observation of high concentrations of POHCs 1n blank sorbent
cartridges Indicates that procedures for cleanup, monitoring,
shipment, and storage of sorbent cartridges by a particular user be
Investigated to eliminate this problem.
7.5.1.7 If any Internal standard recoveries fall outside the
control limits established in Section 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3500 for sample preparation procedures.
8.2 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this
program consist of an Initial demonstration of laboratory capability
and the analysis of blank Tenax and Tenax/charcoal cartridges spiked
with the analytes of Interest. The laboratory 1s required to
maintain performance records to define the quality of data that are
generated. Ongoing performance checks must be compared with
established performance criteria to determine if results are within
the expected precision and accuracy limits of the method.
8.2.1 Before performing any analyses, the analyst must demonstrate
the ability to generate acceptable precision and accuracy with this
method. This ability is established as described in Paragraph 7.2.
8.2.2 The laboratory must spike all Tenax and Tenax/charcoal
cartridges with the internal standard(s) to monitor continuing laboratory
performance. This procedure 1s described 1n Paragraph 7.2.
8.3 To establish the ability to generate acceptable accuracy and
precision, the analyst must spike blank Tenax and Tenax/charcoal cartridges
with the analytes of interest at two concentrations in the working range.
5040 - 8
Revision 0
Date September 1986
-------
8.3.1 The average response factor (R) and the standard deviation
(S) for each must be calculated.
8.3.2 The average recovery and standard deviation must fall within
the expected range for determination of volatile POHCs using this method.
The expected range for recovery of volatile POHCs using this method 1s
50-150%.
8.4 The analyst must calculate method, performance criteria for the
1nternal standard(s).
8.4.1 Calculate upper and lower control limits for method
performances using the average area response (A) and standard
devlatlon(s) for internal standard:
Upper Control Limit (UCL) = A + 3S.
Lower Control Limit (LCL) = A - 3S.
The UCL and LCL can be used to construct control charts that are useful
in observing trends in performance. The control limits must be replaced
by method performance criteria as they become available from the
U.S. EPA.
8.5 The laboratory is required to spike all sample cartridges (Tenax and
Tenax/charcoal) with internal standard.
8.6 Each day, the analyst must demonstrate through analysis of blank
Tenax and Tenax/charcoal cartridges and reagent water that interferences from
the analytical system are under control.
8.7 The daily GC/MS performance tests required .for this method are
described in Method 8240.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHC's Using VOST.
EPA/600/8-84-007, March 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014a, January 1986.
5040 - 9
Revision
Date September 1986
-------
METHOD S040
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES
FROM VOLATILE ORGANIC SAMPLING TRAIN
1
7.1.1
Aaeemble
purge and trap
deaorptlon
device
Expel
contents of
syringe
through GC
Injection port
7.1.2
Connect
thermal
desorptlon
device;
calibrate
ayatem
7.8.1
7.2.4
7.3
I Piece
J sample
cartridge
In desorptlon
apparatus:
desorb In P-T
Analyze
trap by P-T-D
GC/HS procedure
(Method 8240)
Select Internal
atandard
7.2.5
7.3
Oeaorb Into
GC/HS system
(Method 6240)
Analyze
each
calibration
atanderd for
both cartridges
(aee 7.3]
7.2.31
» Prepare
calibration
atandarde using
flaah avaporat.
technique
7.2.5
7.4.1
Qualitatively
Identify
volatile POHCs
(Method 8240)
Tabulate
area reaponae
and calculate
raaponae factor
7.2.41
Direct gmm flow
through trapa
o
Verify reaponae
factor each day
7.5.1
Use primary
characteristic
Ion for
quantification
7.5.1.1
Calculate
amount of
analyte In
aample
5040 - 10
Revision 0
Date September 1986
-------
METHOD 5040
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES
FROM VOLATILE ORGANIC SAMPLING TRAIN
(Continued)
7.5.i.elOuallfy
data
Is concentr.
Sum
•mount of POHCs
of interest
over Z traps
with regard
to validity:
report blank
data separately
Oo Internal
stand, recoveries
fall outside
control
limit
accuracy of the
data for all
•nalytes from
that cartridge
Blank correct
using paired
t-test
7.5.1.3 Find
mean
trip
different from
field blanks?
and standard
deviation of
combined field
and trip blanks
Use field blank
as blank value
Determine
if sample is
different
from blank
Is cample
different from
blank?
Blank correct
•mission value
of a
particular POHC
Use measured
sample value to
calculate a
•mlaslon value
5040 - 11
Revision o
Date September 1986
-------
4.2 SAMPLE PREPARATION METHODS
4.2.2 CLEANUP
FOUR - 8
Revision
Date September 1986
-------
METHOD 3600
CLEANUP
1.0 SCOPE AND APPLICATION
1.1 General;
1.1.1 Injection of extracts into a gas or liquid chromatograph can
cause extraneous peaks, deterioration of peak resolution and column
efficiency, and loss of detector sensitivity and can greatly shorten the
lifetime of expensive columns. The following techniques have been
applied to extract purification: partitioning between immiscible
solvents; adsorption chromatography; gel permeation chromatography;
chemical destruction of interfering substances with acid, alkali, or
oxidizing agents; and distillation. These techniques may be used
individually or in various combinations, depending on the extent and
nature of the co-extractives.
1.1.2 It is an unusual situation, e.g., with some water samples,
when extracts can be directly determined without further treatment. Soil
and waste extracts often require a combination of cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC), to eliminate the
high boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
1.2 Specific:
1.2.1 Adsorption column chromatography: Alumina (Methods 3610 and
3611), Florisil (Method 3620), and silica gel (Method 3630) are useful
.for separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity.
1.2.2 Acid-base partitioning: Useful for separating acidic or
basic organics from neutral organics. It has been applied to analytes
such as the chlorophenoxy herbicides and phenols.
1.2.3 Gel permeation chromatography (GPC): The most universal
cleanup technique for a broad range of semivolatile organics and
pesticides. It is capable of separating high molecular-weight material
from the sample analytes. It has been used successfully for all the
semivolatile base, neutral, and acid compounds associated with the EPA
Priority Pollutant and the Superfund Hazardous Substance Lists. GPC is
usually not applicable for eliminating extraneous peaks on a chromatogram
which interfere with the analytes of interest.
1.2.4 Sulfur cleanup: Useful in eliminating sulfur from sample
extracts, which may cause chromatographic interference with analytes of
interest.
3600 - 1
Revision 0
Date September 1986
-------
1.2.5 Table 1 Indicates the recommended cleanup techniques for the
Indicated groups of compounds. This information can also be used as
guidance for compounds that are not listed. Compounds that are
chemically similar to these groups of compounds should follow a similar
elution pattern.
2.0 SUMMARY OF METHOD
2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES
3.1 Analytical interferences may be caused by contaminants 1n solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free of Interferences, under
the conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
-/
4.1 Refer to the specific cleanup method for apparatus and materials
needed.
5.0 REAGENTS
5.1 Refer to the specific cleanup method for the reagents needed.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Prior to using the cleanup procedures, samples should undergo
solvent extraction. Chapter Two, Section 2.3.3, may be used as a guide for
choosing the appropriate extraction procedure based on the physical compo-
sition of the waste and on the analytes of interest in the matrix (see also
Method 3500 for a general description of the extraction technique). For some
organic liquids, extraction prior to cleanup may not be necessary
7.2 In most cases, the extracted sample is then analyzed by one of the
determinative methods available in Section 4.3 of this chapter. If the
analytes of interest are not able to be determined due to interferences,
cleanup is performed.
3600 - 2
Revision 0
Date September 1986
-------
TABLE 1. RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative3
Method
Cleanup
Method Option
Phenols 8040
Phthalate esters 8060
Nitrosamines 8070
Organochlorlne pesticides & PCBs 8080
Nitroaromatlcs and cyclic ketones 8090
Polynuclear aromatic hydrocarbons 8100
Chlorinated hydrocarbons 8120
Organophosphorous pesticides 8140
Chlorinated herbicides 8150
Priority pollutant semivolatiles 8250, 8270
Petroleum waste 8250, 8270
3630b, 3640, 3650, 8040C
3610, ,3620, 3640
3610, 3620, 3640
3620, .3640, 3660
3620, 3640
3611, 3630, 3640
3620, 3640
3620, 3640
8150d
3640, 3650, 3660
3611, 3650
a The GC/MS Methods, 8250 and 8270, are also appropriate,determinative methods
for all analyte groups, unless lower detection limits are required.
b Cleanup applicable to derivatized phenols.
c Method 8040 includes a derivatization technique followed by GC/ECD analysis,
if interferences are encountered using GC/FID.
d Method 8150 Incorporates an acid-base cleanup step as an Integral part of
the method.
3600 - 3
Revision 0
Date September 1986
-------
7.3 Many of the determinative methods specify cleanup methods that
should be used when determining particular analytes; e.g.. Method 8060 (gas
chromatography of phthalate esters) recommends using either Method 3610
(Alumina column cleanup) or Method 3620 (Florisil column cleanup) if Inter-
ferences prevent analysis. However, the experience of the analyst may prove
invaluable in determining which cleanup methods are needed. As indicated 1n
Section 1.0 of this method, many matrices may require a combination of cleanup
procedures in order to ensure proper analytical determinations.
7.4 Guidance for cleanup is specified in each of the methods that
follow. The amount of extract cleanup required prior to the final deter-
mination depends on the selectivity of both the extraction procedure and the
determinative method and the required detection limit.
7.5 Following cleanup, the sample 1s concentrated to whatever volume 1s
required 1n the determinative method. Analysis follows as specified 1n the
determinative procedure (Section 4.3 of this chapter).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered by the cleanup technique before the cleanup 1s
applied to actual samples.
8.2 For sample extracts that are cleaned up, the associated quality
control samples (e.g., spikes, blanks, and duplicates) must also be processed
through the same cleanup procedure.
8.3 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup also be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
Interest and to verify the absence of interferences from reagents.
9.0 METHOD PERFORMANCE
9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES
10.1 Refer to the specific cleanup method.
3600 - 4
Revision 0
Date September 1986
-------
METHOD 36OO
CLEANUP
( — )
7. 1
Oo solvent
extraction
7.Z
Analyze
analyte by
determinative
method from
Sec. 4.3
7.3 Use
» cleanup
method
specified for
the determin-
ative method
Are analytes
undeterminable
due to Inter-
ferences?
Concentrate
•ample to
required volume
3600 - 5
Revision 0
Date September 1986
-------
METHOD 3610
ALUMINA COLUMN CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Scope; Alumina 1s a highly porous and granular form of aluminum
oxide. It is available in three pH ranges (basic, neutral, and acidic) for
use in column chromatography. It 1s used to separate analytes from
interfering compounds of a different chemical polarity.
1.2 General Applications (Gordon and Ford):
1.2.1 Basic (B) pH (9-10): USES: Basic and neutral compounds
stable to alkali, alcohols, hydrocarbons, steroids, alkaloids, natural
pigments. DISADVANTAGES: Can cause polymerization, condensation, and
dehydration reactions; cannot use acetone or ethyl acetate as eluants.
1.2.2 Neutral (N): USES: Aldehydes, ketones, quinones, esters,
lactones, glycoside. DISADVANTAGES: Considerably less active than the
basic form.
1.2.3 Addle (A) pH (4-5): USES: Acidic pigments (natural and
synthetic), strong acids (that otherwise chemlsorb to neutral and basic
alumina).
1.2.4 Activity grades: Acidic, basic, or neutral alumina can be
prepared in various activity grades (I to V), according to the Brockmann
scale, by addition of H20 to Grade 1 (prepared by heating at 400-450*C
until no more H20 is lost). The Brockmann scale (Gordon and Ford,
p. 374) is reproduced below:
Water added (wt. %): 0 3 6 10 15
Activity grade: I II III IV V
RF (p-aminoazobenzene): 0.0 0.13 0.25 0.45 0.55
1.3 Specific applications; This method includes guidance for cleanup of
sample extracts containing phthalate esters and nitrosamines. For alumina
column cleanup of petroleum wastes, see Method 3611.
2.0 SUMMARY OF METHOD
2.1 The column 1s packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed.
Elution of the analytes is effected with a suitable solvent(s), leaving the
interfering compounds on the column. The eluate is then concentrated.
3610 - 1
Revision
Date September 1986
-------
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of Interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Chromatography column; 300-mm x 10-mm I.D., with Pyrex glass wool
at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 mL of elution solvent prior to packing the column with adsorbent.
4.2 Beakers; 500-mL.
4.3 Reagent bottle; 500-mL.
4.4 Muffle furnace.
4.5 Kuderna-Danish (K-D) apparatus;
4.5.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.5.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.5.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.5.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.6 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.7 Water bath; Heated, with . concentric ring cover, capable of
temperature control (+5'C). The bath should be used in a hood.
4.8 Vials; Glass, 2-mL capacity, with Teflon-lined screw cap.
4.9 Erlenmeyer flasks; 50- and 250-mL.
3610 - 2
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 Sodium sulfate; (ACS) Granular, anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
5.2 Eluting solvents;
5.2.1 D1ethyl ether: Pesticide quality or equivalent.
5.2.1.1 Must be free of peroxides, as indicated by EM Quant
test strips (test strips are available from EM Laboratories Inc.,
500 Executive Blvd., Elmsford, New York 10523).
5.2.1.2 Procedures recommended for removal of peroxides are
provided with the test strips. After cleanup, 20 ml ethyl alcohol
preservative must be added to each liter of ether.
5.2.2 Methanol, pentane, hexane, methylene chloride: Pesticide
quality or equivalent.
5.3 Alumi na;
5.3.1 For cleanup of phthalate extracts: Alumina-Neutral, activity
Super I, W200 series (ICN Life Sciences Group, No. 404583). To prepare
for use, place 100 g of alumina into a 500-mL beaker and heat for
approximately 16 hr at 400*C. After heating, transfer to a 500-mL
reagent bottle. Tightly seal and cool to room temperature. When cool,
add 3 mL of reagent water. Mix thoroughly by shaking or rolling for
10 min and let it stand for at least 2 hr. Keep the bottle sealed
tightly.
5.3.2 For cleanup of nitrosamlne extracts: Alumina-Basic, activity
Super I, W200 series (ICN Life Sciences Group, No. 404571, or
equivalent). To prepare for use, place 100 g of alumina into a 500-mL
reagent bottle and add 2 mL of reagent water. Mix the alumina
preparation thoroughly by shaking or rolling for 10 min and let it stand
for at least 2 hr. The preparation should be homogeneous before use.
Keep the bottle sealed tightly to ensure proper activity.
5.4 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3610 - 3
Revision 0
Date September 1986
-------
7.0 PROCEDURE
7.1 Phthalate esters;
7.1.1 Reduce the sample extract volume to 2 ml prior to cleanup.
The extract solvent must be hexane.
. 7.1.2 Place 10 g of alumina Into a chromatographlc column to settle
alumina and.add 1 cm of anhydrous sodium sulfate to the top.
7.1.3 Pre-elute the column with 40 ml of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and, just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2-mL sample extract onto the column using an additional 2 ml of
hexane to complete the transfer. Just prior to exposure of the sodium
sulfate layer to the air, add 35 ml_ of hexane and continue the elutlon of
the column. Discard this hexane eluate.
7.1.4 Next, elute the column with 140 ml of 20% ethyl ether 1n
hexane (v/v) into a 500-mL K-D flask equipped with a 10-mL concentrator
tube. Concentrate the collected fraction. No solvent exchange 1s
necessary. Adjust the volume of the cleaned up extract to whatever
volume 1s required (10.0 ml for Method 8060) and analyze. Compounds that
elute in this fraction are as follows:
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
D1-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate.
7.2 Nitrosamines;
7.2.1 Reduce the sample extract to 2 ml prior to cleanup.
7.2.2 Diphenylamine, if present in the original sample extract,
must be separated from the nitrosamines if N-nitrosodiphenylamine 1s to
be determined by this method.
7.2.3 Place 12 g of the alumina preparation into a 10-mm I.D.
chromatographic column. Tap the column to settle the alumina and add
1-2 cm of anhydrous sodium sulfate to the top.
7.2.4 Pre-elute the column with 10 ml of ethyl ether/pentane
(3:7)(v/v). Discard the eluate (about 2 ml) and just prior to exposure
of the sodium sulfate layer to the air, quantitatively transfer the 2-mL
sample extract onto the column using an additional 2 ml of pentane to
complete the transfer.
3610 - 4
Revision 0
Date September 1986
-------
7.2.5 Just prior to exposure of the sodium sulfate layer to the
air, add 70 ml of ethyl ether/pentane (3:7) (v/v). Discard the first
10 ml of eluate. Collect the remainder of the eluate in a 500-mL K-D
flask equipped with a 10-mL concentrator tube. This fraction contains
N-n1troso-di-n-propylami ne.
7.2.6 Next, elute the column with 60 ml of ethyl ether/pentane
(1:1)(v/v), collecting the eluate in a second 500-mL K-D flask equipped
with a 10-mL concentrator tube. Add 15 mL of methanol to the K-D flask.
This fraction will contain N-nitrosodimethylamine, most of the N-nitroso-
di -n-propylamirie, and any diphenylamine that is present.
7.2.7 Concentrate both fractions, but use pentane to prewet the
Snyder column. When the apparatus is cool, remove the Snyder column and
rinse the flask and its lower joint into the concentrator tube with
1-2 mL of pentane. Adjust the final volume to whatever is required in
the appropriate determinative method (Section 4.3 of this chapter).
Analyze the fractions.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of Interest are
being quantitatively recovered before applying this method to actual samples.
8.2 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. Gordon, A.J. and R.A. Ford, The Chemist's Companion; A Handbook of
Practical Data, Techniques, and References(NewYork:John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.
2. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3610 - 5
Revision 0
Date September 1986
-------
METHOD 361O
ALUMINA COLUMN CLEANUP
7.1.1
Reduce cample
extract volume
to Z mL
7.1.2
7.Z.I
Place
alumina
Into chromato-
graphic column:
aod anhydrous
sodium sulfate
7.1.3
Pre-elute
column with
hexane
7.1.3
Transfer
•ample extract
to column:
•lute column
with hexane
7.1.4
Elute
column
with ethyl
ether in hexane
Into flask
Reduce cample
extract volume
to 2 mL
7.2.3
Place alumina
preparation in
chromatographic
column: ado
anhydrous sodium
•ulfate
7.3.4
Pre-elute column with
ethyl ether/pentane:
transfer to column
•nd edd pentane
7.2.3
Elute with
ethyl ether
In pentane
Into flask
7.a.6
Elute column with
ethyl ether/pentane:
collect eluate In
second flask:
•dd methanol
7.1.4J
Concentrated
collected
fraction;
adjust volume
7.2.7
Concentrate both
fractions; prewet
Snyder column with
pentane: adjust
volume
3610 - 6
Revision p
Date September 1986
-------
METHOD 3611
ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
1.0 SCOPE AND APPLICATION
1.1 Method 3611 was formerly Method 3570 in the Second Edition of this
manual.
1.2 Scope; Alumina is a highly porous and granular form of aluminum
oxide. It is available in three pH ranges (basic, neutral, and acidic) for
use in column chromatography. It is used to separate analytes from
interfering compounds of a different chemical polarity.
1.2 General Applications (Gordon and Ford):
1.2.1 Basic (B) pH (9-10): USES: Basic and neutral compounds
stable to alkali, alcohols, hydrocarbons, steroids, alkaloids, natural
pigments. DISADVANTAGES: Can cause polymerization, condensation, and
dehydration reactions; cannot use acetone or ethyl acetate as eluants.
1.2.2 Neutral (N): USES: Aldehydes, ketones, quinones, esters,
lactones, glycoside. DISADVANTAGES: Considerably less active than the
basic form.
1.2.3 Acidic (A) pH (4-5): USES: Acidic pigments (natural and
synthetic), strong acids (that otherwise chemisorb to neutral and basic
alumina).
1.2.4 Activity grades: Acidic, basic, or neutral alumina can be
prepared in various activity grades (I to V), according to the Brockmann
scale, by addition of H20 to Grade 1 (prepared by heating at 400-450'C
until no more H20 is lost). The Brockmann scale (Gordon and Ford, p.
374) is reproduced below:
Water added (wt. %): 0 3 6 10 15
Activity grade: I II III IV V
RF (p-aminoazobenzene): 0.0 0.13 0.25 0.45 0.55
1.3 Specific applications: This method includes guidance for separation
of petroleum wastes into aliphatic, aromatic, and polar fractions.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed.
Elution of the analytes is effected with a suitable solvent(s), leaving the
interfering compounds on the column. The eluate is then concentrated.
3611 - 1
Revision
Date September 1986
-------
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of Interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
3.3 Caution must be taken to prevent overloading of the chromatographic
column. As the column loading for any of these types of wastes approaches
300 mg of extractable organics, separation recoveries will suffer. If
overloading is suspected, an aliquot of the base-neutral extract prior to
cleanup may be weighed and then evaporated to dryness. A gravimetric
determination on the aliquot will indicate the weight of extractable organics
in the sample.
4.0 APPARATUS AND MATERIALS
4.1 Chroniatography column; 300-mm x 10-mm I.D., with Pyrex glass wool
at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 ml of elution solvent prior to packing the column with adsorbent.
4.2 .Beakers; 500-mL.
4.3 Reagent bottle; 500-mL.
4.4 Muffle furnace.
4.5 Kuderna-Danish (K-D) apparatus;
4.5.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts. .
4.5.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.5.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.5.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.6 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
3611 - 2
Revision 0
Date September 1986
-------
4.7 Water bath; Heated with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.8 Erlenmeyer flasks; 50- and 250-mL.
5.0 REAGENTS
5.1 Sodium sulfate; (ACS) Granular, anhydrous (purified by heating at
400°C for 4 hr in a shallow tray).
5.2 Eluting solvents; Methanol, hexane, methylene chloride (pesticide
quality or equivalent).
i
5.3 Alumina; Neutral 80-325 MCB chromatographic grade or equivalent.
Dry alumina overnight at 130*C prior to use.
5.4 Reagent water; Reagent water is defined as water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 It is suggested that Method 3650, Acid-Base Partition Cleanup, be
performed on the sample extract prior to alumina cleanup.
7.2 Fill the glass chromatographic column to about 20 cm with hexane.
Weigh out 10.0 g of alumina and add the alumina to the column. Gently tap the
column to distribute the alumina evenly (minimize chromatographic voids).
Alternatively, a slurry of alumina in hexane may be used to pack the column.
7.3 Allow the alumina to settle and then add 1.0 g of anhydrous sodium
sulfate on top of the alumina.
7.4 Elute the column with 50 mL of hexane. Let the solvent flow through
the column until the head of the liquid in the column is just above the sodium
sulfate layer. Close the stopcock to stop solvent flow.
7.5 Transfer 1.0 mL of sample extract onto the column. Rinse out
extract vial with 1 mL hexane and add it to the column immediately. To avoid
overloading the column, it is suggested that no more than 300 mg of extrac-
table organics be placed on the column (see Paragraph 3.3).
3611 - 3
Revision
Date September 1986
-------
7.6 Just prior to exposure of the sodium sulfate to the air, elute the
column with a total of 15 ml of hexane. If the extract is in 1 ml of hexane,
and if 1 ml of hexane was used as a rinse, then 13 ml of additional hexane
should be used. Collect the effluent in a 50-mL flask and label this fraction
"base/neutral aliphatics." Adjust the flow rate to 2 mL/min.
7.7 Elute the column with 100 ml of methylene -chloride and collect the
effluent in a 250-mL flask. Label this fraction "base/neutral aromatics."
7.8 Elute the column with 100 ml of methanol and collect the effluent in
a 250-mL flask. Label this fraction "base/neutral polars."
7.9 Concentrate the extracts by the standard K-D technique to whatever
volume is required (1-10 mL) in the appropriate determinative method (Section
4.3 of this chapter). Analyze whichever fractions contain the analytes of
interest.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 The precision and accuracy of the method will depend upon the
overall performance of the sample preparation and analysis.
9.2 A rag oil sample was analyzed by a number of laboratories according
to the procedure outlined in this method. The results of these analyses for
selected components in the rag oil are presented in Table 1. Reconstructed
ion chromatograms from the GC/MS analyses are included as Figures 1 and 2.
10.0 REFERENCES
r
1. Gordon, A.J. and R.A. Ford, The Chemist's Companion; A Handbook of
Practical Data, Techniques, and References(NewYork:John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.
2. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3611 - 4
Revision 0
Date September 1986
-------
Table 1. RESULTS OF ANALYSIS FOR SELECTED COMPONENTS IN RAG OIL
Compound
Naphthalene
Fluorene
Phenanthrene
2-Methyl naphthalene
Dibenzothiophene
Methyl phenanthrene
Methyl di benzothl ophene
Mean
Cone. (ug/g)a
216
140
614
673
1084
2908
2200
Standard
Deviation
42
66
296
120
286
2014
1017
%RSDb
19
47
18
18
26
69
46
• n
Average Surrogate Recoveries
Nitrobenzene-ds 58.6 11
Terphenyl-dj4 83.0 2.6
Phenol-de 80.5 27.6
Naphthalene-dg 64.5 5.0
a Based on five determinations from three laboratories.
b Percent Relative Standard Deviation.
3611 - 5
Revision
Date September 1986
-------
»IC MTAi 0NNMI II .
•1/27/04 Ut*tM CM.li 27CM.I II
SMVLEi RAG OIL HM.9M. lilt OIL O.IOMH SMflE COCO MM. FRAC IOUG 55
RANGE I C I.2WO LABEL i N 0. 4.« QUMIi A A. 1.0 BASEi U ?«, 3
SCMIS 2ft TO 2790
OUT OF 200 10 2W*
HM.O
OJ
CT>
itC
O 73
Oi fD
r+ <
a> ->•
00
C/) O
(T> 3
O
r+
i
CT
C»
uuJ,
7452^.
T
Figure 1. Reconstructed Ion chromatogram from GC/MS analysis of the aromatic
fraction from Rag 011
-------
•1C MTAi CRMM. II
•I/IT/M IfcXlM CM.li 27011 •!
SMflCt tflC OIL FV-I.3H. « IS •.IOMH SMflC CRCO M.IPH. FPrtC IflUC SS
RMCCt C I.27M UttCLt N •. <.S OIWHi A 9. 1.9 BftSCt U 70. 3
OUT OF 2M TO
HM.e
CO
o ^j
01 n>
<-t <
n> -••
CO
co o
n> 3
o
rf
0)1
c»
777379.
Figure 2. Reconstructed 1on chromatogram from GC/MS analysis of the aliphatic
fraction from Rag 011
-------
METHOD 3611
ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
7. 1
o
Cleanup
using Method
3650
7.2
7.6
Elute column with
hexane: collect
eluent In flask;
label 'base-neutral
allphatlcs*
Fill
chromatographlc
column with
hexane: add
alumina
7.3
7.7
Elute column with
methylene chloride;
collect eluent
In flask: label
'base-neutral
aromatlcs"
Add anhydrous
sodium sulfate
on top of
alumina
7 .4
7.B
Elute column with
methanol: collect
eluent In flask;
label 'base—neutral
polars"
Elute column
with hexane
7.9
Concentrate
extracts
7.5
Put
sample
extract onto
column: rinse
extract vial
with hexane
0
3611 - 8
Revision 0
Date September 1986
-------
METHOD 3620
FLORISIL COLUMN CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Florisil, a registered tradename of the Floridin Co., is &
magnesium silicate with acidic properties. It is used for general column
chromatography as a cleanup procedure prior to sample analysis by gas
chromatography.
1.2 General applications; Cleanup of pesticide residues and other
chlorinated hydrocarbons; the separation of nitrogen compounds from
hydrocarbons; the separation of aromatic compounds from aliphatic-aromatic
mixtures; and similar applications for use with fats, oils, and waxes
(Floridin). Additionally, Florisil is considered good for separations with
steroids, esters, ketones, glycerides, alkaloids, and some carbohydrates
(Gordon and Ford).
1.3 Specific applications; This method includes guidance for cleanup of
sample extracts containing the following analyte groups: phthalate esters;
nitrosamines; organochlorine pesticides; nitroaromatics; haloethers;
chlorinated hydrocarbons; and organophosphorous pesticides.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required adsorbent, topped with a
water adsorbent, and then loaded with the sample to be analyzed. Elution is
effected with a suitable sol vent(s) leaving the interfering compounds on the
column. The eluate is then concentrated.
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Beaker; 500-mL.
4.2 Chromatographic column; 300-mm long x 10-mm I.D. or 400-mm long x
20-mm I.D., to be specified in Paragraph 7.0; with Pyrex glass wool at bottom
and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
3620 - 1
Revision 0
Date September 1986
-------
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 ml of elution solvent prior to packing the column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask: 500-mL (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs.
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Muffle furnace.
4.5 Reagent bottle; 500-mL.
4.6 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5'C). The bath should be used in a hood.
4.7 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.8 Erlenmeyer flasks; 50- and 250-mL.
5.0 REAGENTS
5.1 Florisil: Pesticide residue (PR) grade (60/100 mesh); purchase-
activated at 1250*F (677'C), stored in glass containers with ground-glass
stoppers or foil-lined screw caps.
5.1.1 Deact1vat1on of Flor1s1l: for cleanup of phthalate esters.
To prepare for use, place 100 g of Florisil into a 500-mL beaker and heat
for approximately 16 hr at 40°C. After heating, transfer to a 500-mL
reagent bottle. Tightly seal and cool to room temperature. When cool
add 3 mL of reagent water: Mix thoroughly by shaking or rolling for
10 min and let stand for at least 2 hr. Keep the bottle sealed tightly.
5.1.2 Activation of Florisil: for cleanup of nitrosamines,
organochlorine pesticides and PCBs, nitroaromatics, haloethers,
chlorinated hydrocarbons, and organophosphorous pesticides. Just before
use, activate each batch at least 16 hr at 130°C in a glass container
loosely covered with aluminum foil. Alternatively, store the Florisil in
an oven at 130*C. Cool the .Florisil before use in a desiccator.
3620 - 2
Revision 0
Date September 1986
-------
(Florlsil from different batches or sources may vary in adsorptive
capacity. To standardize the amount of Florisil which is used, the use
of 1 auric acid value is suggested. The referenced procedure determines
the adsorption from hexane solution of lauric acid (mg) per g of
Florisil. The amount of Florisil to be used for each column is
calculated by dividing 110 by this ratio and multiplying by 20 g
(Mills).)
5.2 Sodium sulfate (ACS): Granular, anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
5.3 Eluting solvents;
5.3.1 Dlethyl ether: Pesticide quality or equivalent.
5.3.1.1 Must be free of peroxides as indicated by EM Quant
test strips (available from EM Laboratories Inc., 500 Executive
Boulevard, Elmsford, NY 10523).
5.3.1.2 Procedures recommended for removal of peroxides are
provided with the test strips. After cleanup, 20 ml ethyl alcohol
preservative must be added to each liter of ether.
5.3.2 Acetone; hexane; methylene chloride; pentane; petroleum ether
(boiling range 30-60'C): Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Phthalate esters;
7.1.1 Reduce the sample extract volume to 2 mL prior to cleanup.
The extract solvent must be hexane.
7.1.2 Place 10 g of Florisil into a 10-mm I.D. chromatographic
column. Tap the column to settle the Florisil and add 1 cm of anhydrous
sodium sulfate to the top.
7.1.3 Preelute the column with 40 mL of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and, just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2-mL sample extract onto the column using an additional 2 mL of
hexane to complete the transfer. Just prior to exposure of the sodium
sulfate layer to the air, add 40 mL of hexane and continue the elution of
the column. Discard this hexane eluate.
3620 - 3
Revision 0
Date September 1986
-------
7.1.4 Next, elute the column with 100 ml of 20% ethyl ether in
hexane (v/v) into a 500-mL K-D flask equipped with a 10-mL concentrator
tube. Concentrate the collected fraction. No solvent exchange is
necessary. Adjust the volume of the cleaned-up extract to whatever
volume is required (10 ml for Method 8060) and analyze by gas
chromatography. Compounds that elute in this fraction are:
Bi s(2-ethylhexyl)phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
7.2 Nitrosamines;
7.2.1 Reduce the sample extract volume to 2 ml prior to cleanup.
7.2.2 Place 22 g of activated Fjlorisil into a 20-mm I.D.
chromatographic column. Tap the column to settle the Florisil and add
about 5 mm of anhydrous sodium sulfate to the top.
7.2.3 Preelute the column with 40 ml of ethyl ether/pentane (15:85)
(v/v). Discard the eluate and, just prior to exposure of the sodium
sulfate layer to the air, quantitatively transfer the 2-mL sample extract
onto the column using an additional 2 ml of pentane to complete the
transfer.
7.2.4 Elute the column with 90 ml of ethyl ether/pentane (15:85)
(v/v) and discard the eluate. This fraction will contain the
diphenylamine, if it is present in the extract.
7.2.5 Next, elute the column with 100 ml of acetone/ethyl ether
(5:95) (v/v) into a 500-mL K-D flask equipped with a 10-mL concentrator
tube. This fraction will contain all of the nitrosamines listed in the
scope of the method.
7.2.6 Add 15 mL of methanol to the collected fraction, concentrate
using pentane to prewet the K-D column and set the water bath at 70 to
75*C. When the apparatus is cool, remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with 1 to 2 mL of
pentane. Analyze by gas chromatography.
7.3 Organochlorine pesticides, haloethers, and organophosphorous
pesticides (seeTables1 and2forfractionationpatternsof compounds
tested):
7.3.1 Reduce the sample extract volume to 10 mL prior to cleanup.
The extract solvent must be hexane.
3620 - 4
Revision
Date September 1986
-------
7.3.2 Add a weight of Flor1s1l (nominally 20 g), predetermined by
calibration, to a 20-mm I.D. chromatographic column. Settle the Florisil
by tapping the column. Add anhydrous sodium sulfate to the top of the
Florisil to form a layer 1 to 2 cm deep. Add 60 ml of hexane to wet and
rinse the sodium sulfate and Florisil. Just prior to exposure of the
sodium sulfate to air, stop the elution of the hexane by closing the
stopcock on the chromatographic column. Discard the eluate.
7.3.3 Adjust the sample extract volume to 10 ml with hexane and
transfer it from the K-D concentrator tube to the Florisil column. Rinse
the tube twice with 1-2 ml hexane, adding each rinse to the column.
7.3.4 Place a 500-mL K-D flask and clean concentrator tube under
the chromatographic column. Drain the column into the flask until the
sodium sulfate layer is nearly exposed. Elute the column with 200 ml of
6% ethyl ether in hexane (v/v) (Fraction 1) using a drip rate of about
5 mL/min. All of the haloethers are in this fraction. Remove the K-D
flask and set aside for later concentration. Elute the column again,
using 200 mL of 15% ethyl ether in hexane (v/v) (Fraction 2), into a
second K-D flask. Perform a third elution using 200 ml of 50% ethyl
ether in hexane (v/v) (Fraction 3), and a final elution with 200 mL of
100% ethyl ether (Fraction 4), into separate K-D flasks.
7.3.5 Concentrate the eluates by standard K-D techniques using the
water bath at about 85*C (75'C for Fraction 4). Adjust the final volume
to whatever volume is required (1-10 mL). Analyze by gas chromatography.
7.4 Nitroaromatics and isophorone;
7.4.1 Reduce the sample extract volume to 2 mL prior to cleanup.
7.4.2 Prepare a slurry of 10 g
chloride/hexane (1:9) (v/v) and place
chromatographic column. Tap the column
cm of anhydrous sodium sulfate to the
about 2 mL/min.
activated Florisil in methylene
the Florisil into a 10-mrn I.D.
to settle the Florisil and add 1
top. Adjust the elution rate to
7.4.3 Just prior to exposure of the sodium sulfate layer to the
air, quantitatively transfer the sample extract onto the column using an
additional 2 mL of hexane to complete the transfer. Just prior to
exposure of the sodium sulfate layer to the air, add 30 mL of methylene
chloride/hexane (1:9) (v/v) and continue the elution of the column.
Discard the eluate.
7.4.4 Next, elute the column with 30 mL of acetone/methylene
chloride (1:9) (v/v) into a 500-mL K-D flask equipped with a 10-mL
concentrator tube. Concentrate the collected fraction, while exchanging
the solvent to hexane. To exchange the solvent, reduce the elution
solvent to about 10 mL. Add 50 mL of hexane, a fresh boiling chip, and
return the reassembled K-D apparatus to the hot water bath. Adjust the
3620 - 5
Revision 0
Date September 1986
-------
TABLE 1
DISTRIBUTION OF CHLORINATED PESTICIDES, PCBs,
AND HALOETHERS INTO FLORISIL COLUMN FRACTIONS
Parameter
Percent Recovery by Fraction3
1
Aldrin
a-BHC
/7-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Ensosulfan II
Endosulfan sulfate
Endrln
Endrin aldehyde
Haloethers
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
100
100
97
98
100
100
99
98
100
0
37
0
0
4
0
R
100
100
96
97
97
95
97
103
90
95
100
64
7 91
0 106
96
68 26
4
aEluant composition:
Fraction 1-6% ethyl ether In hexane
Fraction 2 - 15% ethyl ether in hexane
Fraction 3 - 50% ethyl ether 1n hexane
R = Recovered (no percent recovery data presented).
SOURCE: U.S. EPA and FDA data.
3620 - 6
Revision 0
Date September 1986
-------
TABLE 2
DISTRIBUTION OF ORGANOPHOSPHOROUS PESTICIDES
INTO FLORISIL COLUMN FRACTIONS
Percent Recovery by Fraction*
Parameter
Azinophos methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
ND
>80
NR
100
NR
ND
ND
NR
100
NR
ND
20
ND
NR
NR
ND
80
ND
ND
Disulfoton 25-40
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Monochrotophos
Naled
Parathion
Parathion methyl
Phorate
Ronnel
Stirophos (Tetrachlorvinphos)
Sulfotepp
TEPP
Tokuthion (Prothiofos)
Trichloronate
aEluant composition: Fraction
Fraction
Fraction
Fraction
V
ND
R
V
ND
ND
NR
0-62
>80
ND
V
ND
>80
>80
1 - 200
2 - 200
3 - 200
4 - 200
>80
V
ND
R
5
V
ND
ND
NR
100
100
ND
V
ND
mL of
mL of
mL of
mL of
V
ND
95
V
ND
ND
NR
ND
ND
6% ethyl
15% ethyl
50% ethyl
100% ethyl
ND
ND
ND
ND
ND
ether in hexane
ether in hexane
ether in hexane
ether
R = Recovered (no percent recovery information presented) (U.S. FDA).
NR = Not recovered (U.S. FDA).
V = Variable recovery (U.S. FDA).
ND = Not determined.
SOURCE: U.S. EPA and FDA data.
3620 - 7
Revision 0
Date September 1986
-------
final volume of the cleaned-up extract to whatever volume is required
(1-10 ml). Compounds that elute in this fraction are:
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Nitrobenzene.
Analyze by gas chromatography.
7.5 Chlorinated hydrocarbons;
7.5.1 Reduce the sample extract volume to 2 ml prior to cleanup.
The extract solvent must be hexane.
7.5.2 Place 12 g of Florisil into a 10-mm I.D. chromatographic
column. Tap the column to settle the Florisil and add 1 to 2 cm of
anhydrous sodium sulfate to the top.
7.5.3 Preelute the column with 100 ml of petroleum ether. Discard
the eluate and, just prior to exposure of the sodium sulfate layer to the
air, quantitatively transfer the sample extract to the column by
decantation and subsequent petroleum ether washings. Discard the eluate.
Just prior to exposure of the sodium sulfate layer to the air, begin
eluting the column with 200 ml of petroleum ether and collect the eluate
in a 500-mL K-D flask equipped with a 10-mL concentrator tube. This
fraction should contain all of the chlorinated hydrocarbons:
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
1,2,4-Trichlorobenzene.
7.5.4 Concentrate the fraction, using hexane to prewet the column.
When the apparatus is cool, remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with hexane. Adjust the
final volume of the cleaned-up extract to whatever volume is required
(1-10 ml). Analyze by gas chromatography.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
3620 - 8
Revision 0
Date September 1986
-------
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples should also be processed through this
cleanup method.
9.0 METHOD PERFORMANCE
9.1 Table 1 Indicates the distribution of chlorinated pesticides, PCB's,
and haloethers in various Florisll column fractions.
9.2 Table 2 indicates the distribution of organophosphorous pesticides
in various Florisil column fractions.
10.0 REFERENCES
1. Gordon, A.J. and R.A. Ford, The Chemist's Companion: A Handbook of
Practical Data, Techniques, and References (New York;John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.
2. Floridin of ITT System, Florisil: Properties, Application, Bibliography,
Pittsburgh, Pennsylvania, 5M381DW.
3. Mills, P.A., "Variation of Florisil Activity; Simple Method for Measuring
Absorbent Capacity and its use in Standardizing Florisil Columns," Journal of
the Association of Official Analytical Chemists, 51., 29, 1968.
4. U.S. Food and Drug Association, Pesticides Analytical Manual (Volume 1),
July 1985.
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3620 - 9
Revision 0
Date September 1986
-------
METHOD 3620
FLORISIL COLUMN CLEANUP
7.1.1
Reduce
volume of
•ample extract
to 2 mL
7.1.2
Place
Florisll
into chromato-
graphic column:
add anhydrous
•odium sulfate
7.2.1
Reduce
volume of
sample extract
to 2 mL
7.2.2
Put
Florlsll
Into chrometo-
graphic column:
add anhydrous
sodium sulfate
7.1.3| Preelute
column
Hlth hexane:
transfer sample
extract: add
hexane
7.2.3
Preelute column with
ethyl ether/pentane:
transfer ex- tract:
add pentane
7.1.4
Elute column
with ethyl
ether in hexane
7.2.4
Elute column
with ethyl
•ther/pentane
7.1.41
Concentrate
fraction:
adjust volume:
analyze
7.2.5
I Elute
column with
acetone/ethyl
ether into
flask
o
0
3620 - 10
Revision 0
Date September 1986
-------
METHOD 3630
FLORISIL COLUMN CLEANUP
(Continued)
Q
OrganochlorIne
pesticides, haloethers
and ornanoohDsnhorous
Reduce
volume of
cample extract
tO Z mL
7.3.2
Nltroaromatlcs
and Isophorone
Add Florlsll to
chromatographlc
column; add
anhydrous medium.
sulfate then hexane:
discard eluate
Chlorinated
hydrocaroons
Reduce
volume of
sample extract
to Z mL
Reduce
volume of
sample extract
to Z mL
7.3.3 Adjust
I sample
extract volume:
transfer to
column: rinse
with hexane
7.5.2
7.4.2
o
Put Florisil slurry
in chromatographlc
" column: add
anhydrous sodium
sulfate
Place Florlsll in
chromatographic
column: add
anhydrous sodium
sulfate
1 Drain
column:
elute column
4 times into
separate flasks
7.3.5
7.4.3
7.3.6
Add
methenol
to fraction:
concentrate
Transfer sample
extract onto column:
add methylene
Chloride/hexane:
discard eluate
7.5.3
Preelute column with
petroleum ether;
transfer sample
•xtract to column:
discard eluate
Concentrate
luates: adjust
volume
7.4.4
Elute column with
acetone/ methylene
chloride: exchange
solvent to hexane
7.5.41
Concentrate
fraction:
adjust final
volume
7.4.41
Concentrate
fraction:
adjust final
volume
G>
3620 - 11
Revision 0
Date September 1986
-------
METHOD 3630
SILICA GEL CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Silica gel is a regenerative adsorbent of amorphous silica with
weakly acidic properties. It is produced from sodium silicate and sulfuric
acid. Silica gel can be used for column chromatography and is for separating
the analytes from interfering compounds of a different chemical polarity.
1.2 General applications (Gordon and Ford):
1.2.1. Activated: Heated at 150-160*C for several hours.
USES: Separation of hydrocarbons.
1.2.2 Deactivated: Containing 10-20% water. USES: An adsorbent
for most functionalities with ionic or nonionic characteristics,
including alkaloids, sugar esters, glycosides, dyes, alkali metal
cations, lipids, glycerides, steroids, terpenoids and plasticizers. The
disadvantages of deactivated silica gel are that the solvents methanol
and ethanol decrease adsorbent activity.
1.3 Specific applications; This method includes guidance for cleanup of
sample extracts containing polynuclear aromatic hydrocarbons and derivatized
phenolic compounds.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed.
Elution of the analytes is effected with a suitable solvent(s) leaving the
interfering compounds on the column. The eluate is then concentrated.
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Chromatographic column: 250-mm long x 10-mm I.D.; with Pyrex glass
wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
3630 - 1
Revision 0
Date September 1986
-------
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 ml of elution solvent prior to packing the column with adsorbent.
4.2 Beakers: 500-mL.
4.3 Kuderna-Dam'sh (K-D) apparatus:
4.3.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper Is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask: 500-mL (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs.
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent). ,
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Muffle furnace.
4.5 Reagent bottle: 500-mL.
4.6 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used 1n a hood.
4.7 Boiling chips: Solvent extracted, approximately iO/40 mesh (silicon
carbide or equivalent).
4.8 Erlenmeyer flasks; 50- and 250-mL.
5.0 REAGENTS
5.1 Silica gel; 100/200 mesh desiccant (Davison Chemical grade 923 or
equivalent)"! Before use, activate for at least 16 hr at 130*C in a shallow
glass tray, loosely covered with foil.
5.2 Sodium sulfate (ACS): Granular, anhydrous (purified by heating at
400°C for 4 hr in a shallow tray).
5.'3 Eluting solvents; Cyclohexane, hexane, 2-propanol, toluene,
methylene chloride, pentane (pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING .
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3630 - 2
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Polynuclear aromatic hydrocarbons;
7.1.1 Before the silica gel cleanup technique can be utilized, the
extract solvent must be exchanged to cyclohexane. Add 1 to 10 ml of the
sample extract (in methylene chloride) and a boiling chip to a clean K-D
concentrator tube. Add 4 ml of cyclohexane and attach a two-ball micro-
Snyder. column. Prewet the column by adding 0.5 ml of methyl ene chloride
to the top. Place the micro-K-D apparatus on a boiling (100'C) water
bath so that the concentrator tube is partially immersed in the hot
water. Adjust the vertical position of the apparatus and the water
temperature as required to complete concentration in 5 to 10 min. At the
proper rate of distillation the balls of the column will actively chatter
but the chambers will not flood. When the apparent volume of the liquid
reaches 0.5 ml, remove the K-D apparatus and allow it to drain and cool
for at least 10 min. Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with a minimum amount of cyclohexane.
Adjust the extract volume to about 2 m!_.
7.1.2 Prepare a slurry of 10 g of activated silica gel in methylene
chloride and place this into a 10-mm I.D. chromatographic column. Tap
the column to settle the silica gel and elute the methylene chloride.
Add 1 to 2 cm of anhydrous sodium sulfate to the top of the silica gel.
7.1.3 Preelute the column with 40 ml of pentane. The rate for all
elutlons should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, transfer the 2 ml
cyclohexane sample extract onto the column using an additional 2 ml
cyclohexane to complete the transfer. Just prior to exposure of the
sodium sulfate layer to the air, add 25 mL of pentane and continue the
elution of the column. Discard this pentane eluate.
7.1.4 Next, elute the column with 25 ml of methylene chloride/-
pentane (2:3)(v/v) into a 500-mL K-D flask equipped with a 10-mL
concentrator tube. Concentrate the collected fraction to whatever volume
1s required (1-10 ml). Proceed with HPLC or GC analysis. Components
that elute 1n this fraction are:
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)f1uoranthene
Benzo(ghi)perylene
Benzo(k)f1uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
3630 - 3
Revision
Date September 1986
-------
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
7.2 Derivatized phenols;
7.2.1 This silica gel
extracts that have undergone
described in Method 8040.
cleanup procedure is performed on sample
pentafluorobenzyl bromide derivatization as
7.2.2 Place 4.0 g of activated silica gel into a 10-mm I.D.
chromatographic column. Tap the column to settle the silica gel and add
about 2 g of anhydrous sodium sulfate to the top of the silica gel.
7.2.3 Preelute the column with 6 ml of hexane. The rate for all
elutions should-be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, pi pet onto the column
2 ml of the hexane solution that contains the derivatized sample or
standard. Elute the column with 10.0 mL of hexane and discard the
eluate.
7.2.4 Elute the column, in order, with: 10.0 ml of 15% toluene in
hexane (Fraction 1); 10.0 mL of 40% toluene in hexane (Fraction 2); 10.0
ml of 75% toluene in hexane (Fraction 3); and 10.0 ml of 15% 2-propanol
in toluene (Fraction 4). All elution mixtures are prepared on a
volume:volume basis. Elution patterns for the phenolic derivatives are
shown in Table 1. Fractions may be combined, as desired, depending upon
the specific phenols of interest or level of interferences. Proceed with
GC analysis (Method 8040).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for
Method 3600 for cleanup procedures.
specific quality control procedures and
8.2 The analyst should demonstrate that the compounds of Interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Table 1 provides performance
phenolic derivatives using this method.
information on the fractionation of
3630 - 4
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. Gordon, A.J., and R.A. Ford, The Chemist's Companion; A Handbook of
Practical Data, Techniques, and References,(NewYork:John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.
2. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3630 - 5
Revision
Date September 1986
-------
TABLE 1. SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
Percent Recovery by Fraction1
Parameter 1 23
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethyl phenol
2, 4-Dichl orophenol
2,4, 6-Tri chl orophenol
4-Chl oro-3-methyl phenol
Pentachl orophenol
4-Nitrophenol
{
90
90
95
95
50 50
84
75 20
1
9
10
7
1
14
1
90
90
Eluant composition:
Fraction 1-15% toluene in hexane.
Fraction 2-40% toluene in hexane.
Fraction 3-75% toluene in hexane.
Fraction 4-15% 2-propanol in toluene.
3630 - 6
Revision
Date September 1986
-------
METHOD 3630
SILICA GEL CLEANUP
7.1
Exchange
extract solvent to
cyclonexane: distill
using mlcro-Snyder
column: adjust
extract volume
to 2 mL
7.1.8
Polynuclear
aromatic
hydrocarbon
7.2.11Do penta-
I fluoro-
benzyl bromide
derlvatlzatlon
on sample
extract (8040)
Put
silica
gel. methylene
chloride slurry
In chromato-
grapnlc column
7.2.2
Place activated
silica gel in
chromatographic
column: add anhydrous
sodium sulfate
7.1.8
Elute
methylene
chloride: add
anhydrous
•odium sulfate
7.1.3
7.2.3
Preelute
column
with hexane:
pipet hexane
solution on
column: elute
Preelute column with
pentane: transfer
•xtract onto column;
elute with pentane
7.2.4
Elute
column
with hexane
solutions:
analyze
(Method 6040)
7.1.41
Elute
with nethylcne
chloride/
pentane
7.1.4]
Concentrate
fraction;
adjust volume:
analyze
Analyze
by GC
(Method
6040)
3630 - 7
Revision 0
Date September 1986
-------
METHOD 3640
GEL-PERMEATION CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Gel-permeation chromatography (GPC) is a size exclusion procedure
using organic solvents and hydrophobic gels in the separation of synthetic
macromolecules (Gordon and Ford). The packing gel is porous and is
characterized by the range or uniformity (exclusion range) of that pore size.
In the choice of gels, the exclusion range must be greater than those of the
molecules to be separated (Shugar, et al.).
1.2 General application; GPC is recommended for the elimination from
the sample of lipids, polymers, copolymers, proteins, natural resins and
polymers, cellular components, viruses, steroids, and dispersed high-
molecular-weight compounds (Shugar, et al.).
1.3 Specific application; This method includes guidance for cleanup of
sample extracts containing the compounds listed 1n Tables 2-1 through 2-9 of
Chapter 2.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of preswelled
absorbent and is flushed with solvent for an extended period. The column is
calibrated and then loaded with the sample to be analyzed. Elutlon is
effected with a suitable sol vent(s) and the product 1s then concentrated.
3.0 INTERFERENCES
3.1 A reagent blank should be analyzed for the compound of interest
prior to the use of this method. The level of Interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined 1n this method may be
necessary for reagent purification.
4.0 APPARATUS
4.1 Gel permeation chromatography system; (Analytical Biochemical
Laboratories, Inc. GPC autoprep Model 1002A or equivalent). An automated
system of this type is not required; however, if not used, equivalency of an
alternative system must be shown.
4.1.1 Chromatographtc column; 600- to 700-mm x 25-mm I.D. glass
column fitted for upward flow operation.
4.1.2 B1o-beads S-X3: 70 g per column.
3640 - 1
Revision 0
Date September 1986
-------
4.1.3 Pump: Capable of constant flow of 0.1 to 5 mL/m1n at up to
100 psi.
4.1.4 Injector: With 5-mL loop.
4.1.5 Ultraviolet detector: 254-nm (optional).
4.1.6 Strip-chart recorder: (optional).
4.1.7 Syringe: 10-mL with Luerlok fitting.
4.1.8 Syringe filter holder and filter: BioRad "Prep Disc" sample
filter # 343-0005 and 5-um size filters or equivalent.
4.2 Beakers; 400-mL.
5.0 REAGENTS -
5.1 Methylene chloride; Pesticide quality or equivalent.
5.2 GPC calibration solutions;
5.2.1 Corn oil: 200 mg/mL in methylene chloride.
5.2.2 B1s(2-ethylhexyl)phthaiate and pentachlorophenol solution:
4.0 mg/mL 1n methylene chloride.
5.2,3 Mix the corn oil with the phthalate/phenol solution 1f a UV
detector is used. The concentrations should remain the same.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1i
\
7.0 PROCEDURE
7.1 Packing the column; Place approximately 70 g of Bio Beads SX-3 1n a
400-mL beaker.Cover thebeads with methylene chloride; allow the beads to
swell overnight (before packing the columns). Transfer the swelled beads to
the column and start pumping solvent through the column, from bottom to top,
at 5.0 mL/min. After approximately 1 hr, adjust the pressure on the column to
7-10 ps1 and pump an additional 4 hr to remove air from the column. Adjust
the column pressure periodically as required to maintain 7-10 psi. (See the
instrument manual for more details on packing the column.) The pressure
should not be permitted to exceed 25 psi.
7.2 Calibration of the column; The column can either be calibrated
manually by gravimetric/GC/FID techniques or automatically if a recording UV
detector with a flow through cell is available.
3640 - 2
Revision 0
Date September 1986
-------
7.2.1 Manual calibration: Load 5 mL of the corn oil solution into
sample loop No. 1 and 5 mL of the phthalate-phenol solution into loop
No. 2. Inject the corn oil and collect 10-mL fractions (i.e., change
fractions at 2-min intervals) for 36 min. Inject the phthalate-phenol
solution and collect 15 mL fractions for 60 min. Determine the corn oil
elution pattern by evaporation of each fraction to dryness followed by a
gravimetric determination of the residue. Analyze the phthalate-phenol
fractions by GC/FID using a DB-5 capillary column, a UV spectrophoto-
meter, or a GC/MS system. Plot the concentration of each component in
each fraction versus total eluant volume (or time) from the injection
points. Choose a dump time which allows £ 85% removal of the corn oil
and ]> 85% recovery of the bis(2-ethylhexyl)phthalate. Choose the collect
time to extend at least 10 min after the elution of pentachlorophenol.
Wash the column with methylene chloride at least 15 min between samples.
Typical parameters selected are: Dump time, 30 min (150 mL); collect
time, 36 min (180 mL); and wash time, 15 min (75 mL).
7.2.2 Automated calibration: The column can also be calibrated by
the use of a 254-nm detector in place of gravimetric and GC analyses of
fractions. Use the corn oil/phthalate/phenol mixture when using a UV
detector. Load 5 mL into sample loop No. 1. Use the same criteria for
choosing dump time and collect time as in the manual calibration.
7.2.3 The SX-3 Bio Beads column may be reused for several months,
even if discoloration occurs. Recalibrate the system once a week.
7.3 GPC Extract Cleanup; The extract must be in methylene chloride or,
primarily methylene chloride. All other solvents must be concentrated to 1 mL
and diluted to 10.0 mL with methylene chloride. Prefilter or load all
extracts via the filter holder to avoid particulates that might cause flow
stoppage or damage the valve. Load one 5.0 mL aliquot of the extract onto the
GPC column. Do not apply excessive pressure when loading. Purge the sample
loading tubing thoroughly with solvent between extracts. After especially
dirty extracts, run a GPC blank (methylene chloride) to check for carry-over.
Process the extracts using the dump, collect, and wash parameters determined
from the calibration, and collect the cleaned extracts in 400-mL beakers
tightly covered with aluminum foil.
NOTE: Half of the 10.0 mL extract is lost during the loading of the GPC.
Therefore, divide the sample size by two when calculating analyte
concentration.
7.4 Concentrate the extract by the standard K-D technique (see any of
the extraction methods, Section 4.2 of this chapter). See the
determinative methods (Chapter Four, Section 4.3) for the required final
volume.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedure.
3640 - 3
Revision 0
Date September 1986
-------
8.2 The analyst should demonstrate that the compound(s) of interest are
being quantitatively recovered before applying this method to actual samples.
8.2 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. Gordon, A.J., and R.A. Ford, The Chemist's Companion; A Handbook of
Practical Data. Techniques, and References(NewYork:John Wiley & Sons,
Inc.) pp. 372, 374, and 375, 1972.
2. ShugarG.J., et al., Chemical Technician's Ready Reference Handbook, 2nd
ed. (New York: McGraw-Hill Book Co.) pp. 764-766, 1981.
3. Wise, R.H., D.F. Bishop, R.T. Williams, and B.M. Austern, "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges," U.S. EPA,
Municipal Environmental Research Laboratory, Cincinnati, Ohio 45268.
4. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, Revision, July 1985.
3640 - 4
Revision
Date September 1986
-------
METHOD 3640
GEL-PERMEATION CLEANUP
7. 1
Be
adjust
Pack
CO lumn
with Bio
ads SX-3;
pressure
7.2.1
Manually calibrate
by GC/FIO using OB-S
capillary column:
Uv spectrophotometer
or GC/MS to analyze
fractions
7.2.1
Select dump.
collect, ana
wash times
Manual
alIbrat ion
Automated
calibration
7.2.2 Calibrate
using o
Calibrate
column?
UV detector
ana corn oil/
phthalate/
phenol mixture
Select
dump.
collect, and
Dilute with
metnylene
chloride
wash times:
recalibrate
once a week
Load extract onto GPC
column and process:
purge column
between extracts
7.4
Concentrate
extract:
analyze
V- - - -
3640 - 5
Revision p
Date September 1986
-------
METHOD 3650
ACID-BASE PARTITION CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Method 3650 was formally Method 3530 in the second edition of this
manual.
1.2 This is a liquid-liquid partitioning method to separate acid
analytes from base/neutral analytes using pH adjustment. It may be used for
cleanup of petroleum waste prior to alumina cleanup.
2.0 SUMMARY OF METHOD
2.1 The solvent extract is shaken with water that is strongly basic.
The acid analytes partition into the aqueous layer, whereas, the basic and
neutral compounds stay in the organic solvent. The base/neutral fraction is
concentrated and is ready for further cleanup, if necessary, or analysis. The
aqueous layer is acidified and extracted with an organic solvent. This
extract is concentrated and then ready for analysis for the acid analytes.
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compound of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those
necessary for reagent purification.
outlined in this method may be
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel; 125-mL, with Teflon stopcock.
4.2 Drying column; 20-mm I.D. Pyrex chromatographic column; with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone followed by
50 mL of elution solvent prior to packing the column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus;
4.3.1 Concentrator tube: 10-mL,
equivalent). Ground-glass stopper is
extracts.
graduated (Kontes K5700-1025 or
used to prevent evaporation of
3650 - 1
Revision 0
Date September 1986
-------
4.3.2 Evaporation flask: 500-mL (K-570001-0500 or equivalent).
Attach to concentrator tube with springs.
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K569001-0219 or
equivalent).
4.4 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.6 Vials; Glass, 2-mL capacity with Teflon-lined screw-cap.
4.7 pH Indicator paper; pH range Including the desired extraction pH.
4.8 Erlenmeyer flask; 125-mL.
5.0 REAGENTS
5.1 Reagent water; Reagent water 1s defined as water 1n which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.2 Sodium hydroxide solution ION: (ACS) 40 g NaOH 1n reagent water and
dilute to 100 ml.
5.3 Sodium sulfate; (ACS) Granular, a'nhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
5.4 Sulfuric acid solution (1:1): Slowly add 50 ml ^04 (sp. gr. 1.84)
to 50 ml of reagent water.
5.5 Solvents; Acetone, methanol, ethyl ether, methylene chloride
(pesticide quality or equivalent).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Place 10 mL of the extract or organic liquid waste to be cleaned up
into the separatory funnel.
3650 - 2
Revision
Date September 1986
-------
7.2 Add 20 ml of methylene chloride to the separatory funnel.
7.3 Add 20 ml of reagent water and adjust the pH to 12-13 with sodium
hydroxide.
7.4 Seal and shake the separatory funnel for 1-2 min with periodic
venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 min. If the emulsion interface between layers is more than one-
third of the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends
upon the sample, and may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods.
7.6 Separate the aqueous phase and transfer it to a 125-mL Erlenmeyer
flask. Repeat the extraction two more times using fresh 20 ml portions of
reagent water pH 12-13. Combine the aqueous extracts.
7.7 At this point the analytes will be in the organic and/or in the
aqueous phase. Organic acids and phenols will be in the aqueous phase,
whereas, base/neutral analytes will be in the organic solvent. If the
analytes are in the aqueous phase only, discard the organic phase and proceed
to Paragraph 7.8. If the analytes are in the organic phase, discard the
aqueous phase and proceed to Paragraph 7.10.
7.8 Transfer the aqueous phase to a clean separatory funnel. Adjust the
aqueous layer to a pH of 1-2 with sulfuric acid. Add 20 ml of methylene
chloride to the separatory funnel and shake for 2 min. Allow the solvent to
separate from the aqueous phase and collect the solvent in an Erlenmeyer
flask.
7.9 Add a second 20 ml volume of methylene chloride to the separatory
funnel and re-extract at pH 1-2 a second time, combining the extracts in the
Erlenmeyer flask. Perform a third extraction in the same manner.
7.10 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporation flask.
7.11 Dry the extracts by passing them through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in the K-D
concentrator. Rinse the Erlenmeyer flask which contained the solvent extract
and the column with 20 ml of methylene chloride to complete the quantitative
transfer.
7.12 Add one or two boiling chips to the flask and attach a three-ball
macro-Snyder column. Prewet the Snyder column by adding about 1 ml of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
3650 - 3
Revision 0
Date September 1986
-------
water bath (60°-65°C) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 15-20 min. At the
proper rate of distillation, the balls of the column will actively chatter but
the chambers will not flood. When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus from the water bath and allow it to drain and cool
for at least 10 min. Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 ml of extraction solvent.
7.13 Add another one or two boiling chips to the concentrator tube and
attach a two-ball micro-Snyder column. Prewet the column by adding 0.5 ml of
methylene chloride to the top of the column. Place the K-D apparatus in a hot
water bath (95°-100*C) so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5-10 min. At the
proper rate of distillation the balls of the column will actively chatter but
the chambers will not flood. When the apparent volume of the liquid reaches
0.5 ml, remove the K-D apparatus and allow it to drain for at least 10 min
while cooling. Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 0.2 ml of extraction solvent. Adjust
the final volume to 1.0 ml with solvent.
7^14 The acid fraction is now ready for analysis. If the base/neutral
extract is to undergo further cleanup by the Alumina Column Cleanup for
Petroleum Waste (Method 3611), the extract must be exchanged to hexane. To
the 1-mL base/neutral extract, 5 ml of hexane should be added (solvent
exchanged), and this mixture then reconcentrated to 1 ml using the micro-KD
apparatus. If no further cleanup of the base/neutral extract is required, it
is also ready for analysis.
)•
8.0- QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must be processed through this cleanup
method.
.9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
10.1 None required.
3650 - 4
Revision
Date September 1986
-------
METHOD 3650
ACID-BASE PARTITION CLEANUP
7. 1
Place
extract
or organic
liquid waste
into separatory
funnel
7.2
Add methylene
chloride
7.3
7.5
Complete
phase
separatIon
with mechanical
techniques
Separate
aqueous
phase: Repeat
extract twice:
combine aqueous
extracts
Add reagent
water;
adjust pH
7.7
Discard
aqueous phase
7.4
Seal and snake
•eparatory
f unne1
7.5
Allow
separation
or organic
layer from
water phase
o
On 1 y s V
organic/ Which phase ^v^
• analytes In? ^
Only
7.7
Discard
organic phase
Trans fer
aqueous
phase to
clean funnel:
adjust pH
7.6 I Add
Imethylene
chloride:
shake: separate
and collect In
flask
o
7.9
I Perform
two more
extractions;
combine
extracts
3650 - 5
Revision o
Date September 1986
-------
METHOD 36SO
AGIO-BASE PARTITION CLEANUP
(Continued)
7. 10
Assemble K-O
concentrator
7. 11
Dry and collect
extracts In K-D
concentrator
7 .
Concentrate
extract to 1 ml
using K-O
apparatus
7. 13
Concentrate extract
to O.5 ml uElno K-O
apparatus: adjust
final volume
Is further
extraction needed
for base-
neutral?
Use
Methoo 3611:
change extract
to hexane
Analyze
fractions
3650 - 6
Revision 0
Date September 1986
-------
METHOD 3660
SULFUR CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Elemental sulfur is encountered in many sediment samples (generally
specific to different areas in the country), marine algae, and some industrial
wastes. The solubility of sulfur in various solvents is very similar to the
organochlorine and organophosphorous pesticides; therefore, the sulfur
interference follows along with the pesticides through the normal extraction
and cleanup techniques. In general, sulfur will usually elute entirely in
Fraction 1 of the Florisil cleanup (Method 3620).
1.2 Sulfur will be quite evident in gas chromatograms obtained from
electron capture detectors, flame photometric detectors operated in the sulfur
or phosphorous mode, and Coulson electrolytic conductivity detectors in the
sulfur mode. If the gas chromatograph is operated at the normal conditions
for pesticide analysis, the sulfur interference can completely mask the region
from the solvent peak through Aldrin.
1.3 Three techniques for the elimination of sulfur are detailed within
this method: (1) the use of copper powder; (2) the use of mercury; and
(3) the use of tetrabutylamrnonium-sulfite. Tetrabutylamrnonium-sulfite causes
the least amount of degradation of a broad range of pesticides and organic
compounds, while copper and mercury may degrade organophosporous and some
organochlorine pesticides.
2.0 SUMMARY OF METHOD
2.1 The sample to undergo cleanup is mixed with either copper, mercury,
or tetrabutylammonium (TBA)-sulfite. The mixture is shaken and the extract is
removed from the sulfur cleanup reagent.
3.0 INTERFERENCES
3.1 Removal of sulfur using copper;
3.1.1 The copper must be very reactive; therefore, all oxides of
copper must be removed so that the copper has a shiny, bright appearance.
3.1.2 The sample extract must be vigorously agitated with the
reactive copper for at least one minute.
4.0 APPARATUS AND MATERIALS
4.1 Mechanical shaker or mixer; Such as the Vortex Genie.
4.2 Pi pets; Disposable, Pasteur type.
3660 - 1
Revision 0
Date September 1986
-------
4.3 Centrifuge tubes; Calibrated, 12-mL.
4.4 Glass bottles or vials; 10-mL and 50-mL, with Teflon-lined screw-
caps.
5.0 REAGENTS
5.1 Reagent water; Reagent water Is defined as water 1n which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.2 Nitric acid; Dilute.
5;3 Acetone, hexane, 2-propanol; Pesticide quality or equivalent.
5.4 Copper powder; Remove oxides by treating with dilute nitric acid,
rinse with distilled water to remove all traces of acid, rinse with acetone
and dry under a stream of nitrogen. (Copper, fine granular Mallinckrodt 4649
or equivalent).
5.5 Mercury; Triple distilled.
5.6 Tetrabutylammonium (TBA)-sulfite reagent; Dissolve 3.39 g
tetrabutylammonium hydrogen sulfate in 100 ml reagent water. To remove
impurities, extract this solution three times with 20-mL portions of hexane.
Discard the hexane extracts, and add 25 g sodium sulfite to the water
solution. Store the resulting solution, which is saturated with sodium
sulfite, in an amber bottle with a Teflon-lined screw-cap. This solution can
be stored at room temperature for at least one month.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Removal of sulfur using copper;
7.1.1 Concentrate the sample to exactly 1.0-mL in the Kuderna-
Danish tube.
7.1.2 If the sulfur concentration is such that crystallization
occurs, centrifuge to settle the crystals, and carefully draw off the
sample extract with a disposable pi pet leaving the excess sulfur in the
K-D tube. Transfer the extract to a calibrated centrifuge tube.
7.1.3 Add approximately 2 g of cleaned copper powder (to the 0.5 mL
mark) to the centrifuge tube. Mix for at least 1 min on the mechanical
shaker.
3660 - 2
Revision 0
Date September 1986
-------
7.1.4 Separate the extract from the copper by drawing off the
extract with a disposable pipet and transfer to a clean vial. The volume
remaining still represents 1.0 ml of extract.
NOTE: This separation is necessary to prevent further degradation
of the pesticides.
7.2 Removal of sulfur using mercury;
NOTE: Mercury is a highly toxic metal and therefore, must be used
with great care. Prior to using mercury, it is recommended that the
analyst become acquainted with proper handling and cleanup
techniques associated with this metal.
7.2.1 Concentrate the sample extract to exactly 1.0 ml.
7.2.2 Pipet 1.0 ml of the extract into a clean concentrator tube or
Teflon-sealed vial.
7.2.3 Add one to three drops of mercury to the vial and seal.
Agitate the contents of the vial for 15-30 sec. Prolonged shaking (2 hr)
may be required. If so, use a mechanical shaker.
7.2.4 Separate the sample from the mercury by drawing off the
extract with a disposable pipet and transfer to a clean vial.
7.3 Removal of sulfur using TBA-sulfite;
7.3.1 Concentrate the sample extract to exactly 1.0 ml.
7.3.2 Transfer the 1.0 ml to a 50-mL clear glass bottle or vial
with a Teflon-lined screw-cap. Rinse the concentrator tube with 1 ml of
hexane, adding the rinsings to the 50-mL bottle.
7.3.3 Add 1.0 ml TBA-sulfite reagent and 2 ml 2-propanol, cap the
bottle, and shake for at least 1 min. If the sample is colorless or if
the initial color is unchanged, and if clear crystals (precipitated
sodium sulfite) are observed, sufficient sodium sulfite is present. If
the precipitated sodium sulfite disappears, add more crystalline sodium
sulfite in approximately 100-mg portions until a solid residue remains
after repeated shaking.
7.3.4 Add 5 ml distilled water and shake for at least 1 min. Allow
the sample to stand for 5-10 min. Transfer the hexane layer (top) to a
concentrator tube and use the K-D technique to concentrate the extract to
1.0 ml.
7.4 Analyze the cleaned up extracts by gas chromatography (see the
determinative methods, Section 4.3 of this chapter).
3660 - 3
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 All reagents should be checked prior to use to verify that
interferences do not exist.
9.0 METHOD PERFORMANCE
9.1 Table 1 indicates the effect of using copper and mercury to remove
sulfur on the recovery of certain pesticides.
10.0 REFERENCES
1. Loy, E.W., private communication.
2. Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9 (1971).
3. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, Revision, July 1985.
3660 - 4
Revision
Date September 1986
-------
Table 1. EFFECT OF MERCURY AND COPPER ON PESTICIDES
Pesticide
Percent Recovery9 using;
Mercury
Copper
Aroclor 1254
Lindane
Heptachlor
Aldrin
Heptachlor epoxide
DDE
DDT
BHC
Dieldrin
Endrin
Chi orobenzi late
Malathion
Diazinon
Parathion
Ethion
Trithion
97.10
75.73
39.84
95.52
69.13
92.07
78.78
81.22
79.11
70.83
7.14
0.00
0.00
0.00
0.00
0.00
104.26
94.83
5.39
93.29
96.55
102.91
85.10
98.08
94.90
89.26
0.00
0.00
0.00
0.00
0.00
0.00
a Percent recoveries cited are averages based on duplicate analyses for all
compounds other than for Aldrin and BHC. For Aldrin, four and three
determinations were averaged to obtain the result for mercury and copper,
respectively. Recovery of BHC using copper is based on one analysis.
3660 - 5
Revision 0
Date September 1986
-------
METHOD 3660
SULFUR CLEANUP
Start
Copper
TBA-sulfItc
7.1.1
7.1.3
Centrifuge and
draw off sample
extract
Concentrate
sample extract
7.2.1
Mercury
Concentrate
sample extract
7.2.8
7.3.1
Concentrate
sample extract
Plpet
extract Into
concentrator
tube or vial
Transfer
extract to
centr1fuge
tube
7.2.3
7.3.2
Transfer
extract to
glass bottle
or vial
Add mercury;
agitate
0
7.3.3
Add
TBA-sulflte and
2-propano 1:
shake
O
3660 - 6
Revision o
Date September 1986
-------
METHOD 3660
SULFUR CLEANUP
(Continued)
o
7.1.3
o
Add copper
powder; mix
7.2.4
Separate sample
from mercury
7.1.4
Separate
•xtract from
copper
Add more sodium
sulflte: shake
distilled
water; . shake:
let stand:
concentrate
•extract
3660 - 7
Revision o
Date September 1986
-------
4.3 DETERMINATION OF ORGANIC ANALYTES
4.3.1 GAS CHROMATOGRAPHIC METHODS
FOUR - 9
Revision
Date September 1986
-------
METHOD 8000
GAS CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 Gas chromatography is a quantitative analytical technique useful for
organic compounds capable of being volatilized without being decomposed or
chemically rearranged. Gas chromatography (GC), also known as vapor phase
chromatography (VPC), has two subcategories distinguished by: gas-solid
chromatography (GSC), and gas-liquid chromatography (GLC) or gas-liquid
partition chromatography (GLPC). This last group is the most commonly used,
distinguished by type of column adsorbent or packing.
1.2 The gas chromatographic methods are recommended for use only by, or
under the close supervision of, experienced residue analysts.
2.0 SUMMARY OF METHOD
2.1 Each organic analytical method that follows provides a recommended
technique for extraction, cleanup, and occasionally, derivatization of the
samples to be analyzed. Before the prepared sample is introduced into the GC,
a procedure for standardization must be followed to determine the recovery and
the limits of detection for the analytes of interest. Following sample
introduction into the GC, analysis proceeds with a comparison of sample values
with standard values. Quantitative analysis is achieved through integration
of peak area or measurement of peak height.
3.0 INTERFERENCES
3.1 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe or purging device must be rinsed out between samples with reagent
water or solvent. Whenever an unusually concentrated sample is encountered,
it should be followed by an analysis of a solvent blank or of reagent water to
check for cross contamination. For volatile samples containing large amounts
of water-soluble materials, suspended solids, high boiling compounds or high
organohalide levels, it may be necessary to wash out the syringe or purging
device with a detergent solution, rinse it with distilled water, and then dry
it in a 105°C oven between analyses.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph; analytical system complete with gas chromato-
graph suitable for on-column injections and all required accessories,
including detectors, column supplies, recorder, gases, and syringes. A data
system for measuring peak height and/or peak areas is recommended.
8000 - 1
Revision 0
Date September 1986
-------
4.2 Gas chromatographic columns; See the specific determinative method.
Other packedorcapillary(open-tubular) columns may be used if the
requirements of Section 8.6 are met.
5.0 REAGENTS
5.1 See the specific determinative method for the reagents needed.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Extraction: Adhere to those procedures specified in the referring
determinative method.
7.2 Cleanup and separation; Adhere to those procedures specified in the
referring determinative method.
7.3 The recommended gas chromatographic columns and operating conditions
for the instrument are specified in the referring determinative method.
7.4 Calibration;
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.0 of the determinative method of
interest. Prepare calibration standards using the procedures indicated
in Section 5.0 of the determinative method of interest. Calibrate the
chromatographic system using either the external standard technique
(Section 7.4.2) or the internal standard technique (Section 7.4.3).
7.4.2 External standard calibration procedure:
7.4.2.1 For each analyte of interest, prepare calibration
standards at a minimum of five concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with an appropriate solvent. One of the external
standards should be at a concentration near, but above, the method
detection limit. The other concentrations should correspond to the
expected range of concentrations found in real samples or should
define the working range of the detector.
7.4.2.2 Inject each calibration standard using the technique
that will be used to introduce the actual samples into the gas
chromatograph (e.g, 2- to 5-uL injections, purge-and-trap, etc.).
Tabulate peak height or area responses against the mass injected.
8000 - 2
Revision
Date September 1986
-------
The results can be used to prepare a calibration curve for each
analyte. Alternatively, for samples that are introduced into the
gas chromatograph using a syringe, the ratio of the response to the
amount injected, defined as the calibration factor (CF), can be
calculated for each analyte at each standard concentration. If the
percent relative standard deviation (%RSD) of the calibration factor
is less than 20% over the working range, linearity through the
origin can be assumed, and the average calibration factor can be
used in place of a calibration curve.
Calibration factor = Total Area of Peak*
Mass injected (in nanograms)
*For multiresponse pesticides/PCBs use the total area of all peaks
used for quantitation.
7.4.2.3 The working calibration curve or calibration factor
must be verified on each working day by the injection of one or more
calibration standards. The frequency of verification is dependent
on the detector. Detectors, such as the electron capture detector,
that operate in the sub-nanogram range are more susceptible to
changes in detector response caused by GC column and sample effects.
Therefore, more frequent verification of calibration is necessary.
The flame ionization detector is much less sensitive and requires
less frequent verification. If the response for any analyte varies
from the predicted response by more than +15%, a new calibration
curve must be prepared for that analyte.
R, - Rp
Percent Difference = -*—*—- x 100
Kl
where:
R! = Calibration Factor from first analysis.
R2 = Calibration Factor from succeeding analyses.
7.4.3 Internal standard calibration procedure:
7.4.3.1 To use this approach, the analyst must select one or
more internal standards that are similar in analytical behavior to
the compounds of interest. The analyst must further demonstrate
that the measurement of the internal standard is not affected by
method or matrix interferences. Due to these limitations, no
internal standard applicable to all samples can be suggested.
7.4.3.2 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest by adding volumes
of one or more stock standards to a volumetric flask. To each
calibration standard, add a known constant amount of one or more
internal standards and dilute to volume with an appropriate solvent.
8000 - 3
Revision 0
Date September 1986
-------
One of the standards should be at a concentration near, but above,
the. method detection limit. the other concentrations should
correspond to the expected range of concentrations found In real
samples or should define the working range of the detector.
7.4.3.3 Inject each calibration standard using the same
Introduction technique that will be applied to the actual samples
(e.g, 2- to 5-uL injection, purge-and-trap, etc.). Tabulate the
peak height or area responses against the concentration of each
.compound and Internal standard. Calculate response factors (RF) for
each compound as follows:
RF = (AsC1s)/(A1sCs)
where: .
As = Response for the analyte to be measured.
Ais = Response for the internal standard.
C}s = Concentration of the internal standard, ug/L.
Cs = Concentration of the analyte to be measured, ug/L.
If the RF value over the working range is constant «20% RSD), the
RF can be assumed to be invariant, and the average RF can be used
for calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Afs versus RF.
7.4.3.4 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. The frequency of verification is dependent on the
detector. Detectors, such as the electron capture detector, that
operate in the sub-nanogram range are more susceptible to changes 1n
detector response caused by GC column and sample effects.
Therefore, more frequent verification of calibration is necessary.
The flame ionization detector is much less sensitive and requires
less frequent verification. If the response for any analyte varies
from the predicted response by more than +15%, a new calibration
curve must be prepared for that compound.
7.5 Retention time windows;
7.5.1 Before establishing windows, make sure the GC system 1s
within optimum operating conditions. Make three injections of all single
component standard mixtures and multiresponse products (I.e., PCBs)
throughout the course of a 72-hr period. Serial injections over less
than a 72-hr period result in retention time windows that are too tight.
7.5.2 Calculate the standard deviation of the three absolute
.retention times for each single component standard. For multiresponse
products, choose one major peak from the envelope and calculate the
8000 - 4
Revision 0
Date September 1986
-------
standard deviation of the three retention times for that peak. The peak
chosen should be fairly immune to losses due to degradation and
weathering in samples.
7.5.2.1 Plus or minus three times the standard deviation of
the absolute retention times for each standard will be used to
define the retention time window; however, the experience of the
analyst should weigh heavily 1n the interpretation of chromatograms.
For multiresponse products (i.e., PCBs), the analyst should use the
retention time window but should primarily rely on pattern recog-
nition.
7.5.2.2 In those cases where the standard deviation for a
particular standard is zero, the laboratory must substitute the
standard deviation of a close eluting, similar compound to develop a
valid retention time window.
7.5.3 The laboratory must calculate retention time windows for each
standard on each GC column and whenever a new GC column 1s Installed.
The data must be retained by the laboratory.
7.6 Gas chromatographic analysis:
7.6.1 Introduction of organic compounds into the gas chromatograph
varies depending on the volatility of the compound. Volatile organlcs
are primarily introduced by purge-and-trap (Method 5030). However, there
are limited applications where direct injection is acceptable. Use of
Method 3810 or 3820 as a screening technique for volatile organic
analysis may be valuable with some sample matrices to prevent overloading
and contamination of the GC systems. Semi volatile organlcs are
introduced by direct injection.
7.6.2 The appropriate detector(s) is given in the specific method.
7.6.3 Samples are analyzed in a set referred to as an analysis
sequence. The sequence begins with instrument calibration followed by
sample extracts interspersed with multilevel calibration standards. The
sequence ends when the set of samples has been injected or when
qualitative and/or quantitative QC criteria are exceeded.
7.6.4 Direct Injection: Inject 2-5 uL of the sample extract using
the solvent flush technique. Smaller (1.0-uL) volumes can be Injected 1f
automatic devices are employed. Record the volume injected to the
nearest 0.05 uL and the resulting peak size in area units or peak height.
7.6.5 If the responses exceed the linear range of the system,
dilute the extract and reanalyze. It is ,recommended that extracts be
diluted so that all peaks are on scale. Overlapping peaks are not always
evident when peaks are off scale. Computer reproduction of
chromatograms, manipulated to ensure all peaks are on scale over a 100-
fold range, are acceptable 1f linearity is demonstrated. Peak height
measurements are recommended over peak area integration when overlapping
peaks cause errors in area Integration.
8000 - 5
Revision 0
Date September 1986
-------
7.6.6 If peak detection is prevented by the presence of
interferences, further cleanup is required.
7.6.7 Examples of chromatograms for the compounds of interest are
frequently available in the referring analytical method.
7.6.8 Calibrate the system immediately prior to conducting any
analyses (see Paragraph 7.4). A midlevel standard must also be injected
at intervals specified in the method and at the end of the analysis
sequence. The calibration factor for each analyte to be quantitated,
must not exceed a 15% difference when compared to the initial standard of
the analysis sequence. When this criteria is exceeded, inspect the GC
system to determine the cause and perform whatever maintenance is
necessary (see Section 7.7) before recalibrating and proceeding with
sample analysis. All samples that were injected after the sample
exceeding the criteria must be reinjected.
7.6.9 Establish daily retention time windows for each analyte. Use
the absolute retention time for each analyte from Section 7.6.8 as the
midpoint of the window for that day. The daily retention time window
equals the midpoint + three times the standard deviation determined 1n
Section 7.5.
7.6.9.1 Tentative identification of an analyte occurs when a
peak from a sample extract falls within the daily retention time
window. Normally, confirmation is required: on a second GC column;
by GC/MS if concentration permits; or by other recognized
confirmation techniques. Confirmation may not be necessary if the
composition of the sample matrix is well established by prior
analyses.
7.6.9.2 Validation of GC system qualitative performance: Use
the midlevel standards interspersed throughout the analysis sequence
(Paragraph 7.6.8) to evaluate this criterion. If any of the
standards fall outside their dally retention time window, the system
is out of control. Determine the cause of the problem and correct
it (see Section 7.7).
7.7 Suggested chromatography system maintenance; Corrective measures
may require any one or more of the following remedial actions.
7.7.1 Packed columns: For instruments with injection port traps,
replace the demister trap, clean, and deactivate the glass injection port
insert or replace with a cleaned and deactivated insert. Inspect the
injection end of the column and remove any foreign material (broken glass
from the rim of the column or pieces of septa). Replace the glass wool
with fresh deactivated glass wool. Also, it may be necessary to remove
the first few millimeters of the packing material if any discoloration 1s
noted, also swab out the Inside walls of the column if any residue 1s
noted. , If these procedures fail to eliminate the degradation problem, It
may be necessary to deactivate the metal injector body (described 1n
Section 7.7.3) and/or repack/replace the column.
8000 - 6
Revision 0
Date September 1986
-------
7.7.2 Capillary columns: Clean and deactivate the glass Injection
port insert or replace with a cleaned and deactivated insert. Break off
the first few inches, up to one foot, of the injection port side of the
column. Remove the column and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate the
degradation problem, it may be necessary to deactivate the metal injector
body and/or replace the column.
7.7.3 Metal Injector body: Turn off the oven and remove the
analytical column when oven has cooled. Remove the glass injection port
insert (instruments with off-column injection or Grob). Lower the
injection port temperature to room temperature. Inspect the injection
port and remove any noticeable foreign material.
7.7.3.1 Place a beaker beneath the injector port inside the GC
oven. Using a wash bottle, serially rinse the entire inside of the
injector port with acetone and then toluene; catching the rinsate in
the beaker.
7.7.3.2 Prepare a solution of deactivating agent (Sylon-CT or
equivalent) following manufacturer's directions. After all metal
surfaces inside the injector body have been thoroughly coated with
the deactivation solution, serially rinse the injector body with
toluene, methanol.acetone, and hexane. Reassemble the injector and
replace the GC column.
7.8 Calculations;
7.8.1 External standard calibration: The concentration of each
analyte in the sample may be determined by calculating the amount of
standard purged or injected, from the peak response, using the
calibration curve or the calibration factor determined in Paragraph
7.4.2. The concentration of a specific analyte is calculated as follows:
Aqueous samples;
Concentration (ug/L) = [(Ax) (A) (Vt) (D)]/[(AS) OWVs)]
where:
Ax = Response for the analyte in the sample, units may be in area
counts or peak height.
A = Amount of standard injected or purged, ng.
As = Response for the external standard, units same as for Ax.
V-j = Volume of extract injected, uL. For purge-and-trap analysis,
Vj is not applicable and therefore = 1.
D = Dilution factor, if dilution was made on the sample prior to
analysis. If no dilution was made, D = 1, dimensionless.
8000 - 7
Revision 0
Date September 1986
-------
Vt = Volume of total extract, uL. For purge-and-trap analysis, Vt
is not.applicable and therefore = 1.
Vs = Volume of sample extracted or purged, mL.
Nonaqueous samples;
Concentration (ng/g) = [(Ax)(A)(Vt)(D)]/[(AS)(V^(W)]
where:
W = Weight of sample extracted or purged, g. The wet weight or dry
weight may be used, depending upon the specific applications of
the data.
AXI ASl A, vti DI ancl vi have the same definition as for aqueous
samples.
7.8.2 Internal standard calibration: For each analyte of interest,
the concentration of that analyte in the sample is calculated as follows:
Aqueous samples;
Concentration (ug/L) = [(Ax)(C1s)(D)]/[(A1s)(RF)(Vs)]
where:
Ax = Response of the analyte being measured, units may be in area
counts or peak height.
Cis = Amount of internal standard added to extract or volume purged,
ng.
D = Dilution factor, if a dilution was made on the sample prior to
analysis. If no dilution was made, D = 1, dimensionless.
A-JS = Response of the internal standard, units same as Ax.
RF = Response factor for analyte, as determined in Paragraph
7.4.3.3.
Vs = Volume of water extracted or purged, ml.
Nonaqueous samples;
Concentration (ug/kg) = [(As)(Cis)(D)]/[(Ais)(RF)(Ws)]
where:
Ws = Weight of sample extracted, g. Either a dry weight or wet
weight may be used, depending upon the specific application of
the data.
8000 - 8
Revision
Date September 1986
-------
As. Cis, D, A-js, and RF have the same definition as for aqueous
samples.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program
consist of ah initial demonstration of laboratory capability and an ongoing
analysis of spiked samples to evaluate and document quality data. The
laboratory must maintain records to document the quality of the data
generated. Ongoing data quality checks are compared with established
performance criteria to determine if the results of analyses meet the
performance characteristics of the method. When results of sample spikes
indicate atypical method performance, a quality control check standard must be
analyzed to confirm that the measurements were performed in an in-control mode
of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent water blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a set
of samples is extracted or there is a change in reagents, a reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 For each analytical batch (up to 20 samples), a reagent blank,
matrix spike and matrix spike duplicate/duplicate must be analyzed (the
frequency of the spikes may be different for different monitoring programs).
The blank and spiked samples must be carried through all stages of the sample
preparation and measurement steps.
8.4 The experience of the analyst performing gas chromatography is
invaluable to the success of the methods. Each day that analysis is
performed, the daily calibration sample should be evaluated to determine if
the chromatographic system is operating properly. Questions that should be
asked are: Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g, column changed), recalibration of the system must take place.
8.5 Required Instrument QC;
8.5.1 Section 7.4 requires that the %RSD vary by <20% when
comparing calibration factors to determine if a five point calibration
curve is linear.
8.5.2 Section 7.4 sets a limit of +15% difference when comparing
daily response of a given analyte versus the initial response. If the
limit is exceeded, a new standard curve must be prepared.
8000 - 9
Revision 0
Date September 1986
-------
8.5.3 Section 7.5 requires the establishment of retention time
wi ndows.
8.5.4 Paragraph 7.6.8 sets a limit of +15% difference when
comparing the initial response of a given analyte versus any succeeding
standards analyzed during an analysis sequence.
8.5.5 Paragraph 7.6.9.2 requires that all succeeding standards in
an analysis sequence must fall within the daily retention time window
established by the first standard of the sequence.
8.6 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.6.1 A quality .(QC) check sample concentrate is required
containing each analyte of interest. The QC check sample concentrate may
be prepared from pure standard materials or purchased as certified
solutions. If prepared by the laboratory, the QC check sample
concentrate must be made using stock standards prepared independently
from those used for calibration.
8.6.1.1 The concentration of the QC check sample concentrate
is highly dependent upon the analytes being investigated.
Therefore, refer to Method 3500, Section 8.0 for the required
concentration of the QC check sample concentrate.
8.6.2 Preparation of QC check samples:
8.6.2.1 Volatile organic analytes (Methods 8010, 8020, and
8030): The QC check sample is prepared by adding 200 uL of the QC
check sample concentrate (Section 8.6.1) to 100 ml of reagent water.
8.6.2.2 Semivolatile organic analytes (Methods 8040, 8060,
8080, 8090, 8100, and 8120):TheQCcheck sample is prepared by
adding 1.0 ml of the QC check sample concentrate (8.6.1) to each of
four 1-L aliquots of reagent water.
8.6.3 Four aliquots of the well-mixed QC check sample are analyzed
by the same procedures used to analyze actual samples (Section 7.0 of
each of the methods). For volatile organics, the preparation/analysis
process is purge-and-trap/gas chromatography. For semi volatile organics,
the QC check samples must undergo solvent extraction (see Method 3500)
prior to chromatographic analysis.
8.6.4 Calculate the average recovery (7) in ug/L, and the standard
deviation of the recovery (s) in ug/L, for each analyte of interest using
the four results.
' 8.6.5 For each analyte compare s and K with the corresponding
acceptance criteria for precision and accuracy, respectively, given the
QC Acceptance Criteria Table at the end of each of the determinative
methods. If s and 7 for all analytes of interest meet the acceptance
8000 - 10
Revision 0
Date September 1986
-------
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual 7 falls outside the range for accuracy, then the system
performance is unacceptable for that analyte.
NOTE: The large number of analytes in each of the QC Acceptance
Criteria Tables present a substantial probability that one or more
will fail at least one of the acceptance criteria when all analytes
of a given method are determined.
8.6.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.6.6.1 or 8.6.6.2.
8.6.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with Section
8.6.2.
8.6.6.2 Beginning with Section 8.6.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Section
8.6.2.
8.7 The laboratory must, on an ongoing basis, spike at least one sample
per analytical batch (maximum of 20 samples per batch) to assess accuracy.
For laboratories analyzing one to ten samples per month, at least one spiked
sample per month is required.
8.7.1 The concentration of the spike in the sample should be
determined as follows:
8.7.1.1 If, as in compliance monitoring, the concentration of
a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined in
Section 8.7.2, whichever concentration would be larger.
8.7.1.2 If the concentration of a specific analyte in the
sample is not being checked against a limit specific to that
analyte, the spike should be at the same concentration as the QC
check sample (8.6.2) or 1 to 5 times higher than the background
concentration determined in Section 8.7.2, whichever concentration
would be larger.
8.7.1.3 For semivolatile organics, it may not be possible to
determine the background concentration levels prior to spiking
(e.g., maximum holding times will be exceeded). If this is the
case, the spike concentration should be (1) the regulatory
concentration limit, if any; or, if none (2) the larger of either 5
times higher than the expected background concentration or the QC
check sample concentration (Section 8.6.2).
8000 - 11
Revision 0
Date September 1986
-------
8.7.2 Analyze one unspiked and one spiked sample aliquot to
determine percent recovery of each of the spiked compounds.
8.7.2.1 Volatile organlcs; Analyze one 5-mL sample aliquot to
determine the background concentration (B) of each analyte. If
necessary, prepare a new QC check sample concentrate (Section 8.6.1)
appropriate for the background concentration 1n the sample. Spike a
second 5-mL sample aliquot with 10 uL of the QC check sample
concentrate and analyze it to determine the concentration after
spiking (A) of each analyte. Calculate each percent recovery (p) as
100(A - B)%/T, where T is the known true value of the spike.
8.7.2.2 Semi volatile organics; Analyze one sample aliquot
(extract of 1-Lsample)to determine the background concentration
(B) of each analyte. If necessary, prepare a new QC check sample
concentrate (Section 8.6.1) appropriate for the background
concentration in the sample. Spike a second 1-L sample aliquot with
1.0 mL of the QC check sample concentrate and analyze it to
determine the concentration after spiking (A) of each analyte.
Calculate each percent recovery (p) as 100(A - B)%/T, where T is the
known true value of the spike.
8.7.3 Compare the percent recovery (p) for each analyte with the
corresponding criteria presented in the QC Acceptance Criteria Table
ifound at the end of each of the determinative methods. These acceptance
criteria were calculated to include an allowance for error in measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1. If spiking
was performed at a concentration lower than the QC check sample
concentration (8.6.2), the analyst must use either the QC acceptance
criteria presented in the Tables, or optional QC acceptance criteria
calculated for the specific spike concentration. To calculate optional
acceptance criteria for the recovery of an analyte: (1) Calculate
accuracy (x1) using the equation found 1n the Method Accuracy and
Precision as a Function of Concentration Table (appears at the end of
each determinative method), substituting the spike concentration (T) for
C; (2) calculate overall precision (S1) using the equation in the same
Table, substituting x1 for 7; (3) calculate the range for recovery at the
spike concentration as (lOOx'/T) + 2.44(100S'/T)%.
8.7.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be
analyzed as described in Section 8.8.
8.8 If any analyte fails the acceptance criteria for recovery in Section
8.7, a QC check standard containing each analyte that failed must be prepared
and analyzed.
NOTE: The frequency for the required analysis of a QC check standard
will depend upon the number of analytes being simultaneously tested, the
8000 - 12
Revision 0
Date September 1986
-------
complexity of the sample matrix, and the performance of the laboratory.
If the entire list of analytes given in a method must be measured in the
sample in Section 8.7, the probability that the analysis of a QC check
standard will be required is high. In this case the QC check standard
should be routinely analyzed with the spiked sample.
8.8.1 Preparation of the QC check standard: For volatile organics,
add 10 uL of the QC check sample concentrate (Section 8.6.1 or 8.7.2) to
5 ml of reagent water. For semi volatile organics, add 1.0 ml of the QC
check sample concentrate (Section 8.6.1 or 8.7.2) to 1 L of reagent
water. The QC check standard needs only to contain the analytes that
failed criteria in the test in Section 8.7. Prepare the QC check
standard for analysis following the guidelines given in Method 3500
(e.g., purge-and-trap, extraction, etc.).
8.8.2 Analyzed the QC check standard to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100 (A/T)%, where T is the true value of the standard concentration.
8.8.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in the appropriate Table in
each of the methods. Only analytes that failed the test in Section 8.7
need to be compared with these criteria. If the recovery of any such
analyte falls outside the designated range, the laboratory performance
for that analyte is judged to be out of control, and the problem must be
immediately identified and corrected. The result for that analyte in the
unspiked sample is suspect and may not be reported for regulatory
compliance purposes.
8.9 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After
the analysis of five spiked samples (of the same matrix type) as in Section
8.7, calculate the average percent recovery (p) and the standard deviation of
the percent recovery (sp). Express the accuracy assessment as a percent
recovery interval from JJ - 2sn to p + 2sp. If JJ = 90% and sp = 10%, for
example, the accuracy interval is expressed as 70-110%. Update the accuracy
assessment for each analyte on a regular basis (e.g. after each five to ten
new accuracy measurements).
8.10 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.10.1 For each sample analyzed, calculate the percent recovery of
cuvifnnal'o in tho camnlo
each surrogate in the sample
8.10.2 Once a minimum of thirty samples of the same matrix have
been analyzed, calculate the average percent recovery (p) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.10.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
8000 - 13
Revision
Date September 1986
-------
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
8.10.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Tables A and B of Methods 8240 and 8270,
respectively. The limits given in these methods are multi-laboratory
performance based limits for soil and aqueous samples, and therefore, the
single-laboratory limits established in Paragraph 8.10.3 must fall within
those given in Tables A and B for these matrices.
8.10.5 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.10.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrix-by-matrix basis, annually.
8.11 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the Identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column, specific element detector, or mass spectrometer must
be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL concentrations listed in the
referring analytical methods were obtained using reagent water. Similar
results were achieved using representative wastewaters. The MDL actually
achieved in a given analysis will vary depending on instrument sensitivity and
matrix effects.
9.2 Refer to the determinative method for specific method performance
information.
8000 - 14
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
2. U.S. EPA 40 CFR Part 136, Appendix B. "Guidelines Establishing Test
Procedures for the Analysis of Pollutants Under the Clean Water Act; Final
Rule and Interim Final Rule and Proposed Rule," October 26, 1984.
3. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
8000 - 15
Revision
Date September 1986
-------
METHOD BOOO
GAS CHROMATOGRAPHY
7.1
1 Refer to
determinative
method for
extraction
procedure
7.4.3
Select Internal
standards having
similar behavior to
compounds of interest
7.2
Refer
to deter-
minative method
for cleanup and
separation
procedures
7.4.1
7.4.3.2
7.4.2.1
Prepare
calibration
standards for
each parameter
of Interest
Prepare
calIbratIon
standards
Establish gas
chromatograph
operating parameters;
prepare calibration
standards
7.4.3.3
7.4.2
Inject calibration
standard: prepare
calibration curve
or calibration factor
Inject
colIbratIon
standards;
calculate HF
o
7.4.3.4
7.4.2.3
Verify working
cal IbratIon
curve each day
Verify working
calIbration
curve or RF
each day
7.5
Calculate
retention tlmo
windows
O
8000 - 16
Revision p
Date September 1986
-------
METHOD 8000
GAS CHROMATOGRAPH
(Continued)
o
7.6.1
Use
Method
3810 or 3880
as screening
technique.
If necessary
7.6.1
into
mate
purge
(Met
Introduce
compounds
gas chro-
>graph by
•-and-trap
hod 5030)
volatile ^S 7.6.1 ^s^emlvolat 1 le
}S Type of ^\
* Vorganlc compound?>? *
7.6.1
Introduce
compounds Into
gas chromato-
graph by direct
Injection
7.6.4
extr
sol\
t
recc
Inject
sample
•act using
'ent flush
.echnlque;
>rd volume
Does response
exceed linear
range of
system?
chromatography
system
maintenance
If needed
Dilute extract
and reanalyze
Calculate
concentration of
each analyte. using
appropriate formula
for matrix and typa
of standard
Is peak deten-
tlon prevented by
Interference?
Do further
cleanup
7.6.8
Calibrate
system
Immediately
prior to
analyses
7.6.9
Establish
dally
retention time
windows for
each analyte
8000 - 17
Revision p
Date September 1986
-------
METHOD 8010
HALOGENATED VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
l.i Method 8010 1s used to determine the concentration of various
volatile halogenated organic compounds. Table 1 Indicates compounds that may
be analyzed by this method and lists the method detection limit for each
compound 1n reagent water. Table 2 lists the practical quantisation limit for
other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8010 provides gas chromatographic conditions for the
detection of halogenated volatile organic compounds. Samples can be analyzed
using direct injection or purge-and-trap (Method 5030). Ground water samples
must be analyzed using Method 5030. A temperature program 1s used 1n the gas
chromatograph to separate the organic compounds. Detection is achieved by a
halogen-specific detector (HSD).
2.2 The method provides an optional gas chromatographic column that may
be helpful 1n resolving the analytes from interferences that may occur and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas Chromatograph: analytical system complete with gas
chromatograph suitable for on-column Injections or purge-and-trap sample
introduction and all required accessories, Including detector, analytical
columns, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
8010 - 1
Revision
Date September 1986
-------
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION. LIMITS FOR
HALOGENATED VOLATILE ORGANICS '•;:.,.'
Compound
Benzyl chloride
Bi s (2-chl oroethoxy)methane
Bi s (2-chl oroi sopropyl ) ether
Bromobenzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chl oroacetal dehyde
Chl orobenzene
Chloroethane
Chloroform
1-Chlorohexane
2-Chl oroethyl vinyl ether
Chl oromethane
Chloromethylmethyl ether
Chlorotoluene
Di bromochl oromethane
Dibromomethane
1 , 2-D1 chl orobenzene
1 , 3-Di chl orobenzene
1,4-Di chl orobenzene
Di chl orodi f 1 uoromethane
1,1-Di chl oroethane
1,2-Dichloroethane
1,1-Di chl oroethyl ene
trans-1 , 2-Di chl oroethyl ene
Di chl oromethane
1 , 2-D1 chl oropropane
trans-1 , 3-D1 chl oropropyl ene
1,1,2, 2-Tetrachl oroethane
1,1,1, 2-Tetrachl oroethane
Tetrachl oroethyl ene
1 , 1 , 1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Tr1 chl oroethyl ene
Tri chl orof 1 uoromethane
Tri chl oropropane
Vinyl chloride
Retentlo
(ml
Col. 1
13.7
19.2
13.0
24.2
3.33
10.7
18.0
1.50
16.5
34.9
34.0
35.4
9.30
11.4
8.0
10.1
14.9
15.2
21.6
21.7
12.6
16.5
15.8
7.18
2.67
in time M
n) det
i
• • "• • • '•• • " ' ' I
Col. 2 (
•-.•-;•
...,-..." ; ; ' •• •_
•-• ••:. .: -. ,-i'i
14.6
M9.2 . .>:-
' • '• .'•','.
14.4
- ••»; •. •! : '••'',
18.8, •• » ,
8.68
12.1
5.28
16.6
23.5
22.4
22.3
12.6
15.4
7.72
9.38
16.6
16.6
15.0
13.1
18.1
13.1
5.28
ethod
ectlon
1m1ta
ug/L)
\-;\-'
: " /. ' •
0.10
,0.20
, -.
0.12
• 5
0.25
0.52
0.05
0.13
0.08
0.09
0.15
0.32
0.24
0.07
0.03
0.13
0.10
0.04
0.34
0.03
0.03
0.03
0.02
0.12
0.18
a Using purge-and-trap method (Method 5030)
8010 - 2
Revision 0
Date September 1986
-------
2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
trlx Factor*5
water 10
vel soil 10
m1sc1ble liquid waste 500
evel soil and sludge 1250
ter mlsdble waste 1250
Sample PQLs are highly matrix-dependent. The PQLs listed herein are
rovided for guidance and may not always be achievable.
PQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
queous samples, the factor 1s on a wet-weight basis.
8010 - 3
Revision 0
Date September 1986
-------
4.1.2 Columns:
4.1.2.1 Column 1: 8-ft x O.l-1n I.D. stainless steel or glass
column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
4.1.2.2 Column 2: 6-ft x 0.1-in I.D. stainless steel or glass
column packed with chemically bonded n-octane on Porasil-C 100/120
mesh (Durapak) or equivalent.
4.1.3 Detector: Electrolytic conductivity (HSD).
4.2 Sample introduction apparatus; Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes; 5-mL Luerlok glass hypodermic and a 5-mL, gas-tight with
shutoff valve.
4.4 Volumetric flask; 10-, 50-, 100-, 500-, and 1,000-mL with a ground-
glass stopper.
4.5 Microsyringe; 10-, 25-uL with a 0.006-in I.D. needle (Hamilton 702N
or equivalent) and a 100-uL.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as a water in which an
interferent is not observed at the method detection limit (MDL) of the
parameters of interest.
5.2 Stock standards; Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity of these materials should be prepared in a hood.
5.2.1 Place about 9.8 mL of methanol in a 10-mL tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.2.2 Add the assayed reference material, as described below.
5.2.2.1 Liquids: Using a 100-uL syringe, immediately add two
or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.2.2.2 Gases: To prepare standards for any compounds that
boil below 30*C (e.g., bromomethane, chloroethane, chloromethane,
dichlorodifluoromethane, trichlorofluoromethane, vinyl chloride),
fill a 5-mL valved gas-tight syringe with the reference standard to
the 5.0-mL mark. Lower the needle to 5 mm above the methanol
8010 - 4
Revision 0
Date September 1986
-------
meniscus. Slowly Introduce the reference standard above the surface
of the liquid. The heavy gas rapidly dissolves 1n the methanol.
This may also be accomplished by using a lecture bottle equipped
with a Hamilton Lecture Bottle Septum (#86600). Attach Teflon
tubing to the side-arm relief valve and direct a gentle stream of
gas into the methanol meniscus.
5.2.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
microliter (ug/uL) from the net gain in weight. When compound purity 1s
assayed to be 96% or greater, the weight may be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.2.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at -10*C to -20*C and
protect from light.
5.2.5 Prepare fresh standards every 2 months for gases or for
reactive compounds such as 2-chloroethylvinyl ether. All other standards
must be replaced after 6 months, or sooner if comparison with check
standards indicates a problem.
5.3 Secondary dilution standards: Using stock standard solutions,
prepare 1n methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Section 5.4 will bracket the working range
of the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels are prepared in reagent water from the secondary dilution
of the stock standards. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Each
standard should contain each analyte for detection by this method (e.g., some
or all of the compounds listed in Table 1 may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
5.4.1 Do not inject more than 20 uL of alcoholic standards into 100
ml of reagent water.
5.4.2 Use a 25-uL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.4.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
8010 - 5
Revision 0
Date September 1986
-------
5.4.4 Mix aqueous standards by inverting the flask three times
only.
5.4.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.4.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.4.7 Aqueous standards are not stable and should be discarded
after 1 hr, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hr, if held in sealed vials with zero headspace.
5.5 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples. The
compounds recommended for use as surrogate spikes (Paragraph 5.6) have been
used successfully as internal standards, because of their generally unique
retention times.
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described in
Section 5.4.
5.5.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.2 and 5.3. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ug/mL of each internal standard compound. The
addition of 10 uL of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
5.5.3 Analyze each calibration standard according to Section 7.0,
adding 10 uL of internal standard spiking solution directly to the
syringe.
5.6 Surrogate standards; The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
water blank with surrogate halocarbons. A combination of bromochloromethane,
2-bromo-l-chloropropane, and 1,4-dichlorobutane is recommended to encompass
the range of the temperature program used in this method. From stock standard
solutions prepared as in Section 5.2, add a volume to give 750 ug of each
surrogate to 45 ml of reagent water contained in a 50-mL volumetric flask,
mix, and dilute to volume for a concentration of 15 ng/uL. Add 10 uL of this
surrogate spiking solution directly into the 5-mL syringe with every sample
and reference standard analyzed. If the internal standard calibration
procedure is used, the surrogate compounds may be added directly to the
internal standard spiking solution (Paragraph 5.5.2).
8010 - 6
Revision 0
Date September 1986
-------
5.7 Methanol: pesticide quality or equivalent. Store away from other
solvents.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For medium-level soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set helium gas flow at 40 mL/min flow rate. Set
column temperature at 45*C for 3 min; then program an 8*C/min temperature
rise to 220*C and hold for 15 min.
7.2.2 Column 2: Set helium gas flow at 40 mL/min flow rate. Set
column temperature at 50*C for 3 min; then program a 6*C/min temperature
rise to 170'C and hold for 4 min.
7.3 Calibration: Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample
introduction method that will be used to analyze actual samples (see
Paragraph 7.4.1).
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.4 Gas chromatographic analysis;
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method
(see Paragraph 7.4.1.1). If the internal standard calibration technique
is used, add 10 uL of internal standard to the sample prior to purging.
7.4.1.1 Direct injection; In very limited applications (e.g.,
aqueous process wastes) direct injection of the sample into the GC
system with a 10-uL syringe may be appropriate. The detection limit
is very high (approximately 10,000 ug/L) therefore, it is only
8010 - 7
Revision
Date September 1986
-------
permitted where concentrations in excess of 10,000 ug/L are expected
or for water-soluble compounds that do not purge. The system must
be calibrated by direct injection (bypassing the purge-and-trap
device).
7.4.2 Follow Section 7.6 in Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
columns for a number of organic compounds analyzable using this method.
An example of the separation achieved by Column 1 is shown in Figure 1.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Section 7.8 of
Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution
of the sample with reagent water. The dilution must be performed on a
second aliquot of the sample which has been properly sealed and stored
prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Mandatory quality control to validate the GC system operation 1s
found in Method 8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of interest at a concentration
of 10 ug/mL in methanol.
8.2.2 Table 3 Indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Section 8.10).
8010 - 8
Revision 0
Date September 1986
-------
i
00
o
H-»
o
I
ID
O 73
DJ tt>
r+ <
fT> _i.
CO O
O> 3
ft)
CT
Column: 1% SP-1000 on Carbopacfc-B
Program: 46»C 3 Minute*. 8°/MinuM to 220°C
Detector: Hall 700 A Electrolytic Conductivity
1
s
o
e
o
«M
8 10 12 14 16 18 20 22 24
RETENTION TIME (MINUTES)
26
28
30
32
34
36
00
Figure 1. Gas Chromatogram of halogenated volatile organic*.
-------
8.3.1 If recovery is not within^limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 8.0-500 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the parameter and essentially independent of the sample
matrix. Linear equations to describe these relationships are presented in
Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA Contract
68-03-2635 (in preparation).
4. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
5. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
6. "EPA Method Validation Study 23, Method 601 (Purgeable Halocarbons),"
Report for EPA Contract 68-03-2856 (in preparation).
8010 - 10
Revision
Date September 1986
-------
TABLE 3. CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Bromodi chl oromethane
Bromoform
Bromome thane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Di chlorobenzene
1,3-Di Chlorobenzene
1,4-Di chlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Di chl oropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Methylene chloride
1, 1,2,2-Tetrachloroethane
Tetrachloroethene
1,1, 1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(ug/L)
15.2-24.8
14.7-25.3
11.7-28.3
13.7-26.3
14.4-25.6
15.4-24.6
12.0-28.0
15.0-25.0
11.9-28.1
13.1-26.9
14.0-26.0
9.9-30.1
13.9-26.1
16.8-23.2
14.3-25.7
12.6-27.4
12.8-27.2
14.8-25.2
12.8-27.2
12.8-27.2
15.5-24.5
9.8-30.2
14.0-26.0
14.2-25.8
15.7-24.3
15.4-24.6
13.3-26.7
13.7-26.3
Limit
for s
(ug/L)
4.3
4.7
7.6
5.6
5.0
4.4
8.3
4.5
7.4
6.3
5.5
9.1
5.5
3.2
5.2
6.6
6.4
5.2
7.3
7.3
4.0
9.2
5.4
4.9
3.9
4.2
6.0
5.7
Range
for 7
(ug/L)
10.7-32.0
5.0-29.3
3.4-24.5
11.8-25.3
10.2-27.4
11.3-25.2
4.5-35.5
12.4-24.0
D-34.9
7.9-35.1
1.7-38.9
6.2-32.6
11.5-25.5
11.2-24.6
13.0-26.5
10.2-27.3
11.4-27.1
10.1-29.9
6.2-33.8
6.2-33.8
7.0-27.6
6.6-31.8
8.1-29.6
10.8-24.8
9.6-25.4
9.2-26.6
7.4-28.1
8.2-29.9
Range
P, PS
(%)
42-172
13-159
D-144
43-143
38-150
46-137
14-186
49-133
D-193
24-191
D-208
7-187
42-143
47-132
51-147
28-167
38-155
44-156
22-178
22-178
25-162
8-184
26-162
41-138
39-136
35-146
21-156
28-163
Q = Concentration measured in QC check sample, in ug/L.
s = Standard deviation of four recovery measurements, in ug/L.
7 = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCriteria from 40 CFR Part 136 for Method 601 and were calculated
assuming a QC check sample concentration of 20 ug/L.
8010 - 11
Revision 0
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl etherb
Chloroform
Chl oromethane
Di bromochl oromethane
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
1, 1-Di chloroethane
1, 2-Di chloroethane
1,1-Dichloroethene
trans-1, 2-Di chl oroethene
1 , 2-Di chl oropropane*5
ci s-1 , 3-Di chl oropropeneb
trans-1, 3-Di chl oropropene^
Methylene chloride
1,1, 2, 2-Tetrachl oroethene
Tetrachl oroethene
1,1, 1-Tri chl oroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Accuracy, as
recovery, x1
(ug/L)
1.12C-1.02
0.96C-2.05
0.76C-1.27
0.98C-1.04
l.OOC-1.23
0.99C-1.53
l.OOC
0.93C-0.39
0.77C+0.18
0.94C+2.72
0.93C+1.70
0.95C+0.43
0.93C-0.09
0.95C-1.08
1.04C-1.06
0.98C-0.87
0.97C-0.16
l.OOC
l.OOC
l.OOC
0.91C-0.93
0.95C+0.19
0.94C+0.06
0.90C-0.16
0.86C+0.30
0.87C+0.48
0.89C-0.07
0.97C-0.36
Single analyst
precision, sr'
(ug/L)
0.117+0.04
0.127+0.58
0.287+0.27
0.157+0.38
0.157-0.02
0.147-0.13
0.207
0.137+0.15
0.287-0.31
0.117+1.10
0.207+0.97
0.147+2.33
0.157+0.29
0.087+0.17
0.117+0.70
0.217-0.23
0.117+1.46
0.137
0.187
0.187
0.117+0.33
0.147+2.41
0.147+0.38
0.157+0.04
0.137-0.14
0.137-0.03
0.157+0.67
0.137+0.65
Overal 1
precision,
S1 (ug/L)
0.207+1.00
0.217+2.41
0.367+0.94
0.207+0.39
0.187+1.21
0.177+0.63
0.357
0.197-0.02
0.527+1.31
0.247+1.68
0.137+6.13
0.267+2.34
0.207+0.41
0.147+0.94
0.157+0.94
0.297-0.04
0.177+1.46
0.237
0.327
0.327
0.217+1.43
0.237+2.79
0.187+2.21
0.207+0.37
0.197+0.67
0.237+0.30
0.267+0.91
0.277+0.40
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
aFrom 40 CFR Part 136 for Method 601.
^Estimates based upon the performance in a single laboratory.
8010 - 12
Revision 0
Date September 1986
-------
METHOD 6010
WALOGENATED VOLATILE ORGANICS
Start
7. 1
Introduce compounds
Into gas
chromatograph by
direct Injection or
purge-ano-trap
(Method 5O30)
7.4.4
Record
volume purged
or Injected and
peak sizes
7.2
Set gas
chromatograph
condition
7.3
7.4.5
Calculate
concentration
(Section 7.6.
Method BOOO)
o
Cal lorate
(refer to
Method BOOO)
7 . J. 1
Introduce volatile
compounds Into gas
chromatograph by
Method 5030 or
direct Injection
7.4.2
S<
In M«
for
sequc
Follow
sctlon 7.6
•thod 6000
analys Is
nee. etc .
7.4.6
Analyze using
second GC
column
7.4.7
Dilute second
aliquot of
•ample
8010 - 13
Revision 0
Date September 1986
-------
METHOD 8015
NONHALOGENATED VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 Method 8015 is used to determine the concentration of various
nonhalogenated volatile organic compounds. Table 1 indicates the compounds
that may be investigated by this method.
2.0 SUMMARY OF METHOD
2.1 Method 8015 provides gas chromatographic conditions for the
detection of certain nonhalogenated volatile organic compounds. Samples may
be analyzed using direct injection or purge-and-trap (Method 5030). Ground
water samples must be analyzed by Method 5030. A temperature program is used
in the gas chromatograph to separate the organic compounds. Detection is
achieved by a flame ionization detector (FID).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful in resolving the analytes from
interferences that may occur and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph:
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring
peak heights and/or peak areas is recommended.
4.1.2 Columns:
4.1.2.1 Column 1: 8-ft x 0.1-in I.D. stainless steel or glass
column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
8015 - 1
Revision 0
Date September 1986
-------
TABLE 1. NONHALOGENATED VOLATILE ORGANICS
Aery1 amide
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Paraldehyde (trimer of acetal.dehyde)
8015 - 2
Revision 0
Date September 1986
-------
4.1.2.2 Column 2: 6-ft x 0.1-in I.D. stainless steel or glass
column packed with n-octane on Porasil-C 100/120 mesh (Durapak) or
equivalent.
4.1.3 Detector: Flame ionization (FID).
4.2 Sample introduction apparatus: Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes; A 5-mL Luerlok glass hypodermic and a 5-mL, gas-tight
with shutoff valve.
4.4 Volumetric flask; 10-, 50-, 100-, 500-, and 1,000-mL with a ground-
glass stopper.
4.5 Microsyringe; 10- and 25-uL with a 0.006-in I.D. needle (Hamilton
702N or equivalent) and a 100-uL.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as a water in which an
interferent is not observed at the method detection limit (MDL) of the
analytes of interest.
5.2 Stock standards; Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids.
5.2.1 Place about 9.8 mL of methanol in a 10-mL tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.2.2 Using a 100-uL syringe, immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
5.2.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
microliter (ug/uL) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.2.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at -10*C to -20*C and
protect from light.
5.2.5 Standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
8015 - 3
Revision 0
Date September 1986
-------
5.3 Secondary dilution standards: Using stock standard solutions, pre-
pare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Section 5.4 will bracket the working range
of the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels are prepared in reagent water from the secondary dilution
of the stock standards. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Each
standard.should contain each analyte for detection by this method (e.g., some
or all of the compounds listed in Table 1 may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
5.4.1 Do not inject more than 20 uL of alcoholic standards into
100 ml of reagent water.
5.4.2 Use a 25-uL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.4.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.4.4 Mix aqueous standards by inverting the flask three times
only.
5.4.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
5.4.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.4.7 Aqueous standards are not stable and should be discarded
after 1 hr, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hr, if held in sealed vials with zero headspace.
5.5 •Internal standards (if internal standard calibration is used); To
use this.approach, the analyst must select one or more inter$l standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
8015 - 4
Revision 0
Date September 1986
-------
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described in
Section 5.4.
5.5.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.2 and 5.3. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ug/mL of each internal standard compound. The
addition of 10 uL of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
5.5.3 Analyze each calibration standard according to Section 7.0,
adding 10 uL of internal standard spiking solution directly to the
syringe.
5.6 Surrogate standards: The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
water blank with one or two surrogate compounds recommended to encompass the
range of temperature program used in this method. From stock standard
solutions prepared as in Section 5.2, add a volume to give 750 ug of each
surrogate to 45 mL of reagent water contained in a 50-mL volumetric flask,
mix, and dilute to volume for a concentration of 15 ng/uL. Add 10 uL of this
surrogate spiking solution directly into the 5-mL syringe with every sample
and reference standard analyzed. If the internal standard calibration
procedure is used, the surrogate compounds may be added directly to the
internal standard spiking solution (Paragraph 5.5.2).
5.7 Methanol; pesticide quality or equivalent. Store away from other
solvents.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For medium-level soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended):
7.2.1 Column 1: Set helium gas flow at 40 mL/min flow rate. Set
column temperature at 45°C for 3 min; then program an 8*C/min temperature
rise to 220*C and hold for 15 min.
8015 - 5
Revision
Date September 1986
-------
7.2.2 Column 2: Set helium gas flow at 40 mL/min flow rate. Set
column temperature at 50*C for 3 min; then program a 6*C/min temperature
rise to 170*C and hold for 4 min.
7.3 Calibration: Refer to Method 8000 for proper calibration
techniques.
7.3.1 Calibration must
introduction method that will
Section 7.4.1).
take place using the same sample
be used to analyze actual samples (see
7.3.2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.4 Gas chromatographic analysis:
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection
method. If the internal standard calibration technique is used, add
10 uL of internal standard to the sample prior to purging.
7.4.1.1 Direct injection; In very limited applications (e.g.,
aqueous process wastes), direct injection of the sample into the GC
system with a 10 uL syringe may be appropriate. One such
application is for verification of the alcohol content of an aqueous
sample prior to determining if the sample is ignitable (Methods 1010
or 1020). In this case, it is suggested that direct injection be
used. The detection limit is very high (approximately 10,000 ug/L);
therefore, it is only permitted when concentrations in excess of
10,000 ug/L are expected or for water-soluble compounds that do not
purge. The system must be calibrated by direct injection (bypassing
the purge-and-trap device).
7.4.2 Follow Section 7.6 in Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
7.4.3 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.4 Calculation of concentration is covered in
Method 8000.
Section 7.8 of
7.4.5 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.6 If the response for a peak is off-scale, prepare a dilution
of the sample with reagent water. The dilution must be performed on a
second-aliquot of the sample which has been properly sealed and stored
prior to use. :
8015 - 6
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Mandatory quality control to validate the GC system operation is
found in Method 8000, Section 8.6.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and calibration procedures used.
9.2 Specific method performance information will be provided as it
becomes available.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, in Van Hall, ed., Measurement of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA Contract
68-03-2635 (in preparation).
8015 - 7
Revision 0
Date September 1986
-------
METHOD 8015
NONrlALDGENATEw VOLATILE ORSASICS
Stai-t
7. 1
Introduce compcunos
into gas
cnromatograeh by
direct Injection o.~
purge-ano-t-sp
(Method 503C;
7 .S
Set gas
oTiatog~e
condition
7.3
Cal ibrste
(refe- tc
Metnoc BCOO!
Introduce volatile
compojnos Into gas
ch"-ornBtogf'Bch by
Method 503C o-
dlrect Injection
Follow
Section 7.6
In Methoo 6000
for- analysis
sequence, etc.
o
o
Record
volume purged
or injected and
peak sizes
7.4.4
Calculate
concentration
(Section 7.6.
Method 6000)
O
7.4.5
Analyze using
second GC
column
Yes
/ VI V
Is response for X.
• peak off-scale?
7.4.6
Dilute second
aliquot of
•ample
8015 - 8
Revision 0
Date September 1986
-------
METHOD 8020
AROMATIC VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 Method 8020 1s used to determine the concentration of various
aromatic volatile organic compounds. Table 1 indicates compounds which may be
determined by this method and lists the method detection limit for each
compound In reagent water. Table 2 lists the practical quantitation limit
(PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8020 provides chromatographic conditions for the detection of
aromatic volatile compounds. Samples can be analyzed using direct injection
or purge-and-trap (Method 5030). Ground water samples must be determined
using Method 5030. A temperature program is used in the gas chromatograph to
separate the organic compounds. Detection is achieved by a photo-ionization
detector (PID).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful 1n resolving the analytes from
the interferences and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring
peak heights and/or peak areas is recommended.
8020 - 1
Revision 0
Date September 1986
-------
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS FOR AROMATIC
VOLATILE ORGANICS
Compound
Benzene
Chloroberizene
1,4-Dichlorobenzene
1 , 3-Di chl orobenzene
1 , 2-Di chl orobenzene
Ethyl Benzene
Toluene
Xylenes
Retention
(m1n)
Col. 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75
time
Col. 2
2.75
8.02
16.2
15.0
19.4
6.25
4.25
Method
detection
11m1ta
(ug/L)
0.2
0.2
0.3
0.4
0.4
0.2
0.2
a Using purge-and-trap method (Method 5030).
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil 10
Water miscible liquid waste 500
High-level soil and sludge 1250
Non-water miscible waste 1250
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = {Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples,, the factor is on a wet-weight basis.
8020 T- 2
Revision
Date September 1986
-------
4.1.2 Columns:
4.1.2.1 Column 1: 6-ft x 0.082-in I.D. #304 stainless steel
or glass column packed with 5% SP-1200 and 1.75% Bentone-34 on
100/120 mesh Supelcort or equivalent.
4.1.2.2 Column 2: 8-ft x 0.1-in I.D. stainless steel or glass
column packed with 5% 1,2,3-Tris(2-cyanoethoxy)propane on 60/80 mesh
Chromosorb W-AW or equivalent.
4.1.3 Detector: Photoionization (PID) (h-Nu Systems, Inc. Model
PI-51-02 or equivalent).
4.2 Sample introduction apparatus; Refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes: A 5-mL Luerlok glass hypodermic and a 5-mL, gas-tight
with shutoff valve.
4.4 Volumetric flask: 10-, 50-, 100-, 500-, and 1,000-mL with a ground-
glass stopper.
4.5 Microsyringe: 10- and 25-uL with a 0.006-in I.D. needle (Hamilton
702N or equivalent) and a 100-uL.
5.0 REAGENTS
5.1 Reagent water; Reagent water is defined as a water in which an
interferent is not observed at the method detection limit (MDL) of the
parameters of interest.
5.2 Stock standards: Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids. Because of the toxicity of benzene and 1,4-
dichlorobenzene, primary dilutions of these materials should be prepared in a
hood.
5.2.1 Place about 9.8 mL of methanol in a 10-mL tared ground-g5!ass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.2.2 Using a 100-uL syringe, immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
5.2.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
microliter (ug/uL) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction
8020 - 3
Revision
Date September 1986
-------
to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.2.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at 4*C and protect from
light. •'•
5.2.5 All standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
5.3 Secondary dilution standards; Using stock standard solutions, pre-
pare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards, should be prepared at concentrations such that the aqueous
calibration standards prepared in Paragraph 5.4 will bracket the working range
of the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.4 Calibration standards: Calibration standards at a minimum of five
concentration levels are prepared in reagent water from the,secondary dilution
of the stock standards. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Each
standard should contain each analyte for detection by this method (e.g., some
or all of the compounds listed in Table 1 may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
5.4.1 Do not inject more than 20 uL of alcoholic standards into 100
ml of reagent water.
5.4.2 Use a 25-uL Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.4.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.4.4 Mix aqueous standards by inverting the flask three times
only.
5.4.5- Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask).
8020 - 4
Revision
Date September 1986
-------
5.4.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.4.7 Aqueous standards are not stable and should be discarded
after 1 hr, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hr, If held in sealed vials with zero headspace.
5.5 Internal standards (if internal standard calibration is used): To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples. The
compound, alpha,alpha,alpha-trifluorotoluene recommended for use as a
surrogate spiking compound (Paragraph 5.6) has been used successfully as an
internal standards.
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described in
Section 5.4.
5.5.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.2 and 5.3. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ug/mL of each internal standard compound. The
addition of 10 uL of this standard to 5.0 mL of sample or calibration
standard would be equivalent to 30 ug/L.
5.5.3 Analyze each calibration standard according to Section 7.0,
adding 10 uL of internal standard spiking solution directly to the
syringe.
5.6 Surrogate standards: The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
water blank with surrogate compounds (e.g, alpha.alpha,alpha-trifluorotoluene)
recommended to encompass the range of the temperature program used in this
method. From stock standard solutions prepared as in Section 5.2, add a
volume to give 750 ug of each surrogate to 45 mL of reagent water contained in
a 50-mL volumetric flask, mix, and dilute to volume for a concentration of
15 ng/uL. Add 10 uL of this surrogate spiking solution directly into the 5-mL
syringe with every sample and reference standard analyzed. If the internal
standard calibration procedure is used, the surrogate compounds may be added
directly to the internal standard spiking solution (Paragraph 5.5.2).
5.7 Methanol; pesticide quality or equivalent. Store away from other
solvents.
8020 - 5
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are Introduced Into the gas chromatograph either
by direct Injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For medium-level soils or sediments, methanollc extraction, as
described 1n Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set helium gas flow at 36 mL/m1n flow rate. The
temperature program sequences are as follows: For lower boiling
compounds, operate at 50'C isothermal for 2 min; then program at 6*C/m1n
to 90*C and hold until all compounds have eluted. For higher boiling
range of compounds, operate at 50*C Isothermal for 2 m1n; then program at
3*C/min to 110'C and hold until all compounds have eluted. Column 1
provides outstanding separations for a wide variety of aromatic
hydrocarbons. Column 1 should be used as the primary analytical column
because of its unique ability to resolve para-, meta-, and ortho-aromatic
isomers.
7.2.2 Column 2: Set helium gas flow at 30 mL/min flow rate. The
temperature program sequence 1s as follows: 40*C Isothermal for 2 min;
then 2°C/min to 100'C and hold until all compounds have eluted. Column
2, an extremely high-polarity column, has been used for a number of years
to resolve aromatic hydrocarbons from alkanes in complex samples.
However, because resolution between some of the aromatlcs is not as
efficient as with Column. 1, Column 2 should be.used as a confirmatory
column.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample
Introduction method that will be used to analyze actual samples (see
Section 7.4.1).
7.3.2 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
8020 - 6
Revision
Date September 1986
-------
7.4 Gas chromatographlc analysis;
7.4.1 Introduce volatile compounds Into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection
method. If the internal standard calibration technique is used, add
10 uL of internal standard to the sample prior to purging.
7.4.1.1 Direct injection; In very limited applications (e.g.,
aqueous process wastes), direct Injection of the sample into the GC
system with a 10 uL syringe may be appropriate. The detection limit
is very high (approximately 10,000 ug/L); therefore, it is only
permitted when concentrations in excess of 10,000 ug/L are expected
or for water-soluble compounds that do not purge. The system must
be calibrated by direct injection (bypassing the purge-and-trap
device).
7.4.2 Follow Section 7.6 of Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times and
detection limits for a number of organic compounds analyzable using this
method. An example of the separation achieved by Column 1 is shown in
Figure 1. Figure 2 shows an example of the separation achieved using
Column 2.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Section 7.8 of
Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution
of the sample with reagent water. The dilution must be performed ion a
second aliquot of the sample which has been properly sealed and stored
prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered 1n Method 5030.
8.2 Mandatory quality control to validate the GC system operation is
found in Method 8000, Section 8.6.
8020 - .7
Revision 0
Date September 1986
-------
Column: 5% SP-1200/1.75% Bentone34
Program: 60<>C-2 Minutes. 6°C/Min. to 90°C
Detector: Photoionization
Sample: 0.40 jig/I Standard Mixture
oo
o
ro
o
oo
Ql (V
rf <
(/) O
(t> =3
O
(D
6 8 10 12 14
RETENTION TIME (MINUTES)
16
18
20
22
00
0>
Figure 1. Chromatogram of aromatic volatile organics (column 1 conditions).
-------
Column: 5% 1.2.3-Trii (2-Cyanoetrtoxy)
Propane on Chromosorb—W
Program: 40°C-2 Minutei 2OC/Min. to 100«C
Detector: Photoionization
Samplt: 2.0 MB/1 Standard Mixture
8 12 16
RETENTION TIME (MINUTES)
20
24
Figure 2. Chromatogram of aromatic volatile organics (column 2 conditions).
8020 - 9
Revision Q
Date September 1986
-------
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of Interest at a concentration
of 10 ug/mL in methanol.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 This method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 2.1-500 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the parameter and essentially independent of the sample
matrix. Linear equations to describe these relationships are presented in
Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, in Van Hall (ed.), Measurement of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
8020 - 10
Revision 0
Date September 1986
-------
3. Dowty, B.J., S.R. Antolne, and J.L. Laseter, "Quantitative and Qualitative
Analysis of Purgeable Organics by High Resolution Gas Chromatography and Flame
lonization Detection," in Van Hall, ed., Measurement of Organic Pollutants in
Water and Wastewater. ASTM STP 686, pp. 24-35, 1979.
4. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 11 - Purgeables and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane. Report for EPA Contract
68-03-2635 (in preparation).
5. "EPA Method Validation Study 24, Method 602 (Purgeable Aromatics)," Report
for EPA Contract 68-03-2856 (in preparation).
6. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
7. Provost, L.P., and R.S. Elder, ."Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
8020 - 11
Revision
Date September 1986
-------
TABLE 3. CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Chl orobenzene
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-D1 chl orobenzene
Ethyl benzene
Toluene
,
Range
for Q
(ug/L)
15.4-24.6
16.1-23.9
13.6-26.4
14.5-25.5
13.9-26.1
12.6-27.4
15.5-24.5
Limit
for s
(ug/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for 7
(ug/L)
10.0-27.9
12.7-25.4
10.6-27.6
12.8-25.5
11.6-25.5
10.0-28.2
11.2-27.7
Range
P, PS
t V \
\ /
39-150
55-135
37-154
50-141
42-143
32-160
46-148
Q = Concentration measured 1n QC check sample, 1n ug/L.
s = Standard deviation of four recovery measurements, In ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, Ps = Percent recovery measured.
aCr1ter1a are from 40 CFR Part 136 for Method 602 and were calculated
assuming a QC check sample concentration of 20 ug/L. These criteria are based
directly upon the method performance data in Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 1.
8020 - 12
Revision
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Benzene
Chlorobenzene
1 , 2-D1 chl orobenzene
1,3-01 chlorobenzene
1 , 4-D1 chl orobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x1
(ug/L)
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
0.93C-0.09
0.94C+0.31
0.94C+0.65
Single analyst Overall
precision, sr'
(ug/L)
0.097+0.59
0.097+0.23
0.177-0.04
0.157-0.10
0.157+0.28
0.177+0.46
0.097+0.48
precision,
S1 (ug/L)
0.217+0.56
0.177+0.10
0.227+0.53
0.197+0.09
0.207+0.41
0.267+0.23
0.187-0.71
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, 1n ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, 1n ug/L.
8020 - 13
Revision 0
Date September 1986
-------
METHOD B020
AROMATIC VOLATILE ORGANICS
7. J
Q
Introduce compounds
Into gas
chromatograph by
direct Injection or
purge-ano-trap
(Method 5030)
7.2
7.4.4
Record
volume purged
or injected and
peak sizes
Set gas
chromatosraph
condition
7.3
7.4.5
Calculate
concentration
(Section 7.6.
Method BOOO)
o
Calibrate
(refer tc
Method 6000!
7.4.1
Yes
' \.' B
Are analytically.
Interferences
suspected?
7.4.6
Introduce volatile
compounds into gas
chromatooraph by
Method 5030 or
direct injection
7.4.8
Follow
Section 7.6
in Method BOOO
for analysis
sequence, etc.
Analyze using
second GC
column
Dilute second
aliquot of
sample
8020 - 14
Revision 0
Date September 1986
-------
METHOD 8030
ACROLEIN. ACRYLONITRILE. ACETONITRILE
1.0 SCOPE AND APPLICATION
1.1 Method 8030 is used to determine the concentration of the following
three volatile organic compounds:
Acrolein (Propenal)
Acrylonltrile
Acetonltrile
1.2 Table 1 lists chromatographlc conditions and method detection limits
for acrolein and acrylonitrlle in reagent water. Table 2 lists the practical
quantisation limit (PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8030 provides gas chromatographlc conditions for the
detection of the three volatile organic compounds. Samples can be analyzed
using direct Injection or purge-and-trap (Method 5030). Ground water samples
must be analyzed using Method 5030. A temperature program is used 1n the gas
chromatograph to separate the organic compounds. Detection 1s achieved by a
flame ionization detector (FID).
2.2 The method provides an optional gas chromatographlc column that may
be helpful in resolving the analytes from interferences that may occur and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Methods 5030 and 8000.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detectors, column
supplies, recorder, gases, and syringes. A data system for measuring
peak height and/or peak area 1s recommended.
8030 - 1
Revision 0
Date September 1986
-------
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Retention time Method
(m1n) detection
I1m1ta
Compound Col. 1Col. 2 (ug/L)
Acroleln 10.6 8.2 0.7
Acrylon1tr1le 12.7 9.8 0.5
a Based on using purge-and-trap, Method 5030.
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil 10
Water mlsdble liquid waste 500
High-level soil and sludge 1250
Non-water mlsdble waste 1250
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = .[Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8030 - 2
Revision
Date September 1986
-------
4.1.2 Columns:
4.1.2.1 Column 1: 10-ft x 2-mm I.D. stainless steel or glass
packed with Porapak-QS (80/100 mesh) or equivalent.
4.1.2.2 Column 2: 6-ft x O.l-1n I.D. stainless steel or glass
packed with Chromosorb 101 (60/80 mesh) or equivalent.
4.1.3 Detector: Flame 1on1zat1on (FID).
4.2 Sample Introduction apparatus; Refer to Method 5030 for the
appropriate equipment for sample Introduction purposes.
4.3 Syringes: A 5-mL Luerlok glass hypodermic and a 5-mL, gas-tight
with shutoff valve.
4.4 Volumetric flask; 10-, 50-, 100-, 500-, and 1,000-mL with a ground-
glass stopper.
4.5 Microsyringe; 10- and 25-uL with a 0.006-1n I.D. needle (Hamilton
702N or equivalent) and a 100-uL.
5.0 REAGENTS
5.1 Reagent water; Reagent water 1s defined as a water 1n which an
interferent isnotoEserved at the method detection limit (MDL) of the
parameters of interest.
5.2 Stock standards; Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
methanol using assayed liquids. Because acroleln and acrylonitrlle are
lachrymators, primary dilutions of these compounds should be prepared in a
hood.
5.2.1 Place about 9.8 ml of reagent water 1n a 10-mL tared ground-
glass-stoppered volumetric flask. For acrolein standards the reagent
water must be adjusted to pH 4-5 using hydrochloric add (1:1) or sodium
hydroxide (10 N), if necessary. Weigh the flask to the nearest 0.1 mg.
5.2.2 Using a 100-uL syringe, Immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the water without contacting the neck of the flask.
5.2.3 Reweigh, dilute to volume, stopper, and then mix by Inverting
the flask several times. Calculate the concentration 1n mlcrograms per
microllter (ug/uL) from the net gain 1n weight. When compound purity 1s
assayed to be 96% or greater, the weight may be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an Independent source.
8030 - 3
Revision
Date September 1986
-------
5.2.4 Transfer the stock standard solution Into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at 4*C and protect from
light.
5.2.5 Prepare fresh standards dally.
5.3 Secondary dilution standards; Using stock standard solutions, pre-
pare In reagent water secondarydTTution standards, as needed, that contain
the compounds of Interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Paragraph 5.4 will bracket the working range
of the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatlles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels are prepared in reagent water from the secondary dilution
of the stock standards. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Each
standard should contain each analyte for detection by this method. In order
to prepare accurate aqueous standard solutions, the following precautions must
be observed.
5.4.1 Use a 25-uL Hamilton 702N microsyrlnge or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of standards into water).
5.4.2 Never use plpets to dilute or transfer samples or aqueous
standards.
5.4.3 These standards must be prepared daily.
5.5 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the internal standard 1s not
affected by method or matrix Interferences. Because of these limitations, no
Internal standard can be suggested that is applicable to all samples.
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described 1n
Section 5.4.
5.5.2 Prepare a spiking solution containing each of the internal
standards using the procedures described 1n Sections 5.2 and 5.3. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ug/mL of each internal standard compound. The
addition of 10 uL of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
8030 - 4
Revision 0
Date September 1986
-------
5.5.3 Analyze each calibration standard according to Section 7.0,
adding 10 uL of Internal standard spiking solution directly to the
syringe.
5.6 Surrogate standards; The analyst should monitor both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
water blank with one or two surrogate compounds (e.g., compounds similar in
analytical behavior to the analytes of interest but which are not expected to
be present in the sample) recommended to encompass the range of the
temperature program used in this method. From stock standard solutions
prepared as in Section 5.2, add a volume to give 750 ug of each surrogate to
45 ml of reagent water contained in a 50-mL volumetric flask, mix, and dilute
to volume for a concentration of 15 ng/uL. Add 10 uL of this surrogate
spiking solution directly Into the 5-mL syringe with every sample and
reference standard analyzed. If the Internal standard calibration procedure
is used, the surrogate compounds may be added directly to the Internal
standard spiking solution (Paragraph 5.5.2).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Volatile compounds are Introduced Into the gas chromatograph either
by direct Injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For high-level soils or sediments, methanollc extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set helium gas flow at 30 mL/m1n flow rate. Set
column temperature at 110*C for 1.5 m1n; then heat as rapidly as possible
to 150*C and hold for 20 min.
7.2.2 Column 2: Set helium gas flow at 40 mL/min flow rate. Set
column temperature at 80*C for 4 min; then program at 50*C/m1n to 120°C
and hold for 12 min.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample
introduction method that will be used to analyze actual samples (see
Section 7.4.1).
8030 - 5
Revision
Date September 1986
-------
7.3.2 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.4 Gas chromatographlc analysis;
7.4.1 Introduce volatile compounds Into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct Injection
method. If the Internal standard calibration technique 1s used, add
10 uL of the Internal standard to the sample prior to purging.
7.4.1.1 Direct Injection: In very limited applications (e.g.,
aqueous process wastes), direct Injection of the sample Into the GC
system with a 10 uL syringe may be appropriate. The detection limit
Is very high (approximately 10,000 ug/L); therefore, 1t 1s only
permitted when concentrations In excess of 10,000 ug/L are expected
or for water-soluble compounds that do not purge. The system must
be calibrated by direct Injection (bypassing the purge-and-trap
device).
7.4.2 Follow Section 7.6 of Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes rthe estimated retention times and
detection limits for a number of organic compounds analyzable using this
method. Figure 1 illustrates the chromatographlc separation of acrolein
and of acrylonitrile using Column 1.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Calculation of concentration is covered in Section 7.8 of
Method 8000.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution
of the sample with reagent water. The dilution must be performed on a
second aliquot of the sample which has been properly sealed and stored
prior to use.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8030 - 6
Revision 0
Date September 1986
-------
Column: Porapak-QS
Program. 110°C for 1.5 mm. rapidly
healed to 150°C
Detector: Flame lonization
1.6
30
45
60
7.5
9.0
10.5
120, 135
150
RETENTION TIME. MtN.
Figure 1. Gas chromatogram of acroleln and acrylonltrlle.
8030 - 7
Revision 0
Date September 1986
-------
8.2 Procedures to check the GC system operation are found 1n Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of Interest at a concentration
of 25 ug/mL 1n reagent water.
8.2.2 Table 3 Indicates the calibration and QC acceptance criteria
for this method. Table 4 gives single laboratory accuracy and precision
for the analytes of Interest. The contents of both Tables should be used
to evaluate a laboratory's ability to perform and generate acceptable
data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine If recovery 1s within limits (limits established by
performing QC procedure outlined 1n Method 8000, Section 8.10).
8.3.1 If recovery 1s not within limits, the following 1s required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and Internal standards. Also, check
Instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 In a single laboratory, the average recoveries and standard
deviations presented 1n Table 4 were obtained using Method 5030. Seven
replicate samples were analyzed at each spike level.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample Introduction technique, and by the calibration procedure used.
10.0 REFERENCES
1. Bellar, T.A. and J.J. Uchtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A. and J.J. Uchtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," 1n Van Hall, ed., Measurement of Organic Pollutants 1n Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
8030 - 8
Revision
Date September 1986
-------
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters, Category 11: Purgeables and Category 12: Acrolein,
Acrylonitrile, and Dichlorodifluoromethane, Report for EPA Contract 68-03-2635
(in preparation).
4. Going, J., et al., Environmental Monitoring Near Industrial Sites -
Acrylonitrile, Office of Toxic Substances, U.S. EPA, Washington, DC, EPA
560/6-79-003, 1979.
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63, 1983.
7. Kerns, E.H., et al. "Determination of Acrolein and Acrylonitrile in Water
by Heated Purge and Trap Technique," U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, 1980.
8. "Evaluation of Method 603," Final Report for EPA Contract 68-03-1760 (in
preparation).
8030 - 9
Revision
Date September 1986
-------
TABLE 3. CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Acrolein
Acrylonitrile
Range
for Q
(ug/L).
45.9-54.1
41.2-58.8
Limit
for S
(ug/L)
4.6
9.9
Range
for 7
(ug/L)
42.9-60.1
33.1-69.9
Range
P. PS
(%)
88-118
71-135
Q = Concentration measured in QC check sample, in ug/L.
S = Standard deviation of four recovery measurements, in ug/L.
7 = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
Criteria from 40 CFR Part 136 for Method 603 and were calculated
assuming a QC check sample concentration of 50 ug/L.
TABLE 4. SINGLE LABORATORY ACCURACY AND PRECISION
Parameter
Acrolein
Acrylonitrile
Spi ke
cone.
(ug/L)
5.0
50.0
5.0
50.0
5.0
100.0
5.0
50.0
20.0
100.0
10.0
100.0
Average
recovery
(ug/L)
5.2
51.4
4.0
44.4
0.1
9.3
4.2
51.4
20.1
101.3
9.1
104.0
Standard
deviation
(ug/L)
0.2
0.7
0.2
0.8
0.1
1.1
0.2
1.5
0.8
1.5
0.8
3.2
Average
percent
recovery
104
103
80
89
2
9
84
103
100
101
91
104
Sample
matrix3
RW
RW
POTW
POTW
IW
IW
RW
RW
POTW
POTW
IW
IW
aRW = Reagent water.
POTW = Prechlorination secondary effluent from a municipal sewage treatment
plant.
IW = Industrial wastewater containing an unidentified acrolein reactant.
8030 - 10
Revision 0
Date September 1986
-------
METHOD 8030
ACROLEIN. ACRYLONITRILE. ACETONITRILE
7.1
Introduce compounas
Into B>S
chromatograph by
direct Injection or
purge-ana-tr,ap
(Method S030)
o
7 .Z
Set gas
chromatograph
condition
7.3
Calibrate
(refer to
Method BOOO)
7.4.1
Introduce volatile
compounds Into gas
chromatograph by
Method SO3O or
direct Injection
7.4.2
Follow
Section 7.6
In Method 8000
for analysis
•eguence. etc.
O
Record
volume purged
or Injected and
peak sizes
Calculate
concentration
(Section 7.6.
Method BOOO)
Are analytical
Interferences
suspected?
Analyze using
second GC
column
la response for
a peak off-acale?
Dilute second
aliquot of
sample
8030 - 11
Revision o
Date September 1986
-------
METHOD 8040
PHENOLS
1.0 SCOPE AND APPLICATION
1.1 Method 8040 1s used to determine the concentration of various
phenolic compounds. Table 1 Indicates compounds that may be analyzed by this
method and lists the method detection limit for each compound 1n reagent
water. Table 2 lists the practical quantltatlon limit (PQL) for other
matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8040 provides gas chromatographic conditions for the
detection of phenolic compounds. Prior to analysis, samples must be extracted
using appropriate techniques (see Chapter Two for guidance). Both neat and
diluted organic liquids (Method 3580, Waste Dilution) may be analyzed by
direct Injection. A 2- to 5-uL sample 1s Injected Into a gas chromatograph
using the solvent flush technique, and compounds in the GC effluent are
detected by a flame 1on1zat1on detector (FID).
2.2 Method 8040 also provides for the preparation of pentafluorobenzyl-
bromlde (PFB) derivatives, with additional cleanup procedures for electron
capture gas chromatography. This 1s to reduce detection limits of some
phenols and to aid the analyst 1n the elimination of interferences.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by running method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
8040 - 1
Revision 0
Date September 1986
-------
TABLE 1. FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS
Method
Retention time Detection
Compound (min) limit (ug/L)
2-sec-Butyl-4,6-dinitrophenol (DNBP)
4-Chloro-3-methylphenol 7.50 0.36
2-Chlorophenol 1.70 0.31
Cresols (methyl phenols)
2-Cyclohexyl-4,6-di ni trophenol
2,4-Dichlorophenol 4.30 0.39
2,6-Dichlorophenol
2,4-Dimethylphenol 4.03 0.32
2,4-Dinitrophenol 10.00 13.0
2-Methyl-4,6-dinitrophenol 10.24 16.0
2-Nitrophenol 2.00 0.45
4-N1trophenol 24.25 2.8
Pentachlorophenol 12.42 7.4
Phenol 3.01 0.14
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol 6.05 0.64
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix , Factorb
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste ' 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
8040 - 2
Revision 0
Date September 1986
-------
accessories, Including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
4.1.2 Columns:
4.1.2.1 Column for underivatized phenols: 1.8-m x 2.0-iron I.D.
glass column packed with 1% SP-1240DA on Supelcoport 80/100 mesh or
equivalent.
4.1.2.2 Column for derivatlzed phenols: 1.8-m x 2-mm I.D.
glass column packed with 5% OV-17 on Chromosorb W-AW-DMCS 80/100
mesh or equivalent.
4.1.3 Detectors: Flame lonization (FID) and electron capture
(ECD).
4.2 Reaction vial; 20-mL, with Teflon-lined cap.
4.3 Volumetric flask; 10-, 50-, and 100-mL, ground-glass stopper.
4.4 Kuderna-Danish (K-D) apparatus;
4.4.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts
4.4.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.4.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.4.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.5 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used 1n a hood.
4.7 Microsyringe; 10-uL.
4.8 Syringe; 5-mL.
5.0 REAGENTS
5.1 Solvents: Hexane, 2-propanol, and toluene (pesticide quality or
equivalent)^
8040 - 3
Revision 0
Date September 1986
-------
5.2 Derlvatization reagent; Add 1 ml pentafluorobenzyl bromide and 1 g
18-crown-6-ether to a 50-mL volumetric flask and dilute to volume with 2-
propanol. Prepare fresh weekly. This operation should be carried out in a
hood. Store at 4'C and protect from light.
5.2.1 Pentafluorobenzyl bromide (alpha-Bromopentafluorotoluene):
97% minimum purity.
NOTE: This chemical is a lachrymator.
5.2.2 18-crown-6-ether (1,4,7,10,13,16-Hexaoxacyclooctadecane):
98% minimum purity.
NOTE: This chemical is highly toxic.
5.3 Potassium carbonate; (ACS) Powdered.
5.4 Stock standard solutions;
5.4.1 Prepare stock standard solution at a concentration of 1.00
ug/uL by dissolving 0.0100 g of assayed reference material in 2-propanol
and diluting to volume in a 10-mL volumetric flask. Larger volumes can
be used at the convenience of the analyst. When compound purity is
assayed to be 96% or greater, the weight can be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.4.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4°C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.4.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.5 Calibration standards; Calibration standards at a minimum of five
concentrationlevelsshouldbe prepared through dilution of the stock
standards with 2-propanol. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC.
Calibration solutions must be replaced after six months, or sooner, if
comparison with check standards indicates a problem.
5.6 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.6.1 Prepare calibration standards at a minimum of five
concentrations for each analyte as described in Paragraph 5.5.
8040 - 4
Revision 0
Date September 1986
-------
5.6.2 To each calibration standard, add a known constant amount of
one or more Internal standards, and dilute to volume with 2-propanol.
5.6.3 Analyze each calibration standard according to Section 7.0.
5.7 Surrogate standards; The analyst should monitor the performance of
the extraction,cleanup (Tf necessary), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with phenolic surrogates (e.g., 2-
fluorophenol and 2,4,6-tribromophenol) recommended to encompass the range of
the temperature program used in this method. Method 3500, Section 5.3.1.1,
details instructions on the preparation of acid surrogates. Deuterated
analogs of analytes should not be used as surrogates for gas chromatographic
analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction:
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a pH of
less than or equal to 2 with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
Extracts obtained from application of either Method 3540 or 3550 should
undergo Acid-Base Partition Cleanup, using Method 3650.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to 2-propanol. The exchange 1s performed during the
micro K-D procedures listed in all of the extraction methods. The
exchange is performed as follows.
7.1.2.1 Following K-D of the extract to 1 mL using the macro-
Snyder column, allow the apparatus to cool and drain for at least 10
min.
7.1.2.2 Increase the temperature of the hot water bath to
95-100'C. Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1-2 mL of 2-propanol. A
5-mL syringe is recommended for this operation. Add one or two
clean boiling chips to the concentrator tube and attach a two-ball
micro-Snyder column. Prewet the column by adding about 0.5 mL of 2-
propanol to the top. Place the K-D apparatus on the water bath so
that the concentrator tube 1s partially immersed in the hot water.
8040 - 5
Revision 0
Date September 1986
-------
Adjust the vertical position of the apparatus and the water
temperature, as required, to complete concentration 1n 5-10 m1n. At
the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 2.5 ml, remove the K-D apparatus
and allow 1t to drain and cool for at least 10 m1n. Add an
additional 2 ml of 2-propanol , add one or two clean boiling chips
to the concentrator tube, and resume concentrating as before. When
the apparent volume of liquid reaches 0.5 ml, remove the K-D
apparatus and allow 1t to drain and cool for at least 10 m1n.
7.1.2.3 Remove the mlcro-Snyder column and rinse Its lower
joint Into the concentrator tube with a minimum amount of 2-
propanol. Adjust the extract volume to 1.0 ml. Stopper the
concentrator tube and store refrigerated at 4*C 1f further
processing will not be performed Immediately. If the extract will
be stored longer than two days, 1t should be transferred to a
Teflon-sealed screw-cap vial. If the extract requires no further
der1vat1zat1on or cleanup, proceed with gas chromatographlc
analysis.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column for underlvatlzed phenols: Set nitrogen gas flow at
30 mL/m1n flow rate. Set column temperature at 80*C and Immediately
program an 8*C/m1n temperature rise to 150*C; hold until all compounds
have eluted.
7.2.2 Column for derlvatlzed phenols: Set 5% methane/95% argon gas
flow at 30 mL/m1n flow rate. Set column temperature at 200'C Isothermal.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques"^Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external calibration may be
used for the underlvatlzed phenols. Refer to Method 8000 for a
description of each of these procedures. If der1vat1zat1on of the
phenols 1s required, the method of external calibration should be used by
Injecting five or more levels of calibration standards that have also
undergone der1vat1zat1on and cleanup prior to Instrument calibration.
7.4 Gas chromatographlc analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique 1s used, add 10 uL of Internal standard to the sample prior to
Injection.
7.4.2 Phenols are to be determined on a gas chromatograph equipped
with a flame 1on1zat1on detector according to the conditions listed for
the 1% SP-1240DA column (Paragraph 7.2.1). Table 1 summarizes estimated
8040 - 6
Revision 0
Date September 1986
-------
retention times and sensitivities that should be achieved by this method
for clean water samples. Practical quantltation limits for other
matrices are list 1n Table 2.
7.4.3 Follow Section 7.6 In Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.4.4 An example of a GC/FID chromatogram for certain phenols is
shown in Figure 1. Other packed or capillary (open-tubular) columns,
chromatographic conditions, or detectors may be used if the requirements
of Section 8.2 are met.
7.4.5 Record the sample volume injected and the resulting peak
sizes (in area units or peak heights).
7.4.6 Using either the Internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
1n the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Section 7.8 of Method 8000 for calculation
equations.
7.4.7 If peak detection using the SP-1240DA column with the flame
ionization detector is prevented by interferences, PFB derivatives of the
phenols should be analyzed on a gas chromatograph equipped with an
electron capture detector according to the conditions listed for the 5%
OV-17 column (Paragraph 7.2.2). The derivatizatlon and cleanup procedure
is outlined in Sections 7.5 through 7.6. Table 3 summarizes estimated
retention times for derivatives of some phenols using the conditions of
this method.
7.4.8 Figure 2 shows a GC/ECD chromatogram of PFB derivatives of
certain phenols.
7.4.9 Record the sample volume Injected and the resulting peak
sizes (in area units or peak heights).
7.4.10 Determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. The method of external calibration should be used
(see Method 8000 for guidance). The concentration of the Individual
compounds In the sample is calculated as follows.
Concentration (ug/L) = [(A)(Vt)(B)(D)]/[(Vt)(X)(C)(E)]
where:
A = Mass of underivatlzed phenol represented by area of peak in sample
chromatogram, determined from calibration curve (see Method 8000
Paragraph 7.4.2), ng.
8040 - 7
Revision 0
Date September 1986
-------
Column: 1% SP-1240DA on Supelcoport
Program: 80°C 0 Minutes 8°/Minute to 150°C
Detector: Flame lonization
8 12 16 20
RETENTION TIME (MINUTES)
24 28
Figure 1. Gas chromatogram of phenols.
8040 - 8
Revision o
Date September 1986
-------
TABLE 3. ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES
Parent compound
Retention
time
(m1n)
Method
detection
limit (ug/L)
4-Chloro-2-methylphenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-01methyl phenol
2,4-D1n1trophenol
2-Methy1-4,6-d1nltrophenol
2-N1trophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-TH chlorophenol
4.8
3.3
5.8
2.9
46.9
36.6
9.1
14.0
28.8
1.8
7.0
1.8
0.58
0.68
0.63
0.77
0.70
0.59
2.2
0.58
8040 - 9
Revision 0
Date September 1986
-------
Column: S% OV-17 on Qiromowrb W-AW
Temperature: 200°C
Detector: Electron Capture
(M CN
1
8 12 16 20 24 28
RETENTION TIME (MINUTES)
32
Figure 2. Gas chromatogram of PFB derivativas of phanols.
8040 - 10
Revision 0
Date September 1986
-------
Vt = Total amount of column eluate or combined fractions from which Vj
was taken, uL.
B = Total volume of hexane added in Paragraph 7.5.5, ml.
D = Total volume of 2-propanol extract prior to der1vat1zat1on, mL.
Vj = Volume injected, uL.
X = Volume of water extracted, ml, or weight of nonaqueous sample
extracted, g, from Section 7.1. Either the dry or wet weight of
the nonaqueous sample may be used, depending upon the specific
application of the data.
C = Volume of hexane sample solution added to cleanup column (Method
3630,, Section 7.2), ml.
E = Volume of 2-propanol extract carried through derivatization in
Paragraph 7.5.1, ml.
7.5 Derivatization; If interferences prevent measurement of peak area
during analysis of theextract by flame ionization gas chromatography, the
phenols must be derivatized and analyzed by electron capture gas
chromatography.
7.5.1 Pipet a 1.0-mL aliquot of the 2-propanol stock standard
solution or of the sample extract into a glass reaction vial. Add 1.0 ml
derivatization reagent (Paragraph 5.3). This amount of reagent 1s
sufficient to derivatize a solution whose total phenolic content does not
exceed 0.3 mg/mL.
7.5.2 Add approximately 3 mg of potassium carbonate to the solution
and shake gently.
7.5.3 Cap the mixture and heat it for 4 hr at 80*C in a hot water
bath.
7.5.4 Remove the solution from the hot water bath and allow it to
cool. - .
7.5.5 Add 10 ml hexane to the reaction vial and shake vigorously
for 1 min. Add 3.0 ml distilled, deionized water to the reaction vial
and shake for 2 min.
7.5.6 Decant the organic layer into a concentrator tube and cap
with a glass stopper. Proceed with cleanup procedure.
7.6 Cleanup;
7.6.1 Cleanup of the derivatized extracts takes place using Method
3630 (Silica Gel Cleanup), in which specific instructions for cleanup of
the derivatized phenols appear.
8040 - 11
Revision 0
Date September 1986
-------
7.6.2 Following column cleanup, analyze the samples using GC/ECD,
as described starting 1n Paragraph 7.4.7.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method used. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found 1n Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each analyte of interest at a concentration
of 100 ug/mL 1n 2-propanol.
8.2.2 Table 4 indicates the calibration and QC acceptance criteria
for this method. Table 5 gives method accuracy and precision as
functions of concentration for the analytes. The contents of both Tables
should be used to evaluate a laboratory's ability to perform and generate
acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine 1f the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery 1s not within limits, the following is required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and internal standards. Also, check
Instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 12 to 450 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the analyte and essentially Independent of the sample
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 5.
8040 - 12
Revision 0
Date September 1986
-------
9.2 The accuracy and precision obtained will be affected by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. Development and Application of Test Procedures for Specific Organic Toxic
Substances In Wastewaters. Category 3 - Chlorinated Hydrocarbons and Category
8 - Phenols. Report for EPA Contract 68-03-2625 (in preparation).
2. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
3. "Determination of Phenols in Industrial and Municipal Wastewaters," Report
for EPA Contract 68-03-2625 (in preparation).
4. "EPA Method Validation Study Test Method 604 (Phenols)," Report for EPA
Contract 68-03-2625 (1n preparation).
5. Kawarahara, F.K. "Microdetermination of Derivatives of Phenols and
Mercaptans by Means of Electron Capture Gas Chromatography," Analytical
Chemistry, 40, 1009, 1968.
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
7. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8040 - 13
Revision
Date September 1986
-------
TABLE 4. QC ACCEPTANCE CRITERIA3
Parameter
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-01 methyl phenol
4, 6-D1 n1 tro-2-methyl phenol
2,4-D1n1trophenol
2-N1trophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
16.6
27.0
25.1
33.3
25.0
36.0
22.5
19.0
32.4
14.1
16.6
Range
for 7
(ug/L)
56.7-113.4
54.1-110.2
59.7-103.3
50.4-100.0
42.4-123.6
31.7-125.1
56.6-103.8
22.7-100.0
56.7-113.5
32.4-100.0
60.8-110.4
Range
P, PS
(%)
99-122
38-126
44-119
24-118
30-136
12-145
43-117
13-110
36-134
23-108
53-119
s = Standard deviation of four recovery measurements, In. ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, Ps = Percent recovery measured.
aCr1ter1a from 40 CFR Part 136 for Method 604. These criteria are based
directly upon the method performance data 1n Table 5. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 5.
8040 - 14
Revision 0
Date September 1986
-------
TABLE 5. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-D1methylphenol
4, 6-D1n1tro-2-methyl phenol
2,4-D1n1trophenol
2-Nttrophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Accuracy, as
recovery, x1
(ug/L)
0.87C-1.97
0.83C-0.84
0.81C+0.48
0.62C-1.64
0.84C-1.01
0.80C-1.58
0.81C-0.76
0.46C+0.18
0.83C+2.07
0.43C+0.11
0.86C-0.40
Single analyst
precision, sr'
(ug/L)
0.117-0.21
0.187+0.20
0.177-0.02
0.307-0.89
0.157+1.25
0.277-1.15
0.157+0.44
0.177+2.43
0.227-0.58
0.207-0.88
0.107+0.53
Overal 1
precision,
S' (ug/L)
0.167+1.41
0.217+0.75
0.187+0.62
0.257+0.48
0.197+5.85
0.297+4.51
0.147+3.84
0.197+4.79
0.237+0.57
0.177+0.77
0.137+2.40
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, 1n ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, 1n ug/L.
S1 = Expected Interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
aFrom 40 CFR Part 136 for Method 604.
8040 - 15
Revision 0
Date September 1986
-------
METHOD BO4O
PHENOLS
c
7.1.1
Choose
' appro-
priate extract-
Ion procedure
(refer to
Chapter 2)
Use method of
external calibration
by Injecting >/- 5
levels of calibration
standards
7.1.2
Exchange
extract-
Ion solvent to
2—propanol
during micro
K-O procedures
7.2
Set gas
chromatography
conditions
7.3
Refer to
Method 8OOO
for proper
calibration
techniques
Is
derIvatlzatlon
of phenols
required?
Perform GC
analysis (see
Method 8OOO)
0
8040 - 16
Revision 0
Date • September 1986
-------
METHOD 6O4O
PHENOLS
(Continued]
Do
interferences
prevent peak
detection
Cleanup using
Method 3630
Record
sample volume
injected ana
peak sizes
Prepare
derlvatlzetion
identity and
quantity of
each
component peak
Analyze PFB
derivatives
using GC/CCD
Calculate
concentration
8040 - 17
Revision Q
Date September 1986
-------
METHOD 8060
PHTHALATE ESTERS
1.0 SCOPE AND APPLICATION
1.1 Method 8060 is used to determine the concentration of various
phthalate esters. Table 1 indicates compounds that may be determined by this
method and lists the method detection limit for each compound in reagent
water. Table 2 lists the practical quantitation limit (PQL) for other
matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8060 provides gas chromatographic conditions for the
detection of ppb levels of phthalate esters. Prior to use of this method,
appropriate sample extraction techniques must be used. Both neat and diluted
organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. A 2- to 5-uL aliquot of the extract is injected into a gas
chromatograph (GC) using the solvent flush technique, and compounds in the GC
effluent are detected by an electron capture detector (ECD) or a flame
ionization detector (FID). Ground water samples should be determined by ECD.
2.2 The method provides a second gas chromatographic column that may be
helpful in resolving the analytes from interferences that may occur and for
analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Phthalate esters contaminate many types of products commonly found
in the laboratory. The analyst must demonstrate that no phthalate residues
contaminate the sample or solvent extract under the conditions of analysis.
Plastics, in particular, must be avoided because phthalates are commonly used
as plasticizers and are easily extracted from plastic materials. Serious
phthalate contamination may result at any time if consistent quality control
is not practiced.
3.3 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.4 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
8060 - 1
Revision 0
Date September 1986
-------
TABLE 1. RETENTION TIME AND DETECTION LIMIT INFORMATION FOR PHTHALATE ESTERS
Retention time (m1n) Method detection
limit (ug/L)
Compound Col. la Col. 2D ECD FID
Benzyl butyl phthalate
B1 s (2-ethyl hexyl Jphthal ate
D1-n-butyl phthalate
D1 ethyl phthalate
Dimethyl phthalate
D1-n-octyl phthalate
*6.94
*8.92
8.65
2.82
2.03
*16.2
**5.11
**10.5
3.50
1.27
0.95
**8.0
0.34
2.0
0.36
0.49
0.29
3.0
15
20
14
31
19
31
aColumn 1: Supelcoport 100A120 mesh coated with 1.5% SP-2250/1.95% SP-
2401 packed 1n a 180-cm x 4-mrn I.D. glass column with carrier gas at 60
mL/m1n flow rate. Column temperature 1s 180*C, except where * Indicates
220*C. Under these conditions the retention time of Aldrln 1s 5.49 m1n
at 180*0 and 1.84 mln at 220'C.
bColumn 2: Supelcoport 100/120 mesh with 3% OV-1 1n a 180-cm x 4-mm I.D.
glass column with carrier gas at 60 mL/m1n flow rate. Column temperature
1s 200*C, except where ** Indicates 220*C. Under these conditions the
retention time of Aldrln 1s 3.18 m1n at 200'C and 1.46 m1n at 220*C.
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES*
Matrix Factor0
Ground water 10
Low-level soil by sonlcation with GPC cleanup 670
High-level soil and sludges by sonlcatlon 10,000
Non-water mlsclble waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
DPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8060 - 2
Revision
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas chromatograph: Analytical system complete with gas
chromatograph suitable for on-column Injections and all required
accessories, Including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: 1.8-m x 4-mm I.D. glass column packed with
1.5% SP-2250/1.95% SP-2401 on Supelcoport 100/120 mesh or
equivalent.
4.1.2.2 Column 2: 1.8-m x 4-mm I.D. glass column packed with
3% OV-1 on Supelcoport 100/120 mesh or equivalent.
4.1.3 Detectors: Flame ionlzation (FID) or electron capture (ECD).
4.2 Volumetric flask; 10-, 50-, and 100-mL, ground-glass stopper.
4.3 Kuderna-Danish (K-D) apparatus;
4.3.1 Concentrator tube; 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper 1s used to prevent evaporation of
extracts
•*
4.3.2 Evaporation flask; 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.3.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.6 Microsyringe; 10-uL.
4.7 Syringe; 5-mL.
4.8 Vials; Glass, 2- and 20-mL capacity with Teflon-lined screw cap.
8060 - 3
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 Solvents; Hexane, acetone, Isooctane (2,2,4-trlmethylpentane)
(pesticide quality or equivalent).
5.2 Stock standard solutions:
5.2.1 Prepare stock standard solutions at a concentration of 1.00
ug/uL by dissolving 0.0100 g of assayed reference material in isooctane
and diluting to volume in a 10-mL volumetric flask. Larger volumes can
be used at the convenience of the analyst. When compound purity is
assayed to be 96% or greater, the weight can be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.2.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4'C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.3 Calibration standards: Calibration standards at a minimum of five
concentrationlevelsshouldbe prepared through dilution of the stock
standards with isooctane. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC.
Calibration solutions must be replaced after six months, or sooner if
comparison with check standards indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest as described in
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with Isooctane.
5.4.3 Analyze each calibration standard according to Section 7.0.
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction, cleanup(when used), and analytical system and the effec-
tiveness of the method in dealing with each sample matrix by spiking each
8060 - 4
Revision 0
Date September 1986
-------
sample, standard, and reagent water blank with one or two surrogates (e.g.,
phthalates that are not expected to be In the sample) recommended to encompass
the range of the temperature program used 1n this method. Method 3500,
Section 5.3.1.1, details Instructions on the preparation of base/neutral
surrogates. Deuterated analogs of analytes should not be used as surrogates
for gas chromatographlc analysis due to coelutlon problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as 1s, pH with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographlc analysis, the extraction solvent
must be exchanged to hexane. The exchange 1s performed during the K-D
procedures listed 1n all of the extraction methods. The exchange 1s
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 m1n.
7.1.2.2 Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube 1s partially Immersed 1n the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 min. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus and allow 1t to drain and
cool for at least 10 m1n. The extract will be handled differently
at this point, depending on whether or not cleanup 1s needed. If
cleanup is not required, proceed to Paragraph 7.1.2.3. If cleanup
is needed, proceed to Paragraph 7.1.2.4.
7.1.2.3 If cleanup of the extract 1s not required, remove the
Snyder column and rinse the flask and Its lower joint Into the
concentrator tube with 1-2 mL of hexane. A 5-mL syringe 1s
recommended for this operation. Adjust the extract volume to
8060 - 5
Revision 0
Date September 1986
-------
10.0 ml. Stopper the concentrator tube and store refrigerated at
4*C if further processing will not be performed Immediately. If the
extract will be stored longer than two days, 1t should be
transferred to a Teflon-sealed screw-cap vial. Proceed with gas
chromatographlc analysis.
7.1.2.4 If cleanup of the extract 1s required, remove the
Snyder column and rinse the flask and Its lower joint Into the
concentrator tube with a minimum amount of hexane. A 5-mL syringe
1s recommended for this operation. Add a clean boiling chip to the
concentrator tube and attach a two-ball mlcro-Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top. Place the
m1cro-K-D apparatus on the water bath (80°C) so that the
concentrator tube 1s partially Immersed 1n the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus and allow 1t to drain and
cool "for at least 10 mln.
7.1.2.5 Remove the mlcrb-Snyder column and rinse the flask and
Its lower joint Into the concentrator tube with 0.2 ml of hexane.
Adjust the extract volume to 2.0 ml and proceed with either Method
3610 or 3620.
7.2 Gas chromatpgraphy conditions (Recommended); The analysis for
phthalate esters mayBeconductedusing eitheraflame 1on1zat1on or an
electron capture detector. The ECD may, however, provide substantially better
sensitivity.
7.2.1 Column 1: Set 5% methane/95% argon carrier gas flow at 60
mL/m1n flow rate. Set column temperature at 180*C Isothermal.
7.2.2 Column 2: Set 5% methane/95% argon carrier gas flow at 60
mL/m1n flow rate. Set column temperature at 200*C Isothermal.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniquesTUse Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.3.2 If cleanup 1s performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elutlon patterns and the
absence of interferents from the reagents.
8060 - 6
Revision 0
Date September 1986
-------
7.4 Gas chromatographlc analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique 1s used, add 10 uL of Internal standard to the sample prior to
Injection.
7.4.2 Follow Section 7.6 1n Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.4.3 Examples of GC/ECD chromatograms for phthalate esters are
shown In Figures 1 and 2.
7.4.4 Record the sample volume Injected and the resulting peak
sizes (1n area units or peak heights).
7.4.5 Using either the Internal or external calibration procedure
(Method 8000), determine the Identity and quantity of each analyte peak
1n the sample chromatogram. See Section 7.8 of Method 8000 for
calculation equations.
7.4.6 If peak detection and Identification are prevented due to
interferences, the hexane extract may undergo cleanup using either Method
3610 or 3620.
7.5 Cleanup;
7.5.1 Proceed with either Method 3610 or 3620, using the 2-mL
hexane extracts obtained from Paragraph 7.1.2.5.
7.5.2: Following cleanup, the extracts should be analyzed by GC, as
described 1n the previous paragraphs and 1n Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered 1n Method 3500 and 1n
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found In Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each analyte of Interest at the following
concentrations 1n acetone: butyl benzyl phthalate, 10 ug/mL; b1s(2-
ethylhexyl) phthalate, 50 ug/mL; d1-n-octyl phthalate, 50 ug/mL; and any
other phthalate, 25 ug/mL.
8060 - 7
Revision
Date September 1986
-------
-Column: 1.5%SP-2250+
1.95% SP-2401 on Suptlcoport
Temperature: 180°C
Detector: Electron Capture
3
I
£
0 2 4 6 8 10 12
RETENTION TIME (MINUTES)
Figure 1. Gas chromatogram of phthalates (example 1).
8060 - 8
Revision p
Date September 1986
-------
Column: 1.5% SP-2250+
1.95% SP-2401 on Sopeleoport
Ttmptraturt: 18C
Otttctor: Eltctron Capture
0 4 8 12 16
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of phthalates (example 2).
8060 - 9
Revision o
Date September 1986
-------
8.2.2 Table 3 Indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of Interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined 1n Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9,1 The method was tested by 16 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 0.7 to 106 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the analyte and essentially independent of the sample
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. Development and Application of Test Procedures for Specific Organic Toxic
Substances 1n Wastewaters. Category 1 - Phthalates. Report for EPA Contract
68-03-2606 (in preparation).
2. "Determination of Phthalates in Industrial and Municipal Wastewaters,"
EPA-600/4-81-063, U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268, October 1981.
3. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8060 - 10
Revision
Date September 1986
-------
4. "EPA Method Validation Study 16, Method 606 (Phthalate Esters)," Report
for EPA Contract 68-03-2606 (in preparation).
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
6. Provost, L,,P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
8060 - 11
Revision
Date September 1986
-------
TABLE 3. QC ACCEPTANCE CRITERIA3
Parameter
B1 s (2-ethy 1 hexy 1 ) phthal ate
Butyl benzyl phthal ate
D1-n-butyl phthal ate
01 ethyl phthal ate
Dimethyl phthal ate
D1-n-octyl phthal ate
Test
cone.
(ug/L)
50
10
25
25
25
50 .
Limit
for s
(ug/L)
38.4
4.2
8.9
9.0
9.5
13.4
Range
for 7
(ug/L)
1.2-55.9
5.7-11.0
10.3-29.6
1.9-33.4
1.3-35.5
D-50.0
Range
P, Ps
(%)
D-158
30-136
23-136
D-149
D-156
D-114
s = Standard deviation of four recovery measurements, In ug/L.
7 = Average recovery for four recovery measurements, in ug/L.
PI PS = Percent recovery measured.
D = Detected; result must be greater than zero.
aCr1ter1a from 40 CFR Part 136 for Method 606. These criteria are based
directly upon the method performance data in Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 4.
8060 - 12
Revision
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di ethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Accuracy, as
recovery, x1
(ug/L)
0.53C+2.02
0.82C+0.13
0.79C+0.17
0.70C+0.13
0.73C+0.17
0.35C-0.71
Single analyst
precision, sr'
(ug/L)
0.807-2.56
0.267+0.04
0.237+0.20
0.277+0.05
0.267+0.14
0.387+0.71
Overall
precision,
S1 (ug/L)
0.737-0.17
0.257+0.07
0.297+0.06
0.457+0.11
0.447+0.31
0.627+0.34
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
aCriteria from 40 CFR Part 136 for Method 606.
8060 - 13
Revision 0
Date September 1986
-------
METHOD B060
PHTHALATE ESTERS
7.1.1
Choose
appropriate
extraction
procedure
(see Chapter 2)
7.1.2
Exchange
extract-
ion solvent to
hexane
during micro
K-O procedure;:
7.3
Set gas
chromatography
conditions
7.3
Refer to
Method 8000
for proper
calibration
techniques
0
7.4
Perform GC
analysis (see
Method 8000)
7.5.1
Cleanup
using Method
361O or 3630)
Is identifica-
tion G detection
prevented by
interfer-
ences
"No
7.3.21
Process
• aeries
of standards
through cleanup
procedure:
analyze by GC
8060 - 14
Revision 0
Date September 1986
-------
METHOD 8080
ORGANOCHLORINE PESTICIDES AND PCBs
1.0 SCOPE AND APPLICATION
1.1 Method 8080 is used to determine the concentration of various
organochlorine pesticides and polychlorinated biphenyls (PCBs). Table 1
indicates compounds that may be determined by this method and lists the method
detection limit for each compound in reagent water. Table 2 lists the
practical quantitation limit (PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8080 provides gas chromatographic conditions for the
detection of ppb levels of certain organochlorine pesticides and PCBs. Prior
to the use of this method, appropriate sample extraction techniques must be
used. Both neat and diluted organic liquids (Method 3580, Waste Dilution) may
be analyzed by direct injection. A 2- to 5-uL sample is injected into a gas
chromatograph (GC) using the solvent flush technique, and compounds in the GC
effluent are detected by an electron capture detector (ECD) or a halogen-
specific detector (HSD).
2.2 The sensitivity of Method 8080 usually depends on the level of
interferences rather than on instrumental limitations. If interferences
prevent detection of the analytes, Method 8080 may also be performed on
samples that have undergone cleanup. Method 3620, Fieri si 1 Column Cleanup, by
itself or followed by Method 3660, Sulfur Cleanup, may be used to eliminate
interferences in the analysis.
3.0 INTERFERENCES
3.1 Refer to Methods 3500 (Section 3.5, in particular), 3600, and 8000.
3.2 Interferences by phthalate esters can pose a major problem in
pesticide determinations when using the electron capture detector. These
compounds generally appear in the chromatogram as large late-eluting peaks,
especially in the 15% and 50% fractions from the Florisil cleanup. Common
flexible plastics contain varying amounts of phthalates. These phthalates are
easily extracted or leached from such materials during laboratory operations.
Cross contamination of clean glassware routinely occurs when plastics are
handled during extraction steps, especially when solvent-wetted surfaces are
handled. Interferences from phthalates can best be minimized by avoiding
contact with any plastic materials. Exhaustive cleanup of reagents and
glassware may be required to eliminate background phthalate contamination.
The contamination from phthalate esters can be completely eliminated with a
mlcrocoulometrlc or electrolytic conductivity detector.
8080 - 1
Revision 0
Date September 1986
-------
TABLE 1. GAS CHROMATOGRAPHY OF PESTICIDES AND PCBsa
Compound
Aldrin
a-BHC
/J-BHC
ff-BHC
7-BHC (Llndane)
Chlordane (technical)
4,4'-DDD
4, 4 '-DDE
4, 4 '-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Heptachlor
Heptachlor epoxlde
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Retention
Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
time (m1n)
Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Method
Detection
limit (ug/L)
0.004
0.003
0.006
0.009
0.004
0.014
o.oii
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
aU.S. EPA. Method 617. Organochlorlde Pesticides and PCBs,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
e = Multiple peak response.
nd = not determined.
8080 - 2
Revision
Date September 1986
-------
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil by sonlcatlon with GPC cleanup 670
High-level soil and sludges by sonlcatlon 10,000
Non-water misdble waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8080 - 3
Revision
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column Injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: Supelcoport (100/120 mesh) coated with 1.5%
SP-2250/1.95% SP-2401 packed in a 1.8-m x 4-mrn I.D. glass column or
equivalent.
4.1.2.2 Column 2: Supelcoport (100/120 mesh) coated with 3%
OV-1 in a 1.8-m x 4-mm I.D. glass column or equivalent.
4.1.3 Detectors: Electron capture (ECD) or halogen specific (HSD)
(i.e., electrolytic conductivity detector).
4.2 Kuderna-Danish (K-D) apparatus;
4.2.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent),. Ground-glass stopper Is used to prevent evaporation of
extracts
4.2.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.2.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.5 Volumetric flasks; 10-, 50-, and 100-mL, ground-glass stopper.
4.6 Microsyrlnge; 10-uL.
4.7 Syri nge; 5-mL.
4.8 Vials; Glass, 2-, 10-, and 20-mL capacity with Teflon-lined screw
cap.
8080 - 4
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 Solvents; Hexane, acetone, toluene, Isooctane (2,2,4-trlmethyl-
pentane) (pestlcTcfe quality or equivalent).
5.2 Stock standard solutions:
5.2.1 Prepare stock standard solutions at a concentration of
1.00 ug/uL by dissolving 0.0100 g of assayed reference material in
Isooctane and diluting to volume 1n a 10-mL volumetric flask. A small
volume of toluene may be necessary to put some pesticides 1n solution.
Larger volumes can be used at the convenience of the analyst. When
compound purity 1s assayed to be 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration 1f
they are certified by the manufacturer or by an independent source.
5.2.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards Indicates a problem.
5.3 Calibration standards: Calibration standards at a minimum of five
concentration levelsforeach parameter of interest are prepared through
dilution of the stock standards with Isooctane. One of the concentration
levels should be at a concentration near, but above, the method detection
limit. The remaining concentration levels should correspond to the expected
range of concentrations found in real samples or should define the working
range of the GC. Calibration solutions must be replaced after six months, or
sooner, 1f comparison with check standards indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the Internal standard 1s not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of Interest as described in
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with Isooctane.
5.4.3 Analyze each calibration standard according to Section 7.0.
8080 - 5
Revision 0
Date September 1986
-------
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction, cleanup(when used), and analytical system and the effec-
tiveness of the method 1n dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with pesticide surrogates. Because
GC/ECD data are much more subject to Interference than GC/MS, a secondary
surrogate 1s to be used when sample Interference Is apparent. D1butyl -
chlorendate (DBC) 1s also subject to add and base degradation. Therefore,
two surrogate standards are added to each sample; however, only one need be
calculated for recovery. DBC 1s the primary surrogate and should be used
whenever possible. However, 1f DBC recovery 1s low or compounds Interfere
with DBC, then the 2,4,5,6-tetrachloro-meta-xylene should be evaluated for
acceptance. Proceed with corrective action when both surrogates are out of
limits for a sample (Section 8.3). Method 3500, Section 5.3.2, indicates the
proper procedure for preparing these surrogates,
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographlc analysis, the extraction solvent
must be exchanged to hexane. The exchange 1s performed during the K-D
procedures listed in all of the, extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.2.2 Increase the temperature of the hot water bath to
about 90*C. Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube is partially immersed 1n the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus and allow it to drain and
cool for at least 10 min.
8080 - 6
Revision 0
Date September 1986
-------
7.1.2.3 Remove the Snyder column and rinse the flask and its
lower joint Into the concentrator tube with 1-2 ml of hexane. A
5-mL syringe 1s recommended for this operation. Adjust the extract
volume to 10.0 ml. Stopper the concentrator tube and store
refrigerated at 4*C, 1f further processing will not be performed
Immediately. If the extract will be stored longer than two days, 1t
should be transferred to a Teflon-sealed screw-cap vial. Proceed
with gas chromatographlc analysis 1f further cleanup 1s not
required.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set 5% methane/95% argon carrier gas flow at
60 mL/m1n flow rate. Column temperature 1s set at 200*C Isothermal.
When analyzing for the low molecular weight PCBs (PCB 1221-PCB 1248), it
is advisable to set the oven temperature to 160*C.
7.2.2 Column 2: Set 5% methane/95% argon carrier gas flow at
60 ml_/m1n flow rate. Column temperature held Isothermal at 200*C. When
analyzing for the low molecular weight PCBs (PCB 1221-PCB 1248), 1t 1s
advisable to set the oven temperature to 140*C.
7.2.3 When analyzing for most or all of the analytes 1n this
method, adjust the oven temperature and column gas flow so that 4,4'-DDT
has a retention time of approximately 12 m1n.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.3.2 Because of the low concentration of pesticide standards
injected on a GC/ECD, column adsorption may be a problem when the GC has
not been used for a day. Therefore, the GC column should be primed or
deactivated by Injecting a PCB or pesticide standard mixture
approximately 20 times more concentrated than the mid-level standard.
Inject this prior to beginning Initial or dally calibration.
7.4 Gas chromatographlc analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique Is used, add 10 uL of Internal standard to the sample prior to
injection.
7.4.2 Follow Section 7.6 1n Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
8080 - 7
Revision 0
Date September 1986
-------
7.4.3 Examples of GC/ECD chromatograms for various pesticides and
PCBs are shown in Figures 1 through 5.
7.4.,4 Prime the column as per Paragraph 7.3.2.
7.4,,5 DDT and endrin are easily degraded in the injection port if
the injection port or front of the column is dirty. This is the result
of buildup of high boiling residue from sample injection. Check for
degradation problems by injecting a mid-level standard containing only
4,4'-DDT and endrin. Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-ODD) and endrin (endrin ketone and endrin aldehyde).
If degradation of either DDT or endrin exceeds 20%, take corrective
action before proceeding with calibration, by following the GC system
maintenance outlined in Section 7.7 of Method 8000. Calculate percent
breakdown as follows:
% breakdown Total DDT degradation peak area (DDE + ODD) ,nn
for 4,4'-DDT " Total DDT peak area (DDT + DDE + ODD) * iuu
% breakdown
for Endrin
Total endrin degradation peak area (endrin aldehyde + endrin ketone) 1QO
Total endrin peak area (endrin + endrin aldehyde + endrin ketone)
7.4.6 Record the sample volume injected and the resulting peak
sizes (in area units or peak heights).
7.4.7 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.4.8 If peak detection and identification are prevented due to
interferences, the hexane extract may need to undergo cleanup using
Method 3620. The resultant extract(s) may be analyzed by GC directly or
may undergo further cleanup to remove Sulfur using Method 3660.
7.5 Cleanup;
7.5.1 Proceed with Method 3620, followed by, if necessary, Method
3660, using the 10-mL hexane extracts obtained from Paragraph 7.1.2.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
7.6 Calculations (exerpted from U.S. FDA, PAM):
7.6.1 Calculation of Certain Residues: Residues which are mixtures
of two or more components present problems in measurement. When they are
found together, e.g., toxaphene and DDT, the problem of quantitation
becomes even more difficult. In the following sections suggestions are
offered for handling toxaphene, chlordane, PCB, DDT, and BHC. A column
10% DC-200 stationary phase was used to obtain the chromatograms in
Figures 6-9.
8080 - 8
Revision 0
Date September 1986
-------
Column: 1.5% SP-225CK
1.95% SP-2401 on Suptlcopon
Ttmptraturi: 200°C
Ofttetor: Eltctron Capture
o
00
u
•X
VJ
4 8 12
RETENTION TIME (MINUTES)
16
Figure 1. Gas ehromatogram of pesticides.
8080 - 9
Revision p
Date September 1986
-------
Column: 1.5*8?-2250*
1.95* SP-2401 on Suptleopon
Ttmptrtture 2t)C°C
Drttctor: Electron Capiurt
I < I t
• I
04 8 12 16
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of chlordane.
8080 - 10
Revision Q
Date September 1986
-------
Column: 1.5% 9-2250+
1J5% SP-2401 on Suptlcopon
T0mptfituri: 200°C
Dmctor: Eltctron Cioturt
10 14 18
RETENTION TIME (MINUTES)
22
26
Figure 3. Gas chromatogram of toxaphene.
8080 - 11
Revision o
Date September 1986
-------
Column: 1.5\SP-2250»
1.95% SP 2401 en Suptlcepon
Ttmperaturt: 200°C
Otttctor: Eltcrron CtPturt
6 10 14 18
RETENTION TIME (MINUTES)
22
Figure 4. Gas chromatogrim of PCS-1254.
8080 - 12
Revision Q
Date September 1986
-------
Column: 1.5* SP-2250*
1.95% SP-2401 on Suptlcooon
Ttrnpcraturf: 200°C
iDtUCtor: Electron Capture
10 14 18
RETENTION TIME (MINUTES)
22
26
Figure 5. Gas chromatogram of PCB-1260.
8080 - 13
Revision 0
Date September 1986
-------
J..L
Fig, 6—Baseline construction for some typical gas chromatographlc peaks.
a, symmetrical separated flat baseline; b and c. overlapping flat baseline;
d, separated (pen does not return to baseline between peaks); e, separated
sloping baseline; f, separated (pen goes below baseline between peaks);
g. «- andy-BHC sloping baseline; h, «-.£-. and Y-BHC sloping baseline;
1, chlordane flat baseline; j. heptachlor and heptachlor epoxlde super-
imposed on chlordane; k, chair-shaped peaks, unsymmetrtcal peak; 1,
p,p'-DDT superimposed on toxaphene.
8080 - 14
Revision p
Date September 1986
-------
Fig. 7a—Baseline construction for multiple residues with standard
toxaphene.
\l
Fig, 7b—Baseline construction for multiple residues with toxa-
phene, DOE and o.p'-, and p.p'-DDT.
8080 - 15
Revision o
Date September 1986
-------
Fig. 8a—Baseline construction for multiple residues: standard toxaphene.
Fig. 8b—Baseline construction for multiple residues: rice bran with BHC,
toxaphene, DOT, and methoxychlor.
8080 - 16
Revision 0
Date September 1986
-------
Fig. 9a—Baseline construction for multiple residues: standard chlordane.
Fig. 9b—Baseline construction for multiple residues: rice bran with chlordane, toxaphene, and DOT.
8080 - 17
Revision Q
Date September 1986
-------
7.6.2 Toxaphene: Quantitative calculation of toxaphene or Strobane
is difficult, but reasonable accuracy can be obtained. To calculate
toxaphene on GC/ECD: (a) adjust sample size so that toxaphene major
peaks are 10-30% full-scale deflection (FSD); (b) inject a toxaphene
standard that is estimated to be within +10 ng of the sample; (c)
construct the baseline of standard toxaphene between it extremities; and
(d) construct the baseline under the sample, using the distances of the
peak troughs to baseline on the standard as a guide (Figures 7, 8, and
9). This procedure is made difficult by the fact that the relative
heights and widths of the peaks in the sample will probably not be
identical to the standard. A toxaphene standard that has been passed
through a Florisil column will show a shorter retention time for peak X
and an enlargement of peak Y.
7.6.3 Toxaphene and DDT: If DDT is present, it will superimpose
itself on toxaphene peak V. To determine the approximate baseline of the
DDT, draw a line connecting the trough of peaks U and V with the trough
of peaks W and X and construct another line parallel to this line which
will just cut the top of peak W (Figure 61). This procedure was tested
with ratios of standard toxaphene-DDT mixtures from 1:10 to 2:1 and the
results of added and calculated DDT and toxaphene by the "parallel lines"
method of baseline construction were within 10% of the actual values in
all cases.
7.6.3.1 A series of toxaphene residues have been calculated
using total peak area for comparison to the standard and also using
area of the last four peaks only in both sample and standard. The
agreement between the results obtained by the two methods justifies
the use of the latter method for calculating toxaphene in a sample
where the early eluting portion of the toxaphene chromatogram is
interfered with by other substances.
7.6.3.2 The baseline for methoxychlor superimposed on
toxaphene (Figure 8b) was constructed by overlaying the samples on a
toxaphene standard of approximately the same concentration (Figure
8a) and viewing the charts against a lighted background.
7.6.4 Chlordane is a technical mixture of at least 11 major
components and 30 or more minor ones. Gas chromatography-mass
spectrometry and nuclear magnetic resonance analytical techniques have
been applied to the elucidation of the chemical structures of the many
chlordane constituents. Figure 9a is a chromatogram of standard chlor-
dane. Peaks E and F are responses to trans- and cis-chlordane, respec-
tively. These are the two major components of technical chlordane, but
the exact percentage of each in the technical material 1s not completely
defined and is not consistent from batch to batch. Other labelled peaks
in Figure 9a are thought to represent: A, monochlorinated adduct of
pentachlorocyclopentadiene with cyclopentadiene; B, coelution of
heptachlor and a-chlordene; C, coelution of /?-chlordene and 7-chlordene;
8080 - 18
Revision 0
Date September 1986
-------
D, a chlordane analog; G, coelutlon of cis-nonachlor and "Compound K," a
chlordane Isomer. The right "shoulder" of peak F is caused by trans-
nonachlor.
7.6.4.1 The GC pattern of a chlordane residue may differ
considerably from that of the technical standard. Depending on the
sample substrate and its history, residues of chlordane can consist
of almost any combination of: constituents from the technical
chlordane; plant and/or animal metabolities; and products of
degradation caused by exposure to environmental factors such as
water and sunlight. Only limited information is available on which
residue GC patterns are likely to occur in which samples types, and
even this information may not be applicable to a situation where the
route of exposure is unusual. For example, fish exposed to a recent
spill of technical chlordane will contain a residue drastically
different from a fish whose chlordane residue was accumulated by
Ingestion of smaller fish or of vegetation, which in turn had
accumulated residues because chlordane was in the water from
agricultural runoff.
7.6.4.2 Because of this Inability to predict a chlordane
residue GC pattern, it is not possible to prescribe a single method
for the quantitation of chlordane residues. The analyst must judge
whether or not the residue's GC pattern is sufficiently similar to
that of a technical chlordane reference material to use the latter
as a reference standard for quantitation.
7.6.4.3 When the chlordane residue does not resemble technical
chlordane, but instead consists primarTTy of Individual,
identifiable peaks, quantitate each peak separately against the
appropriate reference materials and report the Individual residues.
(Reference materials are available for at least 11 chlordane
constituents, metabolites or degradation products which may occur in
the residue.)
7.6.4.4 When the GC pattern of the residue resembles that of
technical chlordane, quantitate chlordane residues by comparing the
total area of the chlordane chromatogram from peaks A through F
(Figure 9a) in the sample versus the same part of the standard
chromatogram. Peak G may be obscured in a sample by the presence of
other pesticides. If G is not obscured, include it in the
measurement for both standard and sample. If the heptachlor epoxide
peak is relatively small, include it as part of the total chlordane
area for calculation of the residue. If heptachlor and/or
heptachlor epoxide are much out of proportion as in Figure 6j,
calculate these separately and subtract their areas from total area
to give a corrected chlordane area. (Note that octachlor epoxide,
metabolite of chlordane, can easily be mistaken for heptachlor
epoxide on a nonpolar GC column.)
8080 - 19
Revision 0
Date September 1986
-------
7.6.4.5 To measure the total area of the chlordane
chromatogram, proceed as 1n Section 7.6.2 on toxaphene. Inject an
amount of technical chlordane standard which will produce a
chromatogram 1n which peaks E and F are approximately the same size
as those In the sample chromatograms. Construct the baseline
beneath the standard from the beginning of peak A to the end of peak
F as shown 1n Figure 9a. Use the distance from the trough between
peaks E and F to the baseline 1n the chromatogram of the standard to
construct the baseline 1n the chromatogram of the sample. Figure 9b
shows how the presence of toxaphene causes the baseline under
chlordane to take an upward angle. When the size of peaks E and F
1n standard and sample chromatograms are the same, the distance from
the trough of the peaks to the baselines should be the same.
Measurement of chlordane area should be done by total peak area 1f
possible.
NOTE: A comparison has been made of the total peak area
Integration method and the addition of peak heights method for
several samples containing chlordane. The peak heights A, B,
C, D, E, and F were measured 1n millimeters from peak maximum
of each to the baseline constructed under the total chlordane
area and were then added together. These results obtained by
the two techniques are too close to Ignore this method of "peak
height addition" as a means of calculating chlordane. The
technique has Inherent difficulties because not all the peaks
are symmetrical and not all are present in the same ratio 1n
standard and 1n sample. This method does offer a means of
calculating results 1f no means of measuring total area 1s
practical.
7.6.5 Polychlorlnated blphenyls (PCBs): Quant1tat1on of residues
of PCB Involves problems similar to those encountered 1n the quantltatlon
of toxaphene, Strobane, and chlordane: 1n each case, the chemical 1s
made up of numerous compounds and so the chromatograms are multi-peak;
also 1n each case the chromatogram of the residue may not match that of
the standard.
7.6.5.1 Mixtures of PCB of various chlorine contents were sold
for many years 1n the U.S. by the Monsanto Co. under the tradename
Aroclor (1200 series and 1016). Though these Aroclors are no longer
marketed, the PCBs remain 1n the environment and are sometime found
as residues 1n foods, especially fish.
7.6.5.2 PCB residues are quantltated by comparison to one or
more of the Aroclor materials, depending on the chromatographlc
pattern of the residue. A choice must be made as to which Aroclor
or mixture of Aroclors will produce a chromatogram most similar to
that of the residue. This may also Involve a judgment about what
proportion of the different Aroclors to combine to produce the
appropriate reference material.
8080 - 20
Revision
Date September 1986
-------
7.6.5.3 Quantltate PCB residues by comparing total area or
height of residue peaks to total area of height of peaks from
appropriate Aroclor(s) reference materials. Measure total area or
height response from common baseline under all peaks. Use only
those peaks from sample that can be attributed to chloroblphenyls.
These peaks must also be present 1n chromatogram of reference
materials. Mixture of Aroclors may be required to provide best
match of GC patterns of sample and reference.
7.6.6 DDT: DDT found 1n samples often consists of both o,p'- and
p,p'-DDT. Residues of DDE and TDE are also frequently present. Each
Isomer of DDT and Its metabolites should be quantltated using the pure
standard of that compound and reported as such.
7.6.7 Hexachlorocyclohexane (BHC, from the former name, benzene
hexachlorlde): Technical grade BHC 1s a cream-colored amorphous solid
with a very characteristic musty odor; 1t consists of a mixture of six
chemically distinct Isomers and one or more heptachloro-cyclohexanes and
octachloro-cyclohexanes.
7.6.7.1 Commercial BHC preparations may show a wide variance
1n the percentage of Individual Isomers present. The elimination
rate of the Isomers fed to rats was 3 weeks for the a-, 7-, and 6-
Isomers and 14 weeks for the /Msomer. Thus 1t may be possible to
have any combination of the various Isomers 1n different food
commodities. BHC found 1n dairy products usually has a large
percentage of /Msomer.
7.6.7.2 Individual Isomers (a, 0, 7, and 6) were Injected Into
gas chromatographs equipped with flame 1on1zat1on, m1crocoulometr1c,
and electron capture detectors. Response for the four Isomers 1s
very nearly the same whether flame 1on1zat1on or m1crocoulometr1c
GLC 1s used. The a-, 7-, and dMsomers show equal electron
affinity. /J-BHC shows a much weaker electron affinity compared to
the others Isomers.
7.6.7.3 Quantltate each Isomer (a, /f, 7, and 6) separately
against a standard of the respective pure Isomer, using a GC column
which separates all the Isomers from one another.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered In Method 3500 and 1n
the extraction method utilized. If extract cleanup was performed, follow the
QC In Method 3600 and 1n the specific cleanup method.
8.2 Mandatory quality control to evaluate the GC system operation 1s
found 1n Method 8000, Section 8.6.
8080 - 21
Revision
Date September 1986
-------
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each single-component parameter of interest
at the following concentrations in acetone: 4,4'-DDD, 10 ug/mL; 4,4'-
DDT, 10 ug/mL; endosulfan II, 10 ug/mL; endosulfan sulfate, 10 ug/mL;
endrin, lOug/mL; and any other single-component pesticide, 2 ug/mL. If
this method is only to be used to analyze for PCBs, chlordane, or
toxaphene, the QC check sample concentrate should contain the most
representative multi-component parameter at a concentration of 50 ug/mL
in acetone.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is; within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance'.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.4 GC/MS confirmation; Any compounds confirmed by two columns may also
be confirmed by GC/MSifthe concentration is sufficient for detection by
GC/MS as determined by the laboratory generated detection limits.
8.4.1 The GC/MS would normally require a minimum concentration of
10 ng/uL in the final extract, for each single-component compound.
8.4.2 The pesticide extract and associated blank should be analyzed
by GC/MS as per Section 7.0 of Method 8270.
8.4.3 The confirmation may be from the GC/MS analysis of the
base/neutral-acid extractables extracts (sample and blank). However, if
the compounds are not detected in the base/neutral-acid extract even
though the .concentration is high enough, a GC/MS analysis of the
pesticide extract should be performed.
8.4.4 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a level
that would demonstrate the ability to confirm the pesticides/PCBs
identified by GC/ECD.
8080 - 22
Revision 0
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three Industrial wastewaters spiked at six
concentrations. Concentrations used 1n the study ranged from 0.5 to 30 ug/L
for single-component pesticides and from 8.5 to 400 ug/L for multl-component
parameters. Single operator precision, overall precision, and method accuracy
were found to be directly related to the concentration of the parameter and
essentially Independent of the sample matrix. Linear equations to describe
these relationships for a flame 1on1zat1on detector are presented 1n Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, optional cleanup techniques, and
calibration procedures used.
10.0 REFERENCES
1. U.S. EPA, "Development and Application of Test Procedures for Specific
Organic Toxic Substances 1n Wastewaters, Category 10: Pesticides and PCBs,"
Report for EPA Contract 68-03-2605.
2. U.S. EPA, "Interim Methods for the Sampling and Analysis of Priority
Pollutants 1n Sediments and F1sh Tissue," Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, October 1980.
3. Pressley, T.A., and J.E. Longbottom, "The Determination of Organohallde
Pesticides and PCBs 1n Industrial and Municipal Wastewater: Method 617," U.S.
EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006, 1982.
4. "Determination of Pesticides and PCB's 1n Industrial and Municipal
Wastewaters, U.S. Environmental Protection Agency," Environmental Monitoring
and Support Laboratory, Cincinnati, OH 45268, EPA-600/4-82-023, June 1982.
5. GoerlUz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9, 1971.
6. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
7. Webb, R.G. and A.C. McCall, "Quantitative PCB Standards for Electron
Capture Gas Chromatography," Journal of Chromatographlc Science, 11, 366,
1973.
8. Millar, J.D., R.E. Thomas and H.J. Schattenberg, "EPA Method Study 18,
Method 608: Organochlorlne Pesticides and PCBs," U.S. EPA/EMSL, Research
Triangle Park, NC, EPA-600/4-84-061, 1984.
9. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
8080 - 23
Revision 0
Date September 1986
-------
10. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
11. U.S. Food and Drug Administration, Pesticide Analytical Manual, Vol. 1,
June 1979.
12. Sawyer, L.D., JAOAC, 56, 1015-1023 (1973), 61 272-281 (1978), 61 282-291
(1978).
13. Official Methods of Analysis of the Association of Official Analytical
Chemists, 12th Edition; Changes 1n Methods, JAOAC 61, 465-466 (1978), Sec.
29.018.
8080 - 24
Revision
Date September 1986
-------
TABLE 3. QC ACCEPTANCE CRITERIA3
Parameter
Aldrln
a-BHC
fl-BHC
ff-BHC
7-BHC
Chlordane
4,4'-DDD
4, 4 '-DDE
4,4'-DDT
D1eldr1n
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrln
Heptachlor
Heptachlor epoxlde
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Test
cone.
(ug/L)
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
2.0
10
10
10
2.0
2.0
50
50
50
50
50
50
50
50
Limit
for s
(ug/L)
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
/ /
' tonge
/ /for 7
(ug/L)
/i! 08-2. 24
/ /. 98-2. 44
(U. 78-2. 60
1.01-2.37
0.86-2.32
27.6-54.3
/4.8-12.6
1. 08-2. 60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2
22.2-57.9
18.7-54.9
Range
P, Ps
/ (V \
\ /
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCriter1a from 40 CFR Part 136 for Method 608. These criteria are based
directly upon the method performance data 1n Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 4.
8080 - 25
Revision 0
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Aldrin
a-BHC
/J-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dleldrin
Endosulfan
Endosulfan
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
x' =
sr' =
S1 =
Accuracy, as
recovery, x1
(ug/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85C+0.14
0.93C-0.13
0.90C+0.02
I 0.97C+0.04
II 0.93C+0.34
Sulfate 0.89C-0.37
0.89C-0.04
0.69C+0.04
epoxide 0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.93C+0.70
0.97C+1.06
0.76C+2.07
0.66C+3.76
Single analyst Overall
precision, sr' precision,
(ug/L)
0.167-0.04
0.137+0.04
0.227+0.02
0.187+0.09
0.127+0.06
0.137+0.13
0.207-0.18
0.137+0.06
0.177+0.39
0.127+0.19
0.107+0.07
0.417-0.65
0.137+0.33
0.207+0.25
0.067+0.13
0.187-0.11
0.097+3.20
0.137+0.15
0.297-0.76
0.217-1.93
0.117+1.40
0.177+0.41
0.157+1.66
0.227-2.37
S1 (ug/L)
0.207-0.01
0.237-0.00
0.337-0.95
0.257+0.03
0.227+0.04
0.187+0.18
0.277-0.14
0.287-0.09
0.317-0.21
0.167+0.16
0.187+0.08
0.477-0.20
0.247+0.35
0.247+0.25
0.167+0.08
0.257-0.08
0.207+0.22
0.157+0.45
0.357-0.62
0.317+3.50
0.217+1.52
0.257-0.37
0.177+3.62
0.397-4.86
Expected recovery for one or more measurements of a sample
containing a concentration of C, 1n
Expected single analyst standard
average concentration of 7, in ug/L
Expected interlaboratory standard
ug/L.
deviation of
•
deviation of
measurements at an
measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8080 - 26
Revision 0
Date September 1986
-------
METHOD aoao
ORGANOCHLORINE PESTICIDES C PCBa
o
7.1.1
I Choose
appropriate
axtractlon
procedure
(see Chapter a)
7.1.8
7.4
Perform GC
analysis (see
Method 8OOO)
Exchange
extract-
ion solvent to
hexone
during micro
K-D procedures
7.5.1
7.Z
Set gas
chromatography
conditions
7.3
Refer to
Method BOOO
for proper
calibration
techniques
Is peak
detection £ Iden-
tification
prevent-
ed?
Cleanup
using Method
3630 and 3660
If necessary
Methods of
calculation of
toxaphena. chlordane.
PCS. DOT. and 6HC are
handled In this
section
7.3.21
I Prime or
deactivate
GC column
prior to dally
calibration
O
8080 - 27
Revision 0
Date September 1986
-------
METHOD 8090
NITROAROMATICS AND CYCLIC KETONES
1.0 SCOPE AND APPLICATION
1.1 Method 8090 is used to determine the concentration of various
nitroaromatic and cyclic ketone compounds. Table 1 indicates compounds that
may be determined by this method and lists the method detection limit for each
compound in reagent water. Table 2 lists the practical quantisation limit
(PQL) for other matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8090 provides gas chromatographic conditions for the
detection of ppb levels of nitroaromatic and cyclic ketone compounds. Prior
to use of this method, appropriate sample extraction techniques must be used.
Both neat and diluted organic liquids (Method 3580, Waste Dilution) may be
analyzed by direct injection. A 2- to 5-uL aliquot of the extract is injected
into a gas chromatograph (GC) using the solvent flush technique, and compounds
in the GC effluent are detected by an electron capture detector (ECD) or a
flame ionization detector (FID). The dinitrotoluenes are determined using
ECD, whereas the other compounds amenable to this method are determined using
FID.
2.2 If interferences prevent proper detection of the analytes, the
method may also be performed on extracts that have undergone cleanup.
3.0 INTERFERENCES
3.1 Refer to Method 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample-processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
8090 - 1
Revision 0
Date September 1986
-------
TABLE 1. GAS CHROMATOGRAPHY OF NITROAROMATICS AND ISOPHORONE
Retention time (m1n) Method detection
Unit (ug/L)
Compound Col. la Col. 2b ECD FID
Isophorone
Nitrobenzene
2,4-D1n1trotoluene
2,6-D1n1trotoluene
D1 nitrobenzene
Naphthoqulnone
4.49
3.31
5.35
3.52
5.72
4.31
6.54
4.75
15.7
13.7
0.02
0.01
5.7
3.6
-
-
aColumn 1: Gas-Chrom Q (80/100 mesh) coated with 1.95% QF-1/1.5% OV-17
packed 1n a 1.2-m x 2-mm or 4-mm I.D. glass column. A 2-mm I.D. column and
nitrogen gas at 44 mL/min flow rate were used when determining isophorone and
nitrobenzene by GC/FID. The column temperature was held Isothermal at 85°C.
A 4-mm I.D. column and 10% methane/90% argon carrier gas at 44 mL/m1n flow
rate were used when determining the dinltrotoluenes by GC/ECD. The column
temperature was held Isothermal at 145°C.
bColumn 2: Gas-Chrom Q (80/100 mesh) coated with 3% OV-101 packed 1n a 3.0-
m x 2-mm or 4-mm I.D. glass column. A 2-mm I.D. column and nitrogen carrier
gas at 44 mL/m1n flow rate were used when determining Isophorone and
nitrobenzene by GC/FID. The column temperature was held isothermal at 100'C.
A 4-mm I.D. column and 10% methane/90% argon carrier gas at 44 mL/min flow
rate were used to determine the dinltrotoluenes by GC/ECD. The column
temperature was held Isothermal at 150°C.
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES*
Matrix Factorb
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
Multiply the Method Detection Limits in Table 1 by the Factor to
determine the PQL for each analyte in the matrix to be analyzed.
8090 - 2
Revision
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: 1.2-m x 2- or 4-mrn I.D. glass column packed
with 1.95% QF-1/1.5% OV-17 on Gas-Chrom Q (80/100 mesh) or
equivalent.
4.1.2.2 Column 2: 3.0-m x 2- or 4-mm I.D. glass column packed
with 3% OV-101 on Gas-Chrom Q (80/100 mesh) or equivalent.
4.1.3 Detectors: Flame ionization (FID) or electron capture (ECD).
4.2 Kuderna-Danish (K-D) apparatus;
4.2.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts
4.2.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.2.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.5 Volumetric flasks; 10-, 50-, and 100-mL, ground-glass stopper.
4.6 Microsyringe: 10-uL.
4.7 Syri nge; 5-mL.
4.8 Vials; Glass, 2-, 10-, and 20-mL capacity with Teflon-lined screw
cap.
8090 - 3
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 Solvents; hexane, acetone (pesticide quality or equivalent.)
5.2 Stock standard solutions;
5.2.1 Prepare stock standard solutions at a concentration of 1.00
ug/uL by dissolving 0.0100 g of assayed reference material in hexane and
diluting to volume in a 10-mL volumetric flask. Larger volumes can be
used at the convenience of the analyst. When compound purity is assayed
to be 96% or greater, the weight can be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards can be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.2.2 Transfer t;.: stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner 1f comparison with check standards indicates a problem.
5.3 Calibration standards; Calibration standards at a minimum of five
concentration levels are prepared through dilution of the stock standards with
hexane. One of the concentration levels should be at a concentration near,
but above, the method detection limit. The remaining concentration levels
should correspond to the expected range of concentrations found 1n real
samples or should define the working range of the GC. Calibration solutions
must be replaced after six months, pr sooner 1f comparison with a check
standard indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of Interest as described 1n
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with hexane.
5.4.3 Analyze each calibration standard according to Section 7.0.
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction, cleanup(when used), and analytical system and the effec-
tiveness of the method 1n dealing with each sample matrix by spiking each
8090 - 4
Revision 0
Date September 1986
-------
sample, standard, and reagent water blank with one or two surrogates (e.g., 2-
fluoroblphenyl) recommended to encompass the range of the temperature program
used 1n this method. Method 3500, Section 5.3.1.1, details Instructions on
the preparation of base/neutral surrogates. Deuterated analogs of analytes
should not be used as surrogates for gas chromatographlc analysis due to
coelutlon problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a pH
between 5 to 9 with methylene chloride, using either Method 3510 or 3520.
Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographlc analysis, the extraction solvent
must be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange may be
performed 1n one of two ways, depending on the data requirements. If the
detection limits cited 1n Table 1 must be achieved, the exchange should
be performed as described starting 1n Section 7.1.4. If these detection
limits are not necessary, solvent exchange is performed as outlined 1n
Section 7.1.3.
7.1.3 Solvent exchange when detection limits In Table 1 are not
required:
7.1.3.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 m1n.
7.1.3.2 Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube 1s partially Immersed 1n the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 min. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus and allow 1t to drain and
cool for at least 10 min. The extract will be handled differently
8090 - 5
Revision
Date September 1986
-------
at this point, depending on whether or not cleanup 1s needed. If
cleanup 1s riot required, proceed to Paragraph 7.1.3.3. If cleanup
1s needed, proceed to Paragraph 7.1.3.4.
7.1.3.3 If cleanup of the extract 1s not required, remove the
Snyder column and rinse the flask and Its lower joint Into the
concentrator tube with 1-2 ml of hexane. A 5-mL syringe 1s
recommended for this operation. Adjust the extract volume to
10.0 ml. Stopper the concentrator tube and store refrigerated at
4*C 1f further processing will not be performed Immediately. If the
extract will be stored longer than two days, it should be
transferred to a Teflon-sealed screw-cap vial. Proceed with gas
chromatographlc analysis.
7.1.3.4 If cleanup of the extract 1s required, remove the
Snyder column and rinse the flask and Its lower joint Into the
concentrator tube with a minimum amount of hexane. A 5-mL syringe
1s recommended for this operation. Add a clean boiling chip to the
concentrator tube and attach a two-ball micro-Snyder column. Prewet
the column by adding about 0.5 mL of hexane to the top. Place the
micro-K-D apparatus on the water bath (80*C) so that the concen-
trator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 min. At the proper rate
of distillation the balls of ,the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 min.
7.1.3.5 Remove the micrp-Snyder column and rinse the flask and
Its lower joint Into the concentrator tube with 0.2 ml of hexane.
Adjust the extract volume to 2.0. ml and proceed with Method 3620.
7.1.4 Solvent exchange when detection limits listed In Table 1 must
be achieved:
7.1.4.1 Following K-D of the methylene chloride extract to
1 ml using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.4.2 Remove the Snyder column and rinse the flask and Its
lower joint Into the concentrator tube with 1-2 mL of methylene
chloride. A 5-mL syringe 1s recommended for this operation. Add
1-2 mL of hexane, a clean boiling chip, and attach a two-ball micro-
Snyder column. Prewet the column by adding 0.5 mL of hexane to the
top. Place the micro-K-D apparatus on the water bath (60-65'C) so
that the concentrator tube is partially immersed 1n the hot water.
Adjust the vertical position of the apparatus and the water
temperature, as required, to complete concentration in 5-10 min. At
the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 0.5 mL, remove the K-D apparatus
and allow it to drain and cool for at least 10 min.
8090 - 6
Revision 0
Date September 1986
-------
7.1.4.3 Remove the mlcro-Snyder column and rinse the flask and
Its lower joint Into the concentrator tube with a minimum amount of
hexane. The volume of the extract should be adjusted to 1.0 ml 1f
the extract will be analyzed without cleanup. If the extract will
require cleanup, adjust the volume to 2.0 ml with hexane. Stopper
the concentrator tube and store refrigerated at 4*C 1f further
processing will not be performed Immediately. If the extract will
be stored longer than two days, 1t should be transferred to a
Teflon-sealed screw-cap vial. Proceed with either gas chromato-
graphlc analysis or with cleanup, as necessary.
7.2 Gas chromatography conditions (Recommended); The determination of
dinitrotoluenesshouldbe performedusingGC/ECD. All other compounds
amenable to this method are to be analyzed by GC/FID.
7.2.1 Column 1: Set 10% methane/90% argon carrier gas flow at
44 ml_/m1n flow rate. For a 2-mm I.D. column, set the temperature at 85*C
Isothermal. For a 4-mm I.D. column, set the temperature at 145*C
isothermal.
7.2.2 Column 2: Set 10% methane/90% argon carrier gas flow at
44 mL/m1n flow rate. For a 2-mm I.D. column, set the temperature at
100°C Isothermal. For a 4-mm I.D. column, set the temperature at 150*C
Isothermal.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques"! Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external standard calibration
may be used. Refer to Method 8000 for a description of each of these
procedures.
7.3.4 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of interferents from the reagents.
7.4 Gas chromatographic analysis;
7.4.1 Refer to Method 8000. If the internal standard calibration
technique 1s used, add 10 uL of internal standard to the sample prior to
injection.
7.4.2 Follow Section 7.6 in Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence when using FID
and after each group of 5 samples in the analysis sequence when using
ECD.
8090 - 7
Revision 0
Date September 1986
-------
7.4.3 An example of a GC/FID chromatogram for nitrobenzene and
isophorone 1s shown 1n Figure 1. Figure 2 1s an example of a GC/ECD
chromatogram of the dlnltrotoluenes.
7.4.4 Record the sample volume Injected and the resulting peak
sizes (1n area units or peak heights).
7.4.5 Using either the Internal or external calibration procedure
(Method 8000), determine the Identity and quantity of each analyte peak
in the sample chromatogram. See Section 7.8 of Method 8000 for
calculation equations.
7.4.6 If peak detection and Identification are prevented due to
interferences, the hexane extract may undergo cleanup using Method 3620.
7.5 Cleanup;
7.5.1 Proceed with Method 3620, using the 2-mL hexane extracts
obtained from either Paragraph 7.1.3.5 or 7.1.4.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered 1n Method 3500 and 1n
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and 1n the specific cleanup method.
8.2 Procedures to check the GC system operation are found 1n Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of interest in acetone at a
concentration of 20 ug/mL for each dinitrotoluene and 100 ug/mL for
isophorone and nitrobenzene.
8.2.2 Table 3 Indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the, analytes of Interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8090 - 8
Revision 0
Date September 1986
-------
COLUMN: 1.5% OV-17 +1.95% QF-1
ON GAS CHROM Q
TEMPERATURE: 85°C.
DETECTOR: FLAME IONIZATION
24 6 8 10 12
RETENTION TIME-MINUTES
Figure 1. Gas chromatogram of nitrobenzene and isophorone.
8090 - 9
Revision Q
Date September 1986
-------
COLUMN: 1.5% OV-17 4-1.95% QM
ON GAS CHROM Q
TEMPERATURE: 145°C.
DETECTOR: ELECTRON CAPTURE
3
g
O
z
o
to
Ul
Z
O
O
K
I
o
V
fN
I
u
2468
RETENTION TIME-MINUTES
Figure 2. Gas chromatogram of dinitrotoluenes.
8090 - 10
Revision 0
Date September 1986
-------
8.3.1 If recovery is not within limits, the following 1s required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and Internal standards. Also, check
Instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 18 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 1.0 to 515 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the parameter and essentially independent of the sample
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 4 - Nitroaromatics and Isophorone,'
Report for EPA Contract 68-03-2624 (in preparation).
2. "Determination of Nitroaromatics and Isophorone in Industrial and
Municipal Wastewaters," EPA-600/4-82-024, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268, June 1982.
3. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
4. "EPA Method Validation Study 19, Method 609 (Nitroaromatics and
Isophorone)," Report for EPA Contract 68-03-2624 (in preparation).
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 1J>, pp. 58-63, 1983.
8090 - 11
Revision 0
Date September 1986
-------
TABLE 3. QC ACCEPTANCE CRITERIA3
Parameter
2,4-D1n1trotoluene
2,6-Dinitrotoluene
Isophorone
Nitrobenzene
Test
cone.
(ug/L)
20
20
100
100
Limit
for s
(ug/L)
5.1
4.8
32.3
33.3
Range
for 7
(ug/L)
3.6-22.8
3.8-23.0
8.0-100.0
25.7-100.0
Range
P, PS
00
6-125
8-126
D-117
6-118
s = Standard deviation of four recovery measurements, in ug/L.
7 = Average recovery for four^recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCriteria from 40 CFR Part 136 for Method 609. These criteria are based
directly upon the method performance data in Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 4.
8090 - 12
Revision
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
2,4-D1n1trotoluene
2,4-D1n1trotoluene
Isophorene
Nitrobenzene
Accuracy, as
recovery, x1
(ug/L)
0.65C+0.22
0.66C+0.20
0.49C+2.93
0.60C+2.00
Single analyst
precision, sr'
(ug/L)
0.207+0.08
0.197+0.06
0.287+2.77
0.257+2.53
Overal 1
precision,
S1 (ug/L)
0.377-0.07
0.367-0.00
0.467+0.31
0.377-0.78
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, 1n ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, 1n ug/L.
S1 = Expected Interlaboratory standard deviation of measurements at an
average concentration found of 7, 1n ug/L.
C = True value for the concentration, 1n ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, 1n ug/L.
8090 - 13
Revision
Date September 1986
-------
METHOD BO9O
NITROAROMATICS AND CYCLIC KETONES
7.1.1
Choose
extract Ion
procedure from
Chapter Z
7.1.3
Rinse
with hexane:
re—concentrate
to .5 mL:
adjust to Z mL
7. 1.3
Yes
Are the MOL
In table Z
required?
Concentrate to
1 mL using K-D
apparatus
Yes
IB cleanup
required?
Cleanup using
Method 362O
7. 1.3
Into cor
tor tut
hexane:
to 1
Rinse
flash
icentra-
>e with
adjust
10 mL
0
7.1.4
Rinse
with hexane:
concetrate to
.5 ml using K-D
Is cleanup
.required?
Yes
7.1.4
Adjust volume
to
1 mL
7.1.4
Adjust volume
to Z mL
7.1.41
Cleanup using
Method 362O
8090 - 14
Revision p
Date September 1986
-------
METHOD 8090
NITROAROMATXCS AND CYCLIC KETONES
(Continued)
7.S
Set GC column
operating
conditions
7.3
Calibrate (see
Method BOOO)
7.4
Perform
GC analysis
(see Method
aoooi
( Stop J
8090 - 15
Revision 0
Date September 1986
-------
METHOD 8100
POLYNUCLEAR AROMATIC HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 Method 8100 is used to determine the concentration of certain
polynuclear aromatic hydrocarbons (PAH). Table 1 Indicates compounds that may
be determined by this method.
1.2 The packed column gas chromatographic method described here cannot
adequately resolve the following four pairs of compounds: anthracene and
phenanthrene; chrysene and benzo(a)anthracene; benzo(b)fluoranthene and
benzo(k)fluoranthene; and dibenzo(a,h)anthracene and indeno(l,2,3-cd)pyrene.
The use of a capillary column instead of the packed column, also described 1n
this method, may adequately resolve these PAHs. However, unless the purpose
of the analysis can be served by reporting a quantitative sum for an
unresolved PAH pair, either liquid chromatography (Method 8310) or gas chroma-
tography/mass spectroscopy (Method 8270) should be used for these compounds.
2.0 SUMMARY OF METHOD
2.1 Method 8100 provides gas chromatographlc conditions for the
detection of ppb levels of certain polynuclear aromatic hydrocarbons. Prior
to use of this method, appropriate sample extraction techniques must be used.
Both neat and diluted organic liquids (Method 3580, Waste Dilution) may be
analyzed by direct injection. A 2- to 5-uL aliquot of the extract 1s Injected
Into a gas chromatograph (GC) using the solvent flush technique, and compounds
1n the GC effluent are detected by a flame lonization detector (FID).
2.2 If interferences prevent proper detection of the analytes of
interest, the method may also be performed on extracts that have undergone
cleanup using silica gel column cleanup (Method 3630).
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
8100 - 1
Revision 0
Date September 1986
-------
TABLE 1. GAS CHROMATOGRAPHY OF POLYNUCLEAR AROMATIC HYDROCARBONS3
Compound Retention time (m1n)
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo b fluoranthene
Benzo J fluoranthene
Benzo k fluoranthene
Benzo (ghl)perylene
Chrysene
10
10
15
20
29
28
28
38
24
.8
.4
.9
.6
.4
.0
.0
.6
.7
D1benz(a,h)acr1d1ne
D1benz(a,J)acr1d1ne
Dlbenzo(a,h)anthracene 36.2
7H-D1benzo(c,g)carbazole
D1benzo(a,e)pyrene
D1benzo(a,h)pyrene
Dlbenzo(a,1)pyrene
Fluoranthene 19.8
Fluorene 12.6
Indeno(l,2,3-cd)pyrene 36.2
3-Methy1cholanthrene
Naphthalene 4.5
Phenanthrene 15.9
Pyrene 20.6
aResults obtained using Column 1,
8100 - 2
Revision
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, Including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights 1s
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: 1.8-m x 2-mm I.D. glass column packed with
3% OV-17 on Chromosorb W-AW-DCMS (100/120 mesh) or equivalent.
4.1.2.2 Column 2: 30-m x 0.25-mm I.D. SE-54 fused silica
capillary column.
4.1.2.3 Column 3: 30-m x 0.32-mm I.D. SE-54 fused silica
capillary column.
4.1.3 Detector: Flame 1on1zat1on (FID).
4.2 Volumetric flask; 10-, 50-, and 100-mL, ground-glass stopper.
4.3 Microsyringe; 10-uL.
5.0 REAGENTS
5.1 Solvents: Hexane, Isooctane (2,2,4-trlmethylpentane) (pesticide
quality or equivalent).
5.2 Stock standard solutions;
5.2.1 Prepare stock standard solutions at a concentration of 1.00
ug/uL by dissolving 0.0100 g of assayed reference material 1n Isooctane
and diluting to volume 1n a 10-mL volumetric flask. Larger volumes can
be used at the convenience of the analyst. When compound purity 1s
assayed to be 96% or greater, the weight can be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration 1f they are
certified by the manufacturer or by an independent source.
5.2.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner 1f comparison with check standards Indicates a problem.
8100 - 3
Revision
Date September 1986
-------
5.3 Calibration standards; Calibration standards at a minimum of five
concentrationlevelsshouldbe prepared through dilution of the stock
standards with isooctane. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC. Cali-
bration solutions must be replaced after six months, or sooner if comparison
with a check standard indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest as described in
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane.
5.4.3 Analyze each calibration standard according to Section 7.0.
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction,cleanup(when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g., 2-
fluorobiphenyl and 1-fluoronaphthalene) recommended to encompass the range of
the temperature program used in this method. Method 3500, Section 5.3.1.1,
details instructions on the preparation of base/neutral surrogates.
Deuterated analogs of analytes should not be used as surrogates for gas
chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and must be analyzed
within 40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral pH with methylene chloride, using either Method 3510 or 3520.
Solid samples are extracted using either Method 3540 or 3550. To achieve
maximum sensitivity with this method, the extract must be concentrated to
1 mL.
8100 - 4
Revision 0
Date September 1986
-------
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set nitrogen carrier gas flow at 40-mL/m1n flow
rate. Set column temperature at 100*C for 4 m1n; then program at 8*C/min
to a final hold at 280*C.
7.2.2 Column 2: Set helium carrier gas at 20-cm/sec flow rate.
Set column temperature at 35*C for 2 m1n; then program at 10*C/min to
265'C and hold for 12 m1n.
7.2.3 Column 3: Set helium carrier gas at 60 cm/sec flow rate.
Set column temperature at 35*C for 2 m1n; then program at 10'C/min to
265*C and hold for 3 m1n.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques.
7.3.1 The procedure for Internal or external standard calibration
may be used. Refer to Method 8000 for a description of each of these
procedures.
7.3.2 If cleanup Is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will validate elution patterns and the
absence of Interferents from the reagents.
7.4 Gas chromatographic analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique is used, add 10 uL of internal standard to the sample prior to
Injection.
7.4.2 Follow Section 7.6 1n Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.4.3 Record the sample volume Injected and the resulting peak
sizes (in area units or peak heights).
7.4.4 Using either the internal or external calibration procedure
(Method 8000), determine the Identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Section 7.8 of Method 8000 for calculation
equations.
7.4.5 If peak detection and identification are prevented due to
interferences, the extract may undergo cleanup using Method 3630.
7.5 Cleanup;
7.5.1 Proceed with Method 3630. Instructions are given in this
method for exchanging the solvent of the extract to hexane.
8100 - 5
Revision 0
Date September 1986
-------
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described 1n the previous paragraphs and 1n Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered 1n Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each analyte at the following concentrations
in acetonltrile: naphthalene, 100 ug/mL; acenaphthylene, 100 ug/mL;
acenaphthene, 100 ug/mL; fluorene, 100 ug/mL; phenanthrene, 100 ug/mL;
anthracene, 100 ug/mL; benzo(k)flubranthene, 5 ug/mL; and any other PAH
at 10 ug/mL.
8.2.2 Table 2 indicates the calibration and QC acceptance criteria
for this method. Table 3 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following procedures
are required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 16 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 0.1 to 425 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
8100 - 6
Revision 0
Date September 1986
-------
the concentration of the analyte and essentially independent of the sample
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 3.
9.2 This method has been tested for linearity of spike recovery from
reagent water and has been demonstrated to be applicable over the
concentration range from 8 x MDL to 800 x MDL with the following exception:
benzo(ghi)perylene recovery at 80 x and 800 x MDL were low (35% and 45%,
respectively).
9.3 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 9 - PAHs," Report for EPA Contract 68-03-
2624 (in preparation).
2. Sauter, A.D., L.D. Betowski, T.R. Smith, V.A. Strickler, R.G. Beimer,
B.N. Colby, and J.E. Wilkinson, "Fused Silica Capillary Column GC/MS for the
Analysis of Priority Pollutants," Journal of HRC&CC 4, 366-384, 1981.
3. "Determination of Polynuclear Aromatic Hydrocarbons in Industrial and
Municipal Wastewaters," EPA-600/4-82-025, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268, September 1982.
4. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
5. "EPA Method Validation Study 20, Method 610 (Polynuclear Aromatic
Hydrocarbons)," Report for EPA Contract 68-03-2624 (in preparation).
6. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
7. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63, 1983.
8100 - 7
Revision 0
Date September 1986
-------
TABLE 2. QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Benzo (ghi ) peryl ene
Benzo (k)fl uoranthene
Chrysene
Dibenzo (a, h) anthracene
Fl uoranthene
Fluorene
Indeno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40.3
45.1
28.7
4.0
4.0
3.1
2.3
2.5
4.2
2.0
3.0
43.0
3.0
40.7
37.7
3.4
Range
for 7
(ug/U
D-105.7
22.1-112.1
11.2-112.3
3.1-11.6
0.2-11.0
1.8-13.8
D-10.7
D-7.0
D-17.5
0.3-10.0
2.7-11.1
D-119
1.2-10.0
21.5-100.0
8.4-133.7
1.4-12.1
Range
P. PS
(%)
D-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
Criteria from 40 CFR Part 136 for Method 610. These criteria are based
directly upon the method performance data 1n Table 3. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 3.
8100 - 8
Revision
Date September 1986
-------
TABLE 3. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f 1 uoranthene
Benzo (ghi)perylene
Benzo (k) f 1 uoranthene
Chrysene
Dlbenzo (a, h) anthracene
Fl uoranthene
Fluorene
Ideno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Accuracy, as
recovery, x1
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44C+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.287+0.04
0.387-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.327-0.18
0.247+0.02
0.227+0.06
0.447-1.12
0.297+0.02
0.397-0.18
0.297+0.05
0.257+0.14
Overall
precision,
S1 (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.537-0.01
0.387-0.00
0.587+0.10
0.697+0.10
0.667-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8100 - 9
Revision 0
Date September 1986
-------
METHOD 8100
POLYNUCLEAR AROMATIC HYDROCARBONS
7.1.1
Choose
» appro-
priate extract-
Ion procedure
(refer to
Chapter 2)
7.2
Set gas
chromatography
conditions
7.3.21
I Process
series of
•tanaards
through cleanup
procedures
.Do GC analysis
(refer to
Method 8000)
7.3
Refer to
Method 8000
for proper
calibration
techniques
Q
7.5. 1
Do cleanup
using Method
3630
8100 - 10
Revision 0
Date September 1986
-------
METHOD 8120
CHLORINATED HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 Method 8120 1s used to determine the concentration of certain
chlorinated hydrocarbons. Table 1 indicates compounds that may be determined
by this method and lists the method detection limit for each compound in
reagent water. Table 2 lists the practical quantitation limit (PQL) for other
matrices.
2.0 SUMMARY OF METHOD
2.1 Method 8120 provides gas chromatographic conditions for the
detection of ppb levels of certain chlorinated hydrocarbons. Prior to use of
this method, appropriate sample extraction techniques must be used. Both neat
and diluted organic liquids (Method 3580, Waste Dilution) may be analyzed by
direct Injection. A 2- to 5-uL aliquot of the extract 1s Injected Into a gas
chromatograph (GC) using the solvent flush technique, and compounds 1n the GC
effluent are detected by an electron capture detector (ECD).
2.2 If Interferences are encountered in the analysis, Method 8120 may
also be performed on extracts that have undergone cleanup using Method 3620.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
3.2 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All of these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph;
4.1.1 Gas chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
8120 - 1
Revision
Date September 1986
-------
TABLE 1. GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Compound
Retention time (nrin)
Col. 1 Col. 2
nd = not determined.
a!50°C column temperature.
bl65°C column temperature.
C100*C column temperature.
Method
Detection
limit (ug/L)
Benzal chloride
Benzotri chloride
Benzyl chloride
2-Chl oronaphthal ene
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Tetrachlorobenzenes
1,2, 4-Tri chl orobenzene
Pentachlorohexane
2.7a
6.6
4.5
5.2
5.6a
7.7
nd
4.9
15.5
3.6°
9.3
6.8
7.6
10. lb
20.0
16. 5^
8.3
22.3
0.94
1.14
1.19
1.34
0.05
0.34
0.40
0.03
0.05
8120 - 2
Revision 0
Date September 1986
-------
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
8120 - 3
Revision
Date September 1986
-------
accessories, Including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights 1s
recommended.
4.1.2 Columns:
4.1.2.1 Column 1: 1.8-m x 2-mm I.D. glass column packed with
1% SP-1000 on Supelcoport (100/120 mesh) or equivalent.
4.1.2.2 Column 2: 1.8-m x 2-mrn I.D. glass column packed with
1.5% OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or equivalent.
!
4.1.3 Detector: Electron capture (ECD).
4.2 Kuderna-Dam'sh (K-D) apparatus;
4.2.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts
4.2.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.2.3 Snyder column: Three-ball macro (Kontes K-5Q3000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.4 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.5 Volumetric flasks; 10-, 50-, and 100-mL, ground-glass stopper.
4.6 Microsyrlnge; 10-uL.
4.7 Syri nge; 5-mL.
4.8 Vials; Glass, 2-, 10-, and 20-mL capacity with Teflon-Hned screw
cap.
5.0 REAGENTS
5.1 Solvents; hexane, isooctane, acetone (pesticide quality or
equivalent).
8120 - 4
Revision
Date September 1986
-------
5.2 Stock standard solutions;
5.2.1 Prepare stock standard solutions at a concentration of
1.00 ug/uL by dissolving 0.0100 g of assayed reference material in
isooctane and diluting to volume in a 10-mL volumetric flask. Larger
volumes can be used at the convenience of the analyst. When compound
purity is assayed to be 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.2.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standards
should be checked frequently for signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
5.3 Calibration standards; Calibration standards at a minimum of five
concentrationlevelsshouldbe prepared through dilution of the stock
standards with isooctane. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC.
Calibration solutions must be replaced after six months, or sooner if
comparison with check standards indicates a problem.
5.4 Internal standards (if internal standard calibration is used); To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest as described in
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with isooctane.
5.4.3 Analyze each calibration standard according to Section 7.0.
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction,cleanup(when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g.,
chlorinated hydrocarbons that are not expected to be in the sample)
recommended to encompass the range of the temperature program used 1n this
method. Method 3500, Section 5.3.1.1, details instructions on the preparation
of base/neutral surrogates. Deuterated analogs of analytes should not be used
as surrogates for gas chromatographic analysis due to coelution problems.
8120 - 5
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as 1s, pH with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographlc analysis, the extraction solvent
must be exchanged to hexane. The exchange 1s performed during the K-D
procedures listed 1n all of the extraction methods. The exchange 1s
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1-mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.2.2 Momentarily remove the Snyder column, add 50 mL of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 mL of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube 1s partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 mL, remove the K-D apparatus and allow it to drain and
cool for at least 10 min. The extract will be handled differently
at this point, depending on whether or not cleanup is needed. If
cleanup is not required, proceed to Paragraph 7.1.2.3. If cleanup
1s needed, proceed to Paragraph 7.1.2.4.
7.1.2.3 If cleanup of the extract is not required, remove the
Snyder column and rinse the flask and Its lower joint into the
concentrator tube with 1-2 mL of hexane. A 5-mL syringe is
recommended for this operation. Adjust the extract volume to
10.0 mL. Stopper the concentrator tube and store refrigerated at
4*C 1f further processing will not be performed Immediately. If the
extract will be stored longer than two days, it should be
transferred to a Teflon-sealed screw-cap vial. Proceed with gas
chromatographlc analysis.
8120 - 6
Revision 0
Date September 1986
-------
7.1.2.4 If cleanup of the extract 1s required, remove the
Snyder column and rinse the flask and Its lower joint Into the
concentrator tube with a minimum amount of hexane. A 5-mL syringe
1s recommended for this operation. Add a clean boiling chip to the
concentrator tube and attach a two-ball mlcro-Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top. Place the
m1cro-K-D apparatus on the water bath (80*C) so that the concen-
trator tube 1s partially Immersed 1n the hot water. Adjust the
vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus and allow 1t to drain and
cool for at least 10 m1n.
7.1.2.5 Remove the mlcro-Snyder column and rinse the flask and
Its lower joint Into the concentrator tube with 0.2 ml of hexane.
Adjust the extract volume to 2.0 ml and proceed with Method 3620.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column 1: Set 5% methane/95% argon carrier gas flow at
25 mL/m1n flow rate. Set column temperature at 65*C Isothermal, unless
otherwise specified (see Table 1).
7.2.2 Column 2: Set 5% methane/95% argon carrier gas flow at
25 mL/min flow rate. Set column temperature at 75*C Isothermal, unless
otherwise specified (see Table 1).
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques"! Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.3.2 If cleanup 1s performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will validate elutlon patterns and the
absence of Interferents from the reagents.
7.4 Gas chromatographlc analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique Is used, add 10 uL of Internal standard to the sample prior to
Injecting.
7.4.2 Follow Section 7.6 1n Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
8120 - 7
Revision 0
Date September 1986
-------
7.4.3 Examples of GC/ECD chromatograms for certain chlorinated
hydrocarbons are shown 1n Figures 1 and 2.
7.4.4 Record the sample volume Injected and the resulting peak
sizes (in area units or peak heights).
7.4.4 Using either the Internal or external calibration procedure
(Method 8000), determine the Identity and quantity of each component peak
1n the sample chromatogram which Corresponds to the compounds used for
calibration purposes. See Section 7.8 of Method 8000 for calculation
equations.
7.4.5 If peak detection and Identification are prevented due to
interferences, the hexane extract may undergo cleanup using Method 3620.
7.5 Cleanup;
7.5.1 Proceed with Method 3620 using the 2-mL hexane extracts
obtained from Paragraph 7.1.2.5.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and 1n Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for .specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and 1n the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method
8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each parameter of interest at the following
concentrations 1n acetone: hexachloro-substituted hydrocarbon, 10 ug/mL;
and any other chlorinated hydrocarbon, 100 ug/mL.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8120 - 8
Revision
Date September 1986
-------
Column: 1.5% OV-1+1.5% OV-225 on Gas Chrom Q
Ttmptraturt: 75°C
Dtttctor: Eltctron Capture
4 8 12 16
RETENTION TIME (MINUTES)
20
Figure 1. Gas chromatogram of chlorinated hydrocarbons (low molecular weight compounds).
8120 - 9
Revision o
Date September 1986
-------
1
I
g
«>
1
I''
?
0
i
-------
8.3.1 If recovery 1s not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
Instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 20 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 1.0 to 356 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the parameter and essentially independent of the sample
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 3 - Chlorinated Hydrocarbons, and
Category 8 - Phenols," Report for EPA Contract 68-03-2625 (in preparation).
2. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
3. "EPA Method Validation Study 22, Method 612 (Chlorinated Hydrocarbons),"
Report for EPA Contract 68-03-2625 (in preparation).
4. "Method Performance for Hexachlorocyclopentadiene by Method 612,"
Memorandum from R. Slater, U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268, December 7, 1983.
5. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
7. "Determination of Chlorinated Hydrocarbons in Industrial and Municipal
Wastewaters," Report for EPA Contract 68-03-2625 (in preparation).
8120 - 11
Revision 0
Date September 1986
-------
TABLE 3. QC ACCEPTANCE CRITERIA3
Parameter
2-Chloronaphthalene
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl orocycl opentadl ene
Hexachl oroethane
1,2, 4-Tr1 chl orobenzene
Test
cone.
(ug/L)
100
100
100
100
10
10
10
10
100
Limit
for s
(ug/L)
37.3
28.3
26.4
20.8
2.4
2.2
2.5
3.3
31.6
Range
for 7
(ug/L)
29.5-126.9
23.5-145.1
7.2-138.6
22.7-126.9
2.6-14.8
D-12.7
D-10.4
2.4-12.3
20.2-133.7
Range
P, PS
(%)
9-148
9-160
D-150
13-137
15-159
D-139
D-lll
8-139
5-149
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
P, Ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCHter1a from 40 CFR Part 136 for Method 612. These criteria are based
directly upon the method performance data 1n Table 4. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 4.
8120 - 12
Revision 0
Date September 1986
-------
Table 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Chloronaphthalene
1 , 2-D1 chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachlorobutadlene
Hexachl orocycl opentadi enea
Hexachl oroethane
1,2, 4-Tri chl orobenzene
Accuracy, as
recovery, x1
(ug/L)
0.75C+3.21
0.85C-0.70
0.72C+0.87
0.72C+2.80
0.87C-0.02
0.61C+0.03
0.47C
0.74C-0.02
0.76C+0.98
Single analyst Overall
precision, sr'
(ug/L)
0.287-1.17
0.227-2.95
0.217-1.03
0.167-0.48
0.147+0.07
0.187+0.08
0.247
0.237+0.07
0.237-0.44
precision,
S1 (ug/L)
0.387-1.39
0.417-3.92
0.497-3.98
0.357-0.57
0.367-0.19
0.537-0.12
0.507
0.367-0.00
0.407-1.37
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
Estimates based upon the performance in a single laboratory.
8120 - 13
Revision 0
Date September 1986
-------
METHOD BISO
CHLORINATED HYDROCARBONS
0
7.1.1
' Choose
appropriate
extraction
procedure
(see Chapter 2)
7 .
Perform GC
analysis (see
Method 8000)
7.1.2
Exchange
extract-
Ion solvent to
hexane
during K—0
procedures
7.2
Set gas
chromatography
conditions
7.5.1
Cleanup
using Method
3E20
7
1 Refer to
Method 6OOO
for proper
calibration
techniques
7.3.2
Process
a series
of standards
through cleanup
procedure:
analyze by GC
8120 - 14
Revision 0
Date September 1986
-------
METHOD 8140
ORGANOPHOSPHORUS PESTICIDES
1.0 SCOPE AND APPLICATION
1.1 Method 8140 Is a gas chromatographic (GC) method used to determine
the concentration of various organosphosphorus pesticides. Table 1 Indicates
compounds that may be determined by this method and lists the method detection
limit for each compound in reagent water. Table 2 lists the practical
quantisation limit (PQL) for other matrices.
1.2 When Method 8140 is used to analyze unfamiliar samples, compound
identifications should be supported by at least two additional qualitative
techniques if mass spectroscopy 1s not employed. Section 8.4 provides gas
chromatograph/mass spectrometer (GC/MS) criteria appropriate for the
qualitative confirmation of compound identifications.
2.0 SUMMARY OF METHOD
2.1 Method 8140 provides gas chromatographic conditions for the
detection of ppb levels of organophosphorus pesticides. Prior to analysis,
appropriate sample extraction techniques must be used. Both neat and diluted
organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. A 2- to 5-uL aliquot of the extract is injected into a gas
chromatograph, and compounds in the GC effluent are detected with a flame
photometric or thermionic detector.
2.2 If interferences are encountered in the analysis, Method 8140 may
also be performed on extracts that have undergone cleanup using Method 3620
and/or Method 3660.
3.0 INTERFERENCES
3.1 Refer to Methods 3500 (Section 3.5, in particular), 3600, and 8000.
3.2 The use of Florisll cleanup materials (Method 3620) for some of the
compounds in this method has been demonstrated to yield recoveries less than
85% and is therefore not recommended for all compounds. Refer to Table 2 of
Method 3620 for recoveries of organophosphorous pesticides as a function of
Florisil fractions. Use of phosphorus- or halogen-specific detectors,
however, often obviates the necessity for cleanup for relatively clean sample
matrices. If particular circumstances demand the use of an alternative
cleanup procedure, the analyst must determine the elution profile and
demonstrate that the recovery of each analyte is no less than 85%.
8140 - 1
Revision 0
Date September 1986
-------
TABLE 1. GAS CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS FOR
ORGANOPHOSPHOROUS PESTICIDES3
Compound
Azlnphos methyl
Bolstar
Chlorpyrlfos
Coumaphos
Demeton-0
Demeton-S
Diazlnon
Dichlorvos
Disulfoton
Ethoprop
Fensulfothlon
Fenthion
Merphos
Mevlnphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos (Tetrachlorvlnphos)
Tokuthion (Prothiofos)
Trlchloronate
GC K
col umn°
la
la
2
la
la
la
2
lb, 3
la
2
la
la
2
lb
3
2
la
2
lb, 3
la
la
Retention
time
(m1n) i
6.80
4.23
6.16
11.6
2.53
1.16
7.73
0.8, 1.50
2.10
3.02
6.41
3.12
7.45
2.41
3.28
3.37
1.43
5.57
8.52, 5.51
3.40
2.94
Method
detection
limit (ug/L)
1.5
0.15
0.3
1.5
0.25
0.25
0.6
0.1
0.20
0.25
1.5
0.10
0.25
0.3
0.1
0.03
0.15
0.3
5.0
0.5
0.15
Development of Analytical Test Procedures for Organic Pollutants in
Wastewater; Report for EPA Contract 68-03-2711 (in preparation).
b$ee Sections 4.2.1 and 7.2 for column descriptions and conditions.
8140 - 2
Revision 0
Date September 1986
-------
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water 10
Low-level soil by sonlcation with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
8140 - 3
Revision
Date September 1986
-------
3.3 Use of a flame photometric detector 1n the phosphorus mode will
minimize Interferences from materials that do not contain phosphorus.
Elemental sulfur, however, may Interfere with the determination of certain
organophosphorus pesticides by flame photometric gas chromatography. Sulfur
cleanup using Method 3660 may alleviate this Interference.
3.4 A halogen-specific detector (I.e., electrolytic conductivity or
mlcrocoulometric) Is very selective for the halogen-containing pesticides and
1s recommended for use with dlchlorvos, naled, and stlrophos.
4.0 APPARATUS AND MATERIALS
4.1 Gas chrpmatograph; Analytical system complete with gas
chromatograph suitable for on-column Injections and all required accessories,
Including detectors, column supplies, recorder, gases, and syringes. A data
system for measuring peak areas and/or peak heights 1s recommended.
4.1.1 Columns:
4.1.1.1 Column la and Ib: 1.8-m x 2-mm I.D. glass, packed
with 5% SP-2401 on Supelcoport, 100/120 mesh (or equivalent).
4.1.1.2 Column 2: 1.8-m x 2-mm I.D. glass, packed with 3% SP-
2401 on Supelcoport, 100/120 mesh (or equivalent).
4.1.1.3 Column 3: 50-cm x l/8-1n O.D. Teflon, packed with 15%
SE-54 on Gas Chrom Q, 100/120 mesh (or equivalent).
4.1.2 Detectors: The following detectors have proven effective 1n
analysis for the analytes listed 1n Table 1 and were used to develop the
accuracy and precision statements 1n Section 9.0.
4.1.2.1 Phosphorus-specific: Nitrogen/Phosphorus (N/P),
operated 1n phosphorus-sensitive mode.
4.1.2.2 Flame Photometric (FPD): FPD 1s more selective for
phosphorus than the N/P.
4.1.2.3 Halogen-specific: Electrolytic conductivity or
mlcrocoulometric. These are very selective for those pesticides
containing halogen substituents.
4.2 Balance; analytical, capable of accurately weighing to the nearest
0.0001 g.
4.3 Vials; Amber glass, 10- to 15-mL capacity with Teflon-Hned screw-
cap.
4.4 Kuderna-Danlsh (K-D) apparatus;
4.4.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts
8140 - 4
Revision 0
Date September 1986
-------
4.4.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.4.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.4.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.5 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5°C). The bath should be used 1n a hood.
4.7 Mlcrosyrlnge; 10-uL.
4.8 Syringe; 5-mL.
4.9 Volumetric flasks; 10-, 50-, and*100-mL, ground-glass stopper.
5.0 REAGENTS
5.1 Solvents: Hexane, acetone, Isooctane (2,2,4-trimethylpentane)
(pesticide quality or equivalent).
5.2 Stock standard solutions;
5.2.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in hexane or other
suitable solvent and dilute to volume in a 10-mL volumetric flask.
Larger volumes can be used at the convenience of the analyst. If
compound purity is certified at 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration 1f
they are certified by the manufacturer or by an independent source.
5.2.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
5.2.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards Indicates a problem.
5.3 Calibration standards; Calibration standards at a minimum of five
concentration levels for each parameter of Interest should be prepared through
dilution of the stock standards with Isooctane. One of the concentration
levels should be at a concentration near, but above, the method detection
8140 - 5
Revision
Date September 1986
-------
limit. The remaining concentration levels should correspond to the expected
range of concentrations found 1n real samples or should define the working
range of the GC. Calibration standards must be replaced after six months, or
sooner 1f comparison with check standards Indicates a problem.
5.4 Internal standards (1f Internal standard calibration 1s used); To
use this approach, the analyst must select one or more Internal standards that
are similar 1n analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the Internal standard 1s not
affected by method or matrix Interferences. Because of these limitations, no
Internal standard can be suggested that 1s applicable to all samples.
5.4.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of Interest as described 1n
Paragraph 5.3.
5.4.2 To each calibration standard, add a known constant amount of
one or more Internal standards, and dilute to volume with hexane or other
suitable solvent.
5.4.3 Analyze each calibration standard according to Section 7.0.
i
5.5 Surrogate standards; The analyst should monitor the performance of
the extraction,cleanup(when used), and analytical system and the
effectiveness of the method 1n dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g.,
organophosphorous pesticides not expected to be present in the sample)
recommended to encompass the range of the temperature program used 1n this
method. Deuterated analogs of analytes should not be used as surrogates for
gas chromatographic analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral, or as 1s, pH with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
may be exchanged to hexane. This Is recommended if the detector used is
halogen-specific. The exchange 1s performed during the K-D procedures
listed in all of the extraction methods. The exchange 1s performed as
follows.
8140 - 6
Revision 0
Date September 1986
-------
7.1.2.1 Following K-D of the methylene chloride extract to
1 ml using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 m1n.
7.1.2.2 Momentarily remove the Snyder column, add 50 ml of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 ml of hexane to prewet the Snyder
column. Place the K-D apparatus on the water bath so that the
concentrator tube 1s partially Immersed 1n the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete concentration 1n 5-10 m1n. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow It to drain and
cool for at least 10 min.
7.1.2.3 Remove the Snyder column and rinse the flask and Us
lower joint Into the concentrator tube with 1-2 ml of hexane. A
5-mL syringe 1s recommended for this operation. Adjust the extract
volume to 10.0 ml. Stopper the concentrator tube and store
refrigerated at 4*C 1f further processing will not be performed
Immediately. If the extract will be stored longer than two days, 1t
should be transferred to a Teflon-sealed screw-cap vial. Proceed
with gas chromatographlc analysis 1f further cleanup 1s not
required.
7.2 Gas chromatography conditions (Recommended);
7.2.1 Column la: Set helium carrier gas flow at 30 mL/m1n flow
rate. Column temperature 1s set at 150*C for 1 m1n and then programmed
at 25*C/m1n to 220'C and held.
7.2.2 Column Ib: Set nitrogen carrier gas flow at 30 mL/m1n flow
rate. Column temperature 1s set at 170*C for 2 m1n and then programmed
at 20*C/m1n to 220*C and held.
7.2.3 Column 2: Set helium carrier gas at 25 mL/m1n flow rate.
Column temperature Is set at 170*C for 7 m1n and then programmed at
!0*C/m1n to 250*C and held.
7.2.4 Column 3: Set nitrogen carrier gas at 30 mL/m1n flow rate.
Column temperature 1s set at 100*C and then Immediately programmed at
25*C/m1n to 200*C and held.
7.3 Calibration; Refer to Method 8000 for proper calibration
techniques^Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
8140 - 7
Revision 0
Date September 1986
-------
7.3.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of Interferents from the reagents.
7.4 Gas chromatographlc analysis;
7.4.1 Refer to Method 8000. If the Internal standard calibration
technique 1s used, add 10 uL of Internal standard to the sample prior to
injection.
7.4.2 Follow Section 7.6 1n Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
7.4.3 Examples of chromatograms for various organophosphorous
pesticides are shown 1n Figures 1 through 4.
7.4.4 Record the sample volume injected and the resulting peak
sizes (in area units or peak heights).
7.4.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Section 7.8 of Method 8000 for calculation
equations.
7.4.6 If peak detection and identification are prevented due to
interferences, the hexane extract may undergo cleanup using Method 3620.
The resultant extract(s) may be analyzed by GC directly or may undergo
further cleanup to remove sulfur using Method 3660.
7.5 Cleanup:
7.5.1 Proceed with Method 3620, followed by, if necessary, Method
3660, using the 10-mL hexane extracts obtained from Paragraph 7.1.2.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described 1n the previous paragraphs and in Method 8000.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered in Method 3500 and in
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and 1n the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method
8000, Section 8.6.
8140 - 8
Revision
Date September 1986
-------
Column: 5% SP-2401 on Suptlcoport
Temperature: 170°C 7 Minutts. then
1 (PC/Minute to 250°C
Detector: Phosphorus-Specific Flame Photometric
45678
RETENTION TIME (MINUTES)
10
11
12
Figure 1. Gas chromatogram of organophosphorus pesticides (Example 1).
8140 - 9
Revision p
Date September 1986
-------
Column: 3% SP-2401
Program: 170°C 7 Minutes. 10°C/Minute
t6250°C
Detector: Phosphorus/Nitrogen
1
765432
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of organophosphorus pesticides (Example 2).
8140 - 10
Revision 0
Date September 1986
-------
Column: 15% SE-54 on Gas Chrom Q
Temperature: 100°C Initial, then
25°C/Minute to 200°C
Detector: Hall Electrolytic Conductivity-Oxidative Mode
8
7654321
RETENTION TIME (MINUTES)
Figure 3. Gas chromatogram of organophosphorus pesticides (Example 3).
8140 - 11
Revision 0
Date September 1986
-------
Column: 5% SP-2401 on Supelcoport
Temperature: 170°C 2 Minutes, then 20°C/Minute to 220°C
Detector: Phosphorus-Specific Flame Photometric
3456
RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of organophosphorus pesticides (Example 4).
8140 - 12
Revision 0
Date September 1986
-------
8.2.1 Select a representative spike concentration for each analyte
to be measured. The quality control check sample concentrate (Method
8000, Section 8.6) should contain each analyte In acetone at a
concentration 1,000 times more concentrated than the selected spike
concentration.
8.2.2 Table 3 Indicates Single Operator Accuracy and Precision for
this method. Compare the results obtained with the results given in
Table 3 to determine if the data quality 1s acceptable.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery 1s within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.4 GC/MS confirmation;
8.4.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. The GC/MS operating
conditions and procedures for analysis are those specified in Method
8270.
8.4.2 When available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
8.4.3 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps
may include the use of alternate packed or capillary GC columns and
additional cleanup.
9.0 METHOD PERFORMANCE
9.1 Single-operator accuracy and precision studies have been conducted
using spiked wastewater samples. The results of these studies are presented
in Table 3.
8140 - 13
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. Pressley, T.A. and J.E. Longbottom, "The Determination of Organophosphorus
Pesticides in Industrial and Municipal Wastewater: Method 614," U.S. EPA/EMSL,
Cincinnati, OH, EPA-600/4-82-004, 1982.
2. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists 48, 1037, 1965.
3. U.S. EPA, "Analysis of Volatile Hazardous Substances by GC/MS: Pesticide
Methods Evaluation," Letter Reports 6, 12A, and 14, EPA Contract 68-03-2697,
1982.
4. U.S. EPA, "Method 622, Organophosphorous Pesticides," Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268.
8140-14
Revision
Date September 1986
-------
TABLE 3. SINGLE-OPERATOR ACCURACY AND PRECISION3
Parameter
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Dlazinon
Dlchlorvos
Dlsulfoton
Ethoprop
Fensulfothlon
Fenthion
Merphos
Mevinphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos
Tokuthlon
Trlchloronate
Average
recovery
72.7
64.6
98.3
109.0
67.4
67.0
72.1
81.9
100.5
94.1
68.7
120.7
56.5
78.0
96.0
62.7
99.2
66.1
64.6
105.0
Standard
deviation
/ (V \
\ /
18.8
6.3
5.5
12.7
10.5
6.0
7.7
9.0
4.1
17.1
19.9
7.9
7.8
8.1
5.3
8.9
5.6
5.9
6.8
18.6
Spl ke Number
range of
(ug/L) analyses
21-250
4.9-46
1.0-50.5
25-225
11.9-314
5.6
15.6-517
5.2-92
1.0-51.5
23.9-110
5.3-64
1.0-50
15.5-520
25.8-294
0.5-500
4.9-47
1.0-50
30.3-505
5.3-64
20
17
17
18
17
17
7
16
17
18
17
17
18
16
16
21
17
18
16
17
3
Information taken from Reference 4.
8140 - 15
Revision 0
Date September 1986
-------
METHOD 8140
ORGANOPHOSPHOBUS PESTICIDES
( s"rt )
0
7.1.1
» Choose
appropriate
extraction
procedure
(see Chapter 2)
7.4
Perform GC
analysis (see
Method 80001
7.1.31
Exchange
extract-
ion solvent to
hexane
during K-D
procedures
7.2
Set gas
chromatography
conditions
7.S.II
Cleanup
using Method
3630 and 3360
If necessary
7
IM^H
< Refer to
Method 8000
for proper
calibration
techniques
7.3.2
Process
a aeries
of standards
through cleanup
procedure:
analyze by GC
Is
cleanup
necessary?
8140 - 16
Revision 0
Date September 1986
-------
METHOD 8150
CHLORINATED HERBICIDES
1.0 SCOPE AND APPLICATION
1.1 Method 8150 1s a gas chromatographic (GC) method for determining
certain chlorinated acid herbicides. Table 1 indicates compounds that may be
determined by this method and lists the method detection limit for each
compound in reagent water. Table 2 lists the practical quantitation limit
(PQL) for other matrices.
1.2 When Method 8150 is used to analyze unfamiliar samples, compound
identifications should be supported by at least one additional qualitative
technique. This method describes analytical conditions for a second gas
chromatographic column that can be used to confirm measurements made with the
primary column. Section 8.4 provides gas chromatograph/mass spectrometer
(GC/MS) criteria appropriate for the qualitative confirmation of compound
identifications.
1.3 Only experienced analysts should be allowed to work with
diazomethane due to the potential hazards associated with its use (the
compound is explosive and carcinogenic).
2.0 SUMMARY OF METHOD
2.1 Method 8150 provides extraction, esterification, and gas chroma-
tographic conditions for the analysis of chlorinated acid herbicides. Spiked
samples are used to verify the applicability of the chosen extraction
technique to each new sample type. The esters are hydrolyzed with potassium
hydroxide, and extraneous organic material is removed by a solvent wash.
After acidification, the acids are extracted with solvent and converted to
their methyl esters using diazomethane as the derivatizing agent. After
excess reagent is removed, the esters are determined by gas chromatography
employing an electron capture detector, microcoulometric detector, or
electrolytic conductivity detector (Goerlitz and Lamar, 1967). The results
are reported as the acid equivalents.
2.2 The sensitivity of Method 8150 usually depends on the level of
interferences rather than on instrumental limitations.
3.0 INTERFERENCES
3.1 Refer to Method 8000.
3.2 Organic acids, especially chlorinated acids, cause the most direct
interference with the determination. Phenols, including chlorophenols, may
also interfere with this procedure.
8150 - 1
Revision
Date September 1986
-------
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS FOR CHLORINATED
HERBICIDES
Retention time (m1n)a Method
detection
Compound
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Sllvex)
Dalapon
Oicamba
Dlchloroprop
Dinoseb
MCPA
MCPP
Col. la
2.0
4.1
3.4
2.7
-
1.2
-
-
-
—
Col.lb
-
-
-
-
-
4.8
11.2
4.1
3.4
Col. 2 Col. 3
1.6
-
2.4
2.0
5.0
1.0
-
-
-
— —
limit (ug/L)
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
aColumn conditions are given 1n Sections 4.1 and 7.4.
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factorb
Ground water . . 10
Low-level soil by sonlcatlon with GPC cleanup 670
High-level soil and sludges by sonlcatlon 10,000
Non-water mlsdble waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor 1s on a wet-weight basis.
8150 - 2
Revision
Date September 1986
-------
3.3 Alkaline hydrolysis and subsequent extraction of the basic solution
remove many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.
3.4 The herbicides, being strong organic acids, react readily with
alkaline substances and may be lost during analysis. Therefore, glassware and
glass wool must be acid-rinsed, and sodium sulfate must be acidified with
sulfuric acid prior to use to avoid this possibility.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph; Analytical system complete with gas chroma-
tograph suitable for on-column injections and all required accessories,
including detectors, column supplies, recorder, gases, and syringes. A data
system for measuring peak areas and/or peak heights 1s recommended.
4.1.1 Columns:
4.1.1.1 Column la and Ib: 1.8-m x 4-mm I.D. glass, packed
with 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or
equivalent.
4.1.1.2 Column 2: 1.8-m x 4-mm I.D. glass, packed with 5% 0V-
210 on Gas Chrom Q (100/120 mesh) or equivalent.
4.1.1.3 Column 3: 1.98-m x 2-mm I.D. glass, packed with 0.1%
SP-1000 on 80/100 mesh Carbopack C or equivalent.
4.1.2 Detector: Electron capture (ECD).
4.2 Erlenmeyer flasks; 250- and 500-mL Pyrex, with 24/40 ground-glass
joint.
4.3 Beaker; 500-mL.
4.4 Diazomethane generator; Refer to Section 7.3 to determine which
method of diazomethane generation should be used for a particular application.
4.4.1 Dlazald kit: recommended for the generation of diazomethane
using the procedure given in Section 7.3.2 (Aldrich Chemical Co., Cat.
No. 210,025-2 or equivalent).
4.4.2 Assemble from two 20 x 150-mm test tubes, two Neoprene rubber
stoppers, and a source of nitrogen. Use Neoprene rubber stoppers with
holes drilled in them to accommodate glass delivery tubes. The exit tube
must be drawn to a point to bubble diazomethane through the sample
extract. The generator assembly is shown 1n Figure 1. The procedure for
use of this type of generator is given 1n Section 7.3.3.
4.5 Vials; Amber glass, 10- to 15-mL capacity with Teflon-lined screw
cap.
8150 - 3
Revision 0
Date September 1986
-------
glass tubing
nitrogen
CO
i—>
01
o
I
•t*
rubber stopper
O 50
a» n
rt- <
a> ->•
00 O
(V 3
O
rt
(D
tube 1
tube 2
oo
01
Figure 1. Dlazomethane generator.
-------
4.6 Separatory funnel; 2-L, 125-mL, and 60-mL.
4.7 Drying column; 400-mm x 20-mm I.D. Pyrex chromatographlc column
with Pyrex glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed by
50 ml of elutlon solvent prior to packing the column with adsorbent.
4.8 Kuderna-Dam'sh (K-D) apparatus;
4.8.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts
4.8.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.8.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.9 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.10 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
4.11 Microsyringe; 10-uL.
4.12 Wrist shaker; Burrell Model 75 or equivalent.
4.13 Glass wool; Pyrex, add washed.
4.14 Balance; Analytical, capable of accurately weighting to the
nearest 0.0001 g.
4.15 Syri nge; 5-mL.
4.16 Glass rod.
5.0 REAGENTS
5.1 Reagent water; Reagent water 1s defined as a water in which an
interferent 1s not observed at the method detection limit of each parameter of
interest.
8150 - 5
Revision
Date September 1986
-------
5.2 Sulfuric add solution;
5.2.1 (1:1) (v/v) - slowly add 50 ml ^804 (sp. gr. 1.84) to 50 ml
of reagent water.
5.2.2 (1:3) (v/v) - slowly add 25 mL H2So4 (sp. gr. 1.84) to 75 ml
of reagent water.
5.3 Hydrochloric acid; (ACS), (1:9) (v/v) - add one volume of
concentrated HC1 to 9 volumes of reagent water.
5.4 Potassium hydroxide solution; 37% aqueous solution (w/v). Dissolve
37 g ACS grade potassium hydroxide pellets in reagent water and dilute to
100 ml.
5.5 Carbitol (D1ethyle,.c glycol monoethyl ether): (ACS), available from
Aldrlch Chemical Co.
5.6 Solvents;
5.6.1 Acetone, methanol, ethanol, methylene chloride, hexane
(pesticide quality or equivalent).
5.6.2 D1ethyl ether: Pesticide quality or equivalent. Must be
free of peroxides, as indicated by EM Quant test strips (available from
Scientific Products Co., Cat. No. P1126-8, and other suppliers).
Procedures recommended for removal of peroxides are provided with the
test strips. After cleanup, 20 ml ethanol preservative must be added to
each liter of ether.
5.7 Sodium sulfate; (ACS) granular, acidified, anhydrous. Heat treat in
a shallow tray at 400'C for a minimum of 4 hr to remove phthalates and other
interfering organic substances. Alternatively, heat 16 hr at 400-500'C in a
shallow tray or Soxhlet extract with methylene chloride for 48 hr. Acidify by
slurrying 100 g sodium sulfate with enough diethyl ether to just cover the
solid; then add 0.1 ml of concentrated sulfuric acid and mix thoroughly.
Remove the ether under a vacuum. Mix 1 g of the resulting solid with 5 ml of
reagent water and measure the pH of the mixture. It must be below a pH of 4.
Store at 130*C.
5.8 N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald): (ACS) available
from Aldrich Chemical Co.
5.9 Silicic acid; chromatographlc grade, nominal 100 mesh. Store at
130*C.
5.10 Stock standard solutions; Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions.
5.10.1 Prepare stock standard solutions by accurately weighing
about 0.0100 g of pure acids. Dissolve the material in pesticide quality
diethyl ether and dilute to volume 1n a 10-mL volumetric flask. Larger
8150 - 6
Revision 0
Date September 1986
-------
volumes can be used at the convenience of the analyst. If compound
purity 1s certified at 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commerically prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.10.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4'C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
5.10.3 Stock standard solutions must be replaced after 1 year, or
sooner if comparison with check standards indicates a problem.
5.11 Calibration standards: Calibration standards at a minimum of five
concentration levels for each parameter of interest should be prepared through
dilution of the stock standards with diethyl ether. One of the concentration
levels should be at a concentration near, but above, the method detection
limit. The remaining concentration levels should correspond to the expected
range of concentrations found 1n real samples or should define the working
range of the GC. Calibration solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
5.12 Internal standards (if internal standard calibration is used): To
use this approach, the analyst must select one or more internal standards that
are similar 1n analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is applicable to all samples.
5.12.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of Interest as described 1n
Paragraph 5.11.
5.12.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with diethyl ether.
5.12.3 Analyze each calibration standard according to Section 7.0.
5.13 Surrogate standards; The analyst should monitor the performance of
the extraction, cleanup(when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two herbicide surrogates
(e.g., herbicides that are not expected to be present in the sample)
recommended to encompass the range of the temperature program used 1n this
method. Deuterated analogs of analytes should not be used as surrogates for
gas chromatographlc analysis due to coelutlon problems.
8150 - 7
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and analyzed within
40 days of extraction.
7.0 PROCEDURE
7.1 Preparation of solid samples;
7.1.1 Extraction:
7.1.1.1 To a 500-mL, wide-mouth Erlenmeyer flask add 50 g (dry
weight) of the well-mixed, moist solid sample. Adjust the pH to 2
with concentrated HC1 and monitor the pH for 15 min with occasional
stirring. If necessary, add additional HC1 until the pH remains at
2.
7.1.1.2 Add 20 mL acetone to the flask and mix the contents
with the wrist shaker for 20 min. Add 80 mL diethyl ether to the
same flask and shake again for 20 min. Decant the extract and
measure the volume of solvent recovered.
7.1.1.3 Extract the sample twice more using 20 mL of acetone
followed by 80 mL of diethyl ether. After addition of each solvent,
the mixture should be shaken with the wrist shaker for 10 min and
the acetone-ether extract decanted.
7.1.1.4 After the third extraction, the volume of extract
recovered should be at least 75% of the volume of added solvent. If
this is not the case, additional extractions may be necessary.
Combine the extracts in a 2-liter separatory funnel containing
250 mL of 5% acidified sodium sulfate. If an emulsion forms, slowly
add 5 g of acidified sodium sulfate (anhydrous) until the solvent-
water mixture separates. A quantity of acidified sodium sulfate
equal to the weight of the sample may be added, if necessary.
7.1.1.5 Check the pH of the extract. If it is not at or below
pH 2, add more concentrated HC1 until stabilized at the desired pH.
,Gently mix the contents of the separatory funnel for 1 min and allow
the layers to separate. Collect the aqueous phase in a clean beaker
and the extract phase (top layer) in a 500-mL ground-glass
Erlenmeyer flask. Place the aqueous phase back into the separatory
funnel and re-extract using 25 mL of diethyl ether. Allow the
layers to separate and discard the aqueous layer. Combine the ether
extracts in the 500-mL Erlenmeyer flask.
7.1.2 Hydrolysis:
7.1.2.1 Add 30 mL of reagent water, 5 mL of 37% KOH, and one
or two clean boiling chips to the flask. Place a three-ball Snyder
column on the flask, evaporate the diethyl ether on a water bath,
and continue to heat for a total of 90 min.
8150 - 8
Revision 0
Date September 1986
-------
7.1.2.2 Remove the flask from the water bath and allow to
cool. Transfer the water solution to a 125-mL separatory funnel and
extract the basic solutions once with 40 ml and then twice with 20
ml of diethyl ether. Allow sufficient time for the layers to
separate and discard the ether layer each time. The phenoxy acid
herbicides remain soluble in the aqueous phase as potassium salts.
7.1.3 Solvent cleanup:
7.1.3.1 Adjust the pH to 2 by adding 5 ml cold (4'C) sulfurlc
acid (1:3) to the separatory funnel. Be sure to check the pH at
this point. Extract the herbicides once with 40 ml and twice with
20 ml of diethyl ether. Discard the aqueous phase.
7.1.3.2 Combine ether extracts in a 125-mL Erlenmeyer flask
containing 1.0 g of acidified anhydrous sodium sulfate. Stopper and
allow the extract to remain 1n contact with the acidified sodium
sulfate. If concentration and esterification are not to be
performed immediately, store the sample overnight 1n the
refrigerator.
7.1.3.3 Transfer the ether extract, through a funnel plugged
with acid-washed glass wool, into a 500-mL K-D flask equipped with a
10-mL concentrator tube. Use a glass rod to crush caked sodium
sulfate during the transfer. Rinse the Erlenmeyer flask and column
with 20-30 ml of diethyl ether to complete the quantitative
transfer.
7.1.3.4 Add one or two clean boiling chips to the flask and
attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1 ml of diethyl ether to the top. Place the apparatus
on a hot water bath (60*-65'C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask 1s bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 15-20 min. At the proper rate of
distillation, the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 min.
7.1.3.5 Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 ml of diethyl
ether. A 5-mL syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro-Snyder column to the concentrator
tube, and prewet the column by adding 0.5 ml of ethyl ether to the
top. Place the micro-K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 min. When the apparent
volume of the liquid reaches 0.5 ml_, remove the micro-K-D from the
8150 - 9
Revision 0
Date September 1986
-------
bath and allow 1t to drain and cool. Remove the Snyder column and
add 0.1 ml of methanol. Rinse the walls of the concentrator tube
while adjusting the extract volume to 1.0 ml with dlethyl ether.
Proceed to Section 7.3 for esterlflcation.
7.2 Preparation of liquid samples;,
7.2.1 Extraction:
7.2.1.1 Mark the water mlnlscus on the side of the sample
container for later determination of sample volume. Pour the entire
sample Into a 2-liter separatory funnel and check the pH with wide-
range pH paper. Adjust the pH to less than 2 w1th,sulfur1c acid
(1:1).
7.2.1.2 Add 150 ml of diethyl ether to the sample bottle,
seal, and shake for 30 sec to rinse the walls. Transfer the solvent
wash to the separatory funnel and extract the sample by shaking the
funnel for 2 min with periodic venting to release excess pressure.
Allow the organic layer to separate from the water layer for a
minimum of 10 min. If the emulsion interface between layers 1s more
than one-third the size of the solvent layer, the analyst must
employ mechanical techniques to complete the phase separation. The
optimum technique depends upon the sample and may include stirring,
filtration of the emulsion through glass wool, centrifugation, or
other physical methods. Drain the aqueous phase into a 1-liter
Erlenmeyer flask. Collect the solvent extract in a 250-mL ground-
glass Erlenmeyer flask containing 2 ml of 37% KOH. Approximately
80 ml of the diethyl ether will remain dissolved in the aqueous
phase.
7.2.1.3 Repeat the extraction two more times using 50 ml of
diethyl ether each time. Combine the extracts in the Erlenmeyer
flask. (Rinse the 1-liter flask with each additional aliquot of
extracting solvent.)
7.2.2 Hydrolysis:
7.2.2.1 Add one or two clean boiling chips and 15 ml of
reagent water to the 250-mL flask and attach a three-ball Snyder
column. Prewet the Snyder column by adding about 1 ml of diethyl
ether to the top of the column. Place the apparatus on a hot water
bath (60'-65'C) so that the bottom of the flask is bathed with hot
water vapor. Although the diethyl ether will evaporate in about 15
m1n, continue heating for a total of 60 min, beginning from the time
the flask is placed in the water bath. Remove the apparatus and let
stand at room temperature for at least 10 min.
7.2.2.2 Transfer the solution to a 60-mL separatory funnel
using 5-10 ml of reagent water. Wash the basic solution twice by
shaking for 1 min with 20-mL portions of diethyl ether. Discard the
organic phase. The herbicides remain in the aqueous phase.
8150 - 10
Revision 0
Date September 1986
-------
7.2.3 Solvent cleanup:
7.2.3.1 Acidify the contents of the separatory funnel to pH 2
by adding 2 ml of cold (4*C) sulfuric acid (1:3). Test with pH
indicator paper. Add 20 ml diethyl ether and shake vigorously for
2 min. Drain the aqueous layer into a 250-mL Erlenmeyer flask, and
pour the organic layer into a 125-mL Erlenmeyer flask containing
about 0.5 g of acidified sodium sulfate. Repeat the extraction
twice more with 10-mL aliquots of diethyl ether, combining all
solvent in the 125-mL flask. Allow the extract to remain in contact
with the sodium sulfate for approximately 2 hr.
7.2.3.2 Transfer the ether extract, through a funnel plugged
with acid-washed glass wool, into a 500-mL K-D flask equipped with a
10-mL concentrator tube. Use a glass rod to crush caked sodium
sulfate during the transfer. Rinse the Erlenmeyer flask and column
with 20-30 mL of diethyl ether to complete the quantitative
transfer.
7.2.3.3 Add one or two clean boiling chips to the flask and
attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1 mL of diethyl ether to the top. Place the apparatus
on a hot water bath (60*-65*C) so that the concentrator tube is
partially immersed in the hot water and the entire lower rounded
surface of the flask is bathed 1n vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 15-20 min. At the proper rate of
distillation, the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
1 mL, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 min.
7.2.3.4 Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 mL of diethyl
ether. A 5-mL syringe is recommended for this operation. Add a
fresh boiling chip, attach a micro-Snyder column to the concentrator
tube, and prewet the column by adding 0.5 mL of ethyl ether to the
top. Place the micro-K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature as
required to complete concentration in 5-10 min. When the apparent
volume of the liquid reaches 0.5 mL, remove the micro-K-D from the
bath and allow it to drain and cool. Remove the Snyder column and
add 0.1 mL of methanol. Rinse the walls of the concentrator tube
while adjusting the extract volume to 1.0 mL with diethyl ether.
7.2.3.5 Determine the original sample volume by refilling the
sample bottle to the mark with water and transferring to a 1-liter
graduated cylinder. Record the sample volume to the nearest 5 mL.
8150 - 11
Revision 0
Date September 1986
-------
7.3 Esterification;
7.3.1 Two methods may be used for the generation of diazomethane:
the bubbler method (set up shown in Figure 1) and the Dlazald kit method.
The bubbler method is suggested when small batches (10-15) of samples
require esterification. The bubbler method works well with samples that
have low concentrations of herbicides (e.g., aqueous samples) and 1s
safer to use than the Dlazald kit procedure. The Dlazald kit method 1s
good for large quantities of samples needing esterification. The Dlazald
kit method is more effective than the bubbler method for soils or samples
that may contain high concentrations of herbicides (e.g., samples such as
soils that may result in yellow extracts following hydrolysis may be
difficult to handle by the bubbler method). The diazomethane
derivatization (U.S. EPA, 1971) procedures, described below, will react
efficiently with all of the chlorinated herbicides described in this
method and should be used only by experienced analysts, due to the
potential hazards associated with Its use. The following precautions
should be taken:
CAUTION: Diazomethane 1s a carcinogen and can explode under certain
conditions.
- Use a safety screen.
- Use mechanical pipetting aides.
- Do not heat above 90*C — EXPLOSION may result.
- Avoid grinding surfaces, ground-glass joints, sleeve bearings,
glass stirrers -- EXPLOSION may result.
- Store away from alkali metals — EXPLOSION may result.
- Solutions of diazomethane decompose rapidly 1n the presence of
solid materials such as copper powder, calcium chloride, and
boiling chips.
7.3.2 Dlazald kit method: Instructions for preparing diazomethane
are provided with the generator kit.
7.3.2.1 Add 2 mL of diazomethane solution and let sample stand
for 10 min with occasional swirling.
7.3.2.2 Rinse inside wall of ampule with several hundred uL of
d1ethyl ether. Allow solvent to evaporate spontaneously at room
temperature to about 2 mL.
7.3.2.3 Dissolve the residue in 5 mL of hexane. Analyze by
gas chromatography.
7.3.3 Bubbler method: Assemble the diazomethane bubbler (see
Figure 1).
7.3.3.1 Add 5 mL of diethyl ether to the first test tube. Add
1 mL of diethyl ether, 1 mL Of carbitol, 1.5 mL of 37% KOH, and 0.1-
0.2 g Dlazald to the second test tube. Immediately place the exit
tube Into the concentrator tube containing the sample extract.
8150 - 12
Revision 0
Date September 1986
-------
Apply nitrogen flow (10 mL/m1n) to bubble dlazomethane through the
extract for 10 m1n or until the yellow color of dlazomethane
persists. The amount of Dlazald used 1s sufficient for esterifl-
catlon of approximately three sample extracts. An additional 0.1-
0.2 g of Dlazald may be added (after the Initial Dlazald 1s
consumed) to extend the generation of the dlazomethane. There 1s
sufficient KOH present 1n the original solution to perform a maximum
of approximately 20 m1n of total esterlflcation.
7.3.3.2 Remove the concentrator tube and seal 1t with a
Neoprene or Teflon stopper. Store at room temperature 1n a hood for
20 mln.
7.3.3.3 Destroy any unreacted dlazomethane by adding 0.1-0.2 g
silicic add to the concentrator tube. Allow to stand until the
evolution of nitrogen gas has stopped. Adjust the sample volume to
10.0 ml with hexane. Stopper the concentrator tube and store
refrigerated 1f further processing will not be performed
Immediately. It 1s recommended that the methylated extracts be
analyzed Immediately to minimize the trans-ester1f1cat1on and other
potential reactions that may occur. Analyze by gas chromatography.
7.4 Gas chromatography conditions (Recommended);
7.4.1 Column la: Set 5% methane/95% argon carrier gas flow at 70-
mL/m1n flow rate. Column temperature Is set at 185'C Isothermal.
7.4.2 Column Ib: Set 5% methane/95% argon carrier gas flow at 70-
mL/mln flow rate. Column temperature 1s set at 140*C for 6 m1n and then
programmed at !0*C/m1n to 200*C and held.
7.4.3 Column 2: Set 5% methane/95% argon carrier gas at 70-mL/m1n
flow rate. Column temperature 1s set at 185*C Isothermal.
7.4.4 Column 3: Set nitrogen (ultra-high purity) carrier gas at
25-mL/m1n flow rate. Column temperature Is set at 100°C and then
Immediately programmed at 10*C/min to 150*C and held.
7.5 Calibration; Refer to Method 8000 for proper calibration
techniques"! Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.5.1 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.5.2 The following gas chromatographic columns are recommended for
the compounds indicated:
8150 - 13
Revision 0
Date September 1986
-------
Parameter Column
Dicamba la,2
2,4-D la,2
2,4,5-TP la,2
2,4,5-T la,2
2,4-DB la
Dalapon 3
MCPP Ib
MCPA Ib
Dichloroprop Ib
Dinoseb Ib
7.6 Gas chromatographic analysis;
7.6.1 Refer to Method 8000. If the Internal standard calibration
technique Is used, add 10 uL of Internal standard to the sample prior to
Injection.
7.6.2 Follow Section 7.6 1n Method 8000 for Instructions on the
analysis sequence, appropriate dilutions, establishing dally retention
time windows, and Identification criteria. Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.
7.6.3 Examples of chromatograms for various chlorophenoxy
herbicides are shown 1n Figures 2 through 4.
7.6.4 Record the sample volume Injected and the resulting peak
sizes (in area units or peak heights).
7.6.5 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.6.6 If calibration standards have been analyzed in the same
manner as the samples (e.g., have undergone hydrolysis and
esterification), then the calculation of concentration given in Method
8000, Section 7.8 should be used. However, if calibration is done using
standards made from methyl ester compounds (compounds not esterified by
application of this method), then the calculation of concentration must
include a correction for the molecular weight of the methyl ester versus
the acid herbicide.
7.6.7 If peak detection and identification are prevented due to
interferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of standards through the
procedure to validate elution patterns and the absence of interferences
from reagents.
8150 - 14
Revision
Date September 1986
-------
Column: 1.5% SP-2250/1.95% SP-2401 on Supelcopon (100/120 Mesh)
Ttmperature: Isothtrmal at 185°C
Detector: Electron Capture
_L
0 12345
RETENTION TIME (MINUTES)
Figure 2. Gas chomatogram of chlorinated herbicides.
8150 - 15
Revision 0
Date September 1986
-------
Column: 1.5% SP-2260/1.95% SP-2401 on Supelcoport (100/120 Mesh)
Program: 140°C for 6 Mm, 10°C/Mmute to 200°C
Detector: Electron Capture
466
RETENTION TIME (MINUTES)
10
12
Figure 3. Gas chromatogram of chlorinated herbicides.
8150 - 16
Revision 0
Date September 1986
-------
J
Column: 0.1% SP-1000 on 80/100 Mtsh Ccrbopak C
Program: 100°C, 10°C/Min to 160°C
Dttictor: Electron Capture
o
0246
RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of dalapon, column 3.
8150 - 17
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered 1n Method 3500 and 1n
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method
8000, Section 8.6.
8.2.1 Select a representative spike concentration for each compound
{add or ester) to be measured. Using stock standards, prepare a quality
control check sample concentrate in acetone 1,000 times more concentrated
than the selected concentrations.
8.2.2 Table 3 Indicates Single Operator Accuracy and Precision for
this method. Compare the results obtained with the results given 1n
Table 3 to determine if the data quality 1s acceptable.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery 1s within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery is not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.4 GC/MS confirmation;
8.4.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. Refer to Method 8270
for the appropriate GC/MS operating conditions and analysis procedures.
8.4.2 When available, chemical ionization mass spectra may be
employed to aid the qualitative identification process.
8.4.3 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps
may include the use of alternate packed or capillary GC columns or
additional cleanup.
8150 - 18
Revision 0
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 In a single laboratory, using reagent water and effluents from
publicly owned treatment works (POTW), the average recoveries presented in
Table 3 were obtained. The standard deviations of the percent recoveries of
these measurements are also included in Table 3.
10.0 REFERENCES
1. U.S. EPA, National Pollutant Discharge Elimination System, Appendix A,
Fed. Reg., 38, No. 75, Pt. II, Method for Chlorinated Phenoxy Acid Herbicides
in Industrial Effluents, Cincinnati, Ohio, 1971.
2. Goerlitz, D.G., and W.L. Lamar, "Determination of Phenoxy Acid Herbicides
in Water by Electron Capture and Mlcrocoulometric Gas Chromatography," U.S.
Geol. Survey Water Supply Paper, 1817-C, 1967.
3. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
4. U.S. EPA, "Extraction and Cleanup Procedure for the Determination of
Phenoxy Acid Herbicides In Sediment," EPA Toxicant and Analysis Center, Bay
St. Louis, Mississippi, 1972.
5. "Pesticide Methods Evaluation," Letter Report 133 for EPA Contract No. 68-
03-2697. Available from U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
6. McNair, H.M. and E.J. BonelH, "Basic Chromatography," Consolidated
Printing, Berkeley, California, p. 52, 1969.
7. Elchelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry,"
Analytical Chemistry, 47, 995, 1975.
8. Glaser, J.A. et.al., "Trace Analysis for Wastewaters," Environmental
Science & Technology, _15, 1426, 1981.
9. U.S. EPA, "Method 615. The Determination of Chlorinated Herbicides 1n
Industrial and Municipal Wastewater," Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, 45268, June 1982.
8150 - 19
Revision
Date September 1986
-------
TABLE 3. SINGLE-OPERATOR ACCURACY AND PRECISION3
Parameter
2,4-D
Dalapon
2,4-DB
Dlcamba
Dlchlorprop
Dinoseb
MCPA
"
MCPP
2,4,5-T
2,4,5-TP
Sample
Type
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
Spike
(ug/L)
10.9
10.1
200
- 23.4
23.4.
468
10.3
10.4
208
1.2
1.1
22.2
10.7
10.7
213
0.5
102
2020
2020
21400
2080
2100
20440
1.1
1.3
25.5
1.0
1.3
25.0
Mean
Recovery
(%)
75
77
65
66
96
81
93
93
77
79
86
82
97
72
100
86
81
98
73
97
94
97
95
85
83
78
88
88
72
Standard
deviation
(%)
4
4
5
8
13
9
3
3
6
7
9
6
2
3
2
4
3
4
3
2
4
3
2
6
4
5
5
4
5
aAll results based upon seven replicate analyses. Ester1f1cation
performed using the bubbler method. Data obtained from reference 9.
DW = Reagent water
MW = Municipal water
8150 ->20
Revision 0
Date September 1986
-------
METHOD B1SO
CHLORINATED HERBICIDES
7.2.1
Extract 3 times
with diethyl
ether
Lloulo
v Solid
Type of sample xvvsample
for preparation '
7. > . 1
Extract
sample 3
times with
acetone ana
diethyl ether
7.2.1
Combine
extracts
7.2.2
7.1.1
Combine
extracts
Do solvent
cleanup
7.2.3
7.1.1.5
Allow
layers
to separate:
re-extract
and discard
aqueous phase
Proceed with
hydrolysis
7.1.2
Oo solvent
cleanup
7.1.3
Proceed with
hydrolysis
o
8150 - 21
Revision 0
Date September 1986
-------
METHOD 81SO
CHLORINATED HERBICIDES
(Continued)
7.3.3
Assemble
dlazomethane
bubbler:
generate
dlazometnane
7 .3.2
Prepare
dlazometnane
according
to Kit
Instructions
7.4
Set gas
chromatography
conditions
7.5
Cal Ibrate
according to
Method 8000
7.5.3
7.6.7
7.6
Analyze by GC
(refer to
Method BOOO)
Process
series of
standards
through system.
cleanup
Choose
GC column for
compound to be
analyzed
8150 - 22
Revision 0
Date September 1986
-------
4.3 DETERMINATION OF ORGANIC ANALYTES
4.3.2 GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC METHODS
FOUR - 10
Revision
Date September 1986
-------
METHOD 8240
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 Method 8240 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all
types of samples, regardless of water content, including ground water, aqueous
sludges, caustic liquors, acid liquors, waste solvents, oily wastes, mousses,
tars, fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments.
1.2 Method 8240 can be used to quantify most volatile organic compounds
that have boiling points below 200'C [vapor pressure is approximately equal to
mm Hg @ 25°C] and that are insoluble or slightly soluble in water. Volatile
water-soluble compounds can be included in this analytical technique, however,
for the more soluble compounds, quantitation limits are approximately ten
times higher because of poor purging efficiency. The method is also limited
to compounds that elute as sharp peaks from a GC column packed with
graphitized carbon lightly coated with a carbowax. Such compounds include
low-molecular-weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides. See Table 1 for a list of
compounds, retention times, and their characteristic ions that have been
evaluated on a purge-and-trap GC/MS system.
1.3 The practical quantitation limit (PQL) of Method 8240 for an
individual compound is approximately 5 ug/kg (wet weight) for soil/sediment
samples, 0.5 mg/kg (wet weight) for wastes, and 5 ug/L for ground water (see
Table 2). PQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the
detector.
1.4 Method 8240 is based upon a purge-and-trap, gas chromatographic/mass
spectrometric (GC/MS) procedure. This method is restricted to use by, or
under the supervision of, analysts experienced in the use of purge-and-trap
systems and gas chromatograph/mass spectrometers, and skilled in the inter-
pretation of mass spectra and their use as a quantitative tool.
1.5 To increase purging efficiencies of acrylonitrile and acrolein,
refer to Methods 5030 and 8030 for proper purge-and-trap conditions.
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications).
The components are separated via the gas chromatograph and detected using a
mass spectrometer, which is used to provide both qualitative and quantitative
information. The chromatographic conditions, as well as typical mass
spectrometer operating parameters, are given.
8240 - 1
Revision 0
Date September 1986
-------
TABLE 1. RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Retention
Compound Time (m1n)
Acetone
Acroleln
Acrylom'trile
Benzene
Bromochloromethane (I.S.)
Bromodi chl oromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
2-Butanone
Carbon dlsulflde
Carbon tetrachloride
Chlorobenzene
Chlorobenzene-ds (I.S.)
Chlorodlbromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Dlbromomethane
l,4-D1chloro-2-butane
Dlchlorodlfluoromethane
l,l-D1chloroethane
1,2-Dlchloroethane
1,2-01 chl oroethane-d4 (surr.)
1,1-Dlchloroethene
trans-l,2-D1chloroethene
1 , 2-D1 chl oropropane
c1s-l,3-D1chloropropene
trans-l,3-D1chloropropene
1,4-01 fluorobenzene (I.S.)
Ethanol
Ethyl benzene
Ethyl methacrylate
2-Hexanone
lodomethane
Methylene chloride
4-Methyl -2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-dg (surr.)
__
—
—
17.0
9.3
14.3
28.3
19.8
3.1
—
—
13.7
24.6
—
—
4.6
18.6
11.4
2.3
—
—
—
—
10.1
12.1
9.0
10.0
15.7
15.9
17.2
19.6
—
26.4
—
—
—
6.4
—
—
22.1
22.2
23.5
— —
Primary Ion
43
56
53
78
128
83
95
173
94
72
76
117
112
117
129
64
63
83
50
93
75
85
63
62
65
96
96
63
75
75
114
31
106
69
43
142
84
43
104
83
164
92
98
Secondary Ion(s)
58
55, 58
52, 51
52, 77
49, 130,
85, 129
174, 176
171, 175,
96, 79
57, 43
78
119, 121
114, 77
82, 119
208, 206
66, 49
65, 106
85, 47
52, 49
174, 95
53, 89
87, 50,
65, 83
64, 98
102
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
45, 27,
91
41, 39,
58, 57,
127, 141
49, 51,
58, 100
78, 103
85, 131,
129, 131,
91, 65
70, 100
51
252
101
46
99
100
86
133
166
8240 - 2
Revision 0
Date September 1986
-------
TABLE 1. - Continued
Retention
Compound Time (min) Primary Ion Secondary Ion(s)
1,1,1-Trichloroethane 13.4 97 99, 117
1,1,2-Trichloroethane 17.2 97 83, 85, 99
Trichloroethene 16.5 130 95, 97, 132
Trichlorofluoromethane 8.3 101 103, 66
1,2,3-Trichloropropane — 75 110, 77, 61
Vinyl acetate — 43 86
Vinyl chloride 3.8 62 64, 61
Xylene — 106 91
8240 - 3
Revision 0
Date September 1986
-------
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR VOLATILE ORGANICSa
Practical
Quant1tat1on
L1m1tsb
Volatiles
1. Chloromethane
2. Bromomethane
3. Vinyl Chloride
4. Chloroethane
5. Methyl ene Chloride
6. Acetone
7. Carbon D1sulf1de
8. 1,1-Dichloroethene
9. 1,1-01 chloroethane
10. trans-l,2-D1chloroethene
11. Chloroform
12. 1,2-Di chloroethane
13. 2-Butanone
14. I,l,l-Tr1 chloroethane
15. Carbon Tetrachloride
16. Vinyl Acetate
17. Bromodl chloromethane
18. 1,1,2,2-Tetrachloroethane
19. 1,2-Dichloropropane
20. trans-l,3-D1chloropropene
21. Trlchloroethene
22. Dibromochloromethane
23. I,l,2-Tr1 chloroethane
24. Benzene
25. cis-l,3-Dichloropropene
26. 2-Chloroethyl Vinyl Ether
27. Bromoform
28. 2-Hexanone
29. 4-Methyl-2-pentanone
30. Tetrachloroethene
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
78-93-3
71-55-6
56-23-5
108-05-4
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
110-75-8
75-25-2
591-78-6
108-10-1
127-18-4
Ground water
ug/L
10
10
10
10
5
100
5
5
5
5
5
5
100
5
5
50
5
5
5
5
5
5
5
5
5
10
5
50
50
5
Low Soil /Sediment
ug/Kg
10
10
10
10
5
100
5
5
5
5
5
5
100
5
5
50
5
5
5
5
5
5
5
5
5
10
5
50
50
5
8240 - 4
Revision 0
Date September 1986
-------
TABLE 2. - Continued
Practical
Quantitation
L1mitsb
Ground water Low Soil/Sediment
Volatiles CAS Number ug/L ug/Kg
31.
32.
33.
34.
35.
Toluene
Chlorobenzene
Ethyl Benzene
Styrene
Total Xylenes
108-88-3
108-90-7
100-41-4
100-42-5
5
5
5
5
5
5
5
5
5
5
aSample PQLs are highly matrix-dependent. The PQLs listed herein are provided
for guidance and may not always be achieveable. See the following information
for further guidance on matrix-dependent PQLs.
listed for soil /sediment are based on wet weight. Normally data is
reported on a dry weight basis; therefore, PQLs will be higher, based on the
% moisture in each sample.
Other Matrices; Factor1
Water miscible liquid waste 50
High-level soil & sludges 125
Non-water miscible waste 500
*PQL = [PQL for ground water (Table 2)] X [Factor]. For non-aqueous
samples, the factor is on a wet-weight basis.
8240 - 5
Revision
Date September 1986
-------
2.2 If the above sample Introduction techniques are not applicable, a
portion of the sample is dispersed in methanol to dissolve the volatile
organic constituents. A portion of the methanolic solution is combined with
water in a specially designed purging chamber. It is then analyzed by purge-
and-trap GC/MS following the normal water method.
2.3 The purge-and-trap process: An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are trapped. After
purging is completed, the sorbent column is heated and backflushed with inert
gas to desorb the components onto a gas chromatographic column. The gas
chromatographic column is heated to elute the components, which are detected
with a mass spectrometer.
3.0 INTERFERENCES
3.1 Interferences purged or coextracted from the samples will vary
considerably from source to source, depending upon the particular sample or
extract being tested. The analytical system, however, should be checked to
ensure freedom from interferences, under the analysis conditions, by analyzing
method blanks.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal
into the sample during shipment and storage. A field blank prepared from
reagent water and carried through the sampling and handling protocol can serve
as a check on such contamination.
3.3 Cross-contamination can occur whenever high-level and low-level
samples are analyzed sequentially. Whenever an unusually concentrated sample
is analyzed, it should be followed by the analysis of reagent water to check
for cross-contamination. The purge-and-trap system may require extensive
bake-out and cleaning after a high-level sample.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
3.5 Impurities in the purge gas and from organic compounds out-gasing
from the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from contam-
ination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-TFE plastic coating, non-TFE thread sealants, or flow
controllers with rubber components in the purging device should be avoided.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes; 10-uL, 25-uL, 100-uL, 250-uL, 500-uL, and 1,000 uL.
These syringes shouldbe equipped with a 20-gauge (0.006-in I.D.) needle
8240 - 6
Revision 0
Date September 1986
-------
having a length sufficient to extend from the sample Inlet to within 1 cm of
the glass frit 1n the purging device. The needle length will depend upon the
dimensions of the purging device employed.
4.2 Syringe valve; Two-way, with Luer ends (three each), 1f applicable
to the purging device.
4.3 Syringe; 5-mL, gas-tight with shutoff valve.
4.4 Balance; Analytical, capable of accurately weighing 0.0001 g, and a
top-loading balance capable of weighing 0.1 g.
4.5 Glass scintillation vials; 20-mL, with screw caps and Teflon liners
or glass culture tubes with a screw cap and Teflon Uner.
4.6 Volumetric flasks; 10-mL and 100-mL, class A with ground-glass
stoppers.
4.7 Vials; 2-mL, for GC autosampler.
4.8 Spatula; Stainless steel.
4.9 Disposable pi pets; Pasteur.
4.10 Heater or heated oil bath; Should be capable of maintaining the
purging chamber to within 1°C over the temperature range of ambient to 100*C.
4.11 Purge-and-trap device; The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.11.1 The recommended purging chamber 1s designed to accept 5-mL
samples with a water column at least 3 cm deep. The gaseous headspace
between the water column and the trap must have a total volume of less
than 15 mL. The purge gas must pass through the water column as finely
divided bubbles with a diameter of less than 3-mm at the origin. The
purge gas must be introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be utilized, provided
equivalent performance is demonstrated.
4.11.2 The trap must be at least 25 cm long and have an Inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene
oxide polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It 1s
recommended that 1.0 cm of methyl si 11 cone-coated packing be inserted at
the inlet to extend the life of the trap (see Figure 2). If 1t Is not
necessary to analyze for dichlorodifluoromethane or other f1uorocarbons
of similar volatility, the charcoal can be eliminated and the polymer
increased to fill 2/3 of the trap. If only compounds boiling above 35*C
are to be analyzed, both the silica gel and charcoal can be eliminated
8240 - 7
Revision 0
Date September 1986
-------
OPTIONAL
FOAM TRAP
>pfi«- Exit V
V-14m,
14 Inch 0. D. Exit
10 mm Glass Frit
Medium Porosity
14 Inch 0. D.
mm 0. D.
Inlet Vt Inch 0. D.
Sample Inlet
2-Way Syringe Valve
17 cm, 20 Gauge Syringe Needle
6 mm 0. D. Rubber Septum
mm 0. D.
Inlet
14 Inch 0. D.
1/16 Inch 0. D.
Stainless Steel
13x Molecular
Sieve Purge
Gas Filter
Purge Gas
Flow Control
Figure 1. Purging chamber.
8240 - 8
Revision p
Date September 1986
-------
Packing Procedure
Construction
Glass Wool S mm
Grade 15 |
Silica Gel 8cm
Tenax 15cm
3%OV-1 1cm;
Glass Wool 5 mm
Compression
Fitting Nut
and Ferrules
14 Ft. 7Ii/Foot
Resistance Wire
Wrapped Solid
Thermocouple/
Controller
Sensor
Electronic
Temperature
Control and
Pyrometer
Tubing 25cm
0.105 In. I.D.
0.125 In.O.D.
Stainless Steel
Trap Inlet
Figure 2. Trap packings and construction to include desorb capability for Method 8240.
8240 - 9
Revision 0
Date September 1986
-------
and the polymer Increased to fill the entire trap. Before Initial use,
the trap should be conditioned overnight at 180*C by backflushlng with an
Inert gas flow of at least 20 ml/mln. Vent the trap effluent to the
room, not to the analytical column. Prior to dally use, the trap should
be conditioned for 10 mln at 180*C with backflushlng. The trap may be
vented to the analytical column during dally conditioning; however, the
column must be run through the temperature program prior to analysis of
samples.
4.11.3 The desorber should be capable of rapidly heating the trap
to 180*C for desorption. The polymer section of the trap should not be
heated higher than 180°C, and the remaining sections should not exceed
220*C during bake-out mode. The desorber design illustrated in Figure 2
meets these criteria.
4.11.4 The purge-and-trap device may be assembled as a separate
unit or may be coupled to a gas chromatograph, as shown 1n Figures 3 and
4.
4.11.5 Trap Packing Materials:
4.11.5.1 2,6-Diphenylene oxide polymer: 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.li.5.2 Methyl sllicone packing: OV-1 (3%) on Chromosorb-W,
60/80 mesh or equivalent.
4.11.5.3 Silica gel: 35/60 mesh, Davison, grade 15 or
equivalent.
4.11.5.4 Coconut charcoal: Prepare from Barnebey Cheney,
CA-580-26 lot #M-2649 by crushing through 26 mesh screen.
4.12 Gas chromatograph/mass spectrometer system:
4.12.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.12.2 Column: 6-ft x 0.1-in. I.D. glass, packed with 1% SP-1000
on Carbopack-B (60/80 mesh) or equivalent.
4.12.3 Mass spectrometer: Capable of scanning from 35-260 amu
every 3 sec or less, using 70 volts (nominal) electron energy in the
electron Impact mode and producing a mass spectrum that meets all the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) are Injected
through the gas chromatograph inlet.
4.12.4 GC/MS Interface: Any: GC-to-MS interface that gives accep-
table calibration points at 50 ng or less per Injection for each of the
analytes and achieves all acceptable performance criteria (see Table 3)
may be used. GC-to-MS interfaces constructed entirely of glass or of
8240 - 10
Revision 0
Date September 1986
-------
CARRIER GAS FLOW CONTROL
PRESSURE REGULATOR
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
LIQUID INJECTION PORTS
/ ^ COLUMN OVEN
1 "non ' ,__ CONFIRMATORY COLUMN
TO DETECTOR
*—ANALYTICAL COLUMN
OPTIONAL 4-PORT COLUMN
SELECTION VALVE
TRAP INLET
x RESISTANCE WIRE
CHEATER CONTROL
TRAP 'OFF*
arc
PURGING
DEVICE
Nott:ALL LINES BETWEEN
TRAP AND GC
SHOULD BE HEATED
TO 80*C
Figure 3. Schematic of purge-and-trap device — purge mode for Method 8240.
CARRIER GAS
CONTROL
REGULATOR
TOR. I
-*M
LIQUID INJECTION PORTS
PURGE GAS ._\,
FLOW CONTROL] 4
*-A
_iL
Kl MOLECULAR 5
SIEVE FILTER ^
/,
COLUMN OVEN
n p n
' U' J
r CONFIRMATORY CCLU.'.IX
nnnn-I^100^010"
. ,.-u.-'jL'U { ^-ANALYTICAL COLUMN
\OPTIONAL 4-PORT COLUMN
SELECTION VALVE
6-PORT TRAP INLET
PURGING
DEVICE
CONTROL
Note:
ALL LINES BETWEEN
TRAP AND GC
SHOULD BE HEATED
TO 30°C.
Figure 4. Schematic of purge-and-trap device — desorb mode for Method 8240.
8240 - 11
Revision 0
Date September 1986
-------
TABLE 3. BFB KEY ION ABUNDANCE CRITERIA
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
8240 - 12
Revision 0
Date September 1986
-------
glass-lined materials are recommended. Glass can be deactivated by
sllanlzing with dlchlorodimethylsllane.
4.12.5 Data system: A computer system that allows the continuous
acquisition and storage on machine-readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have software
that allows searching any GC/MS data file for ions of a specified mass
and plotting such ion abundances versus time or scan number. This type
of plot is defined as an Extracted Ion Current Profile (EICP). Software
must also be available that allows integrating the abundances 1n any EICP
between specified time or scan-number limits. The most recent version of
the EPA/NIH Mass Spectral Library should also be available.
5.0 REAGENTS
5.1 Stock solutions: Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard solu-
tions in methanol, using assayed liquids or gases, as appropriate.
5.1.1 Place about 9.8 ml of methanol in a 10-mL tared ground-
glass-stoppered volumetric flask. Allow the flask to stand, unstoppered,
for about 10 min or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
5.1.2 Add the assayed reference material, as described below.
5.1.2.1 Liquids; Using a 100-uL syringe, immediately add two
or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.1.2.2 Gases; To prepare standards for any compounds that
boil below 30*C (e.g., bromomethane, chloroethane, chloromethane, or
vinyl chloride), fill a 5-mL valved gas-tight syringe with the
reference standard to the 5.0-mL mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly Introduce the reference stan-
dard above the surface of the liquid. The heavy gas will rapidly
dissolve in the methanol. Standards may also be prepared by using a
lecture bottle equipped with a Hamilton Lecture Bottle Septum
(186600). Attach Teflon tubing to the side-arm relief valve and
direct a gentle stream of gas into the methanol meniscus.
5.1.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
microliter (ug/uL) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction
to calculate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration 1f they are
certified by the manufacturer or by an independent source.
8240 - 13
Revision
Date September 1986
-------
5.1.4 Transfer the stock standard solution Into a Teflon-sealed
screw cap bottle. Store, with minimal headspace, at -10°C to -20°C and
protect from light.
5.1.5 Prepare fresh standards every two months for gases. Reactive
compounds such as 2-chloroethylvinyl ether and styrene may need to be
prepared more frequently. All other standards must be replaced after six
months, or sooner 1f comparison with check standards indicates a problem.
5.2 Secondary dilution standards; Using stock standard solutions,
prepare in methanol secondarydilution standards containing the compounds of
interest, either singly or mixed together. Secondary dilution standards must
be stored with minimal headspace and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.3 Surrogate standards; The surrogates recommended are toluene-dg,
4-bromofluorobenzene, and l,2-dichloroethane-d4. Other compounds may be used
as surrogates, depending upon the analysis requirements. A stock surrogate
solution in methanol should be prepared as described in Section 5.1, and a
surrogate standard spiking solution should be prepared from the stock at a
concentration of 250 ug/10 ml in methanol. Each sample undergoing GC/MS
analysis must be spiked with 10 uL of the surrogate spiking solution prior to
analysis.
5.4 Internal standards: The recommended internal standards are bromo-
chloromethane, 1,4-difluorobenzene, and chlorobenzene-ds. Other compounds may
be used as internal standards as long as they have retention times similar to
the compounds being detected by GC/MS. Prepare internal standard stock and
secondary dilution standards in methanol using the procedures described in
Sections 5.1 and 5.2. It is recommended that the secondary dilution standard
should be prepared at a concentration of 25 ug/mL of each internal standard
compound. Addition of 10 uL of this standard to 5.0 ml of sample or cali-
bration standard would be the equivalent of 50 ug/L.
5.5 4-Bromofluorobenzene (BFB) standard: A standard solution containing
25 ng/uL of BFB in methanol should be prepared.
5.6 Calibration standards; Calibration standards at a minimum of five
concentration levels should be prepared from the secondary dilution of stock
standards (see Sections 5.1 and 5.2). Prepare these solutions in reagent
water. One of the concentration levels should be at a concentration near, but
above, the method detection limit. The remaining concentration levels should
correspond to the expected range of concentrations found in real samples or
should not exceed the working range of the GC/MS system. Each standard should
contain each analyte for detection by this method (e.g., some or all of the
compounds listed in Table 1 may be included). Store for one week only in a
vial with no headspace. \
5.7 Matrix spiking standards; Matrix spiking standards should be
prepared from volatile organic compounds which' will be representative of the
compounds being investigated. The suggested compounds are 1,1-dichloroethene,
8240 - 14
Revision 0
Date September 1986
-------
trlchloroethene, chlorobenzene, toluene, and benzene. The standard should be
prepared in methanol, with each compound present at a concentration of 250
ug/10.0 ml.
5.8 Great care must be taken to maintain the Integrity of all standard
solutions. It is recommended that all standards be stored at -10'C to -20'C
in screw-cap amber bottles with Teflon liners.
5.9 Reagent water; Reagent water is defined as water in which an inter-
ferent is not observed at the method detection limit (MDL) of the parameters
of interest.
5.9.1 Reagent water may be generated by passing tap water through a
carbon filter bed containing about 453 g of activated carbon (Calgon
Corp., Filtrasorb-300 or equivalent).
5.9.2 A water purification system (Millipore Super-Q or equivalent)
may be used to generate reagent water.
5.9.3 Reagent water may also be prepared by boiling water for 15
min. Subsequently, while maintaining the temperature at 90*C, bubble a
contaminant-free inert gas through the water for 1 hr. While it is still
hot, transfer the water to a narrow-mouth screw-cap bottle and seal with
a Teflon-lined septum and cap.
5.10 Methanol; Pesticide quality or equivalent. Store apart from other
solvents.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Direct injection; In very limited applications (e.g., aqueous
process wastes), direct injection of the sample into the GC/MS system with a
10 uL syringe may be appropriate. One such application is for verification of
the alcohol content of an aqueous sample prior to determining if the sample is
ignitable (Methods 1010 or 1020). In this case, it is suggested that direct
injection be used. The detection limit is very high (approximately 10,000
ug/L); therefore, it is only permitted when concentrations in excess of 10,000
ug/L are expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-and-trap
device).
8240 - 15
Revision 0
Date September 1986
-------
7.2 Initial calibration for purge-and-trap procedure;
7.2.1 Recommended GC/MS operating conditions:
Electron energy: 70 volts (nominal).
Mass range: 35-260 amu.
Scan time: To give 5 scans/peak but not to exceed
7 sec/scan.
Initial column temperature: 45*C.
Initial column holding time: 3 min.
Column temperature program: 8'C/niin.
Final column temperature: 220'C.
Final column holding time: 15 min.
Injector temperature: 200-225*C.
Source temperature: According to manufacturer's specifications.
Transfer line temperature: 250-300*C.
Carrier gas: Hydrogen at 50 cm/sec or helium at
30 cm/sec.
7.2.2 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50-ng injection or purging of 4-bromof1uorobenzene (2-uL
injection of the BFB standard). \ Analyses must not begin until these
criteria are met.
7.2.3 Assemble a purge-and-trap device that meets the specification
in Section 4.11. Condition the trap overnight at 180*C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition
the trap daily for 10 min while backflushing at 180'C with the column at
220*C.
7.2.4 Connect the purge-and-trap device to a gas chromatograph.
7.2.5 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device. Add 5.0 ml of reagent water to the
-purging device. The reagent water is added to the purging device using a
5-mL glass syringe fitted with a J15-cm 20-gauge needle. The needle is
Inserted through the sample inlet shown in Figure 1. The Internal
diameter of the 14-gauge needle that forms the sample inlet will permit
insertion of the 20-gauge needle. Next, using a 10-uL or 25-uL micro-
syringe equipped with a long needle (Paragraph 4.1), take a volume of the
secondary dilution solution containing appropriate concentrations of the
calibration standards (Paragraph 5;6). Add the aliquot of calibration
solution directly to the reagent water in the purging device by inserting
the needle through the sample inlet. When discharging the contents of
the micro-syringe, be sure that the end of the syringe needle is well
beneath the surface of the reagent water. Similarly, add 10 uL of the
internal standard solution (Paragraph 5.4). Close the 2-way syringe
valve at the sample inlet.
7.2.6 Carry out the purge-and-trap analysis procedure as described
in Section 7.4.1.
8240 - 16
Revision
Date September 1986
-------
7.2.7 Tabulate the area response of the characteristic ions (see
Table 1) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
has a retention time closest to the compound being measured (Section
7.5.2). The RF is calculated as follows:
RF = (AxCis)/(AlsCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ajs = Area of the characteristic ion for the specific internal
standard.
C^s = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.2.8 The average RF must be calculated for each compound. A
system performance check should be made before this calibration curve is
used. Five compounds (the System Performance Check Compounds, or SPCCs)
are checked for a minimum average response factor. These compounds are
chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have
RFs of 0.4-0.6 and are used to check compound instability and check for
degradation caused by contaminated lines or active sites 1n the system.
Examples of these occurrences are:
7.2.8.1 Chloromethane; This compound is the most likely
compound to be lost if the purge flow is too fast.
7.2.8.2 Bromoform; This compound is one of the compounds most
likely to be purged very poorly if the purge flow is too slow. Cold
spots and/or active sites in the transfer lines may adversely affect
response. Response of the quantisation ion (m/z 173) is directly
affected by the tuning of BFB at ions m/z 174/176. Increasing the
m/z 174/176 ratio may improve bromoform response.
7.2.8.3 Tetrachloroethane and 1,1-dichloroethane; These
compounds are degraded bycontaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2.9 Using the RFs from the initial calibration, calculate the
percent relative standard deviation (%RSD) for Calibration Check
Compounds (CCCs).
8240 - 17
Revision 0
Date September 1986
-------
%RSD = -- x 100
Y
where:
RSD = relative standard deviation.
x = mean of 5 initial RFs for a compound.
SD = standard deviation of average RFs for a compound.
SD =
N
(x1 - x]
N - 1
The %RSD for each individual CCC should be less than 30 percent. This
criterion must be met in order for the individual calibration to be
valid. The CCCs are: . ,
1,1-Di chloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethyl benzene, and
Vinyl chloride.
7.3 Daily GC/MS calibration;
7.3.1 Prior to the analysis of samples, inject or purge 50-ng of
the 4-bromofluorobenzene standard. The resultant mass spectra for the
BFB must meet all of the criteria given in Table 3 before sample analysis
begins. These criteria must be demonstrated each 12-hr shift.
7.3.2 The initial calibration curve (Section 7.2) for each compound
of interest must be checked and verified once every 12 hr of analysis
time. This is accomplished by analyzing a calibration standard that is
at a concentration near the midpoint concentration for the working range
of the GC/MS by checking the SPCC (Paragraph 7.3.3) and CCC (Paragraph
7.3.4).
7.3.3 System Performance Check Compounds (SPCCs): A system
performance check must be made each 12 hr. If the SPCC criteria are met,
a comparison of response factors is made for all compounds. This is the
same check that is applied during the initial calibration. If the
minimum response factors are not met, the system must be evaluated, and
corrective action must be taken before sample analysis begins. The
minimum response factor for volatile SPCCs is 0.300 (0.250 for Bromo-
form). Some possible problems are standard mixture degradation,
injection port inlet contamination, contamination at the front end of the
analytical column, and active sites in the column or chromatographic
system.
8240 - 18
Revision 0
Date September 1986
-------
7.3.4 Calibration Check Compounds (CCCs): After the system
performance check 1s met, CCCs listed 1n Paragraph 7.2.9 are used to
check the validity of the Initial calibration. Calculate the percent
difference using:
RFT - RFr
% Difference = — i — - x 100
where:
RFj = average response factor from initial calibration.
RFC = response factor from current verification check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent
difference for each CCC is less than 25%, the initial calibration is
assumed to be valid. If the criterion is not met (>25% difference), for
any one CCC, corrective action MUST be taken. Problems similar to those
listed under SPCCs could affect this criterion. If no source of the
problem can be determined after corrective action has been taken, a new
five-point calibration MUST be generated. This criterion MUST be met
before quantitative sample analysis begins.
7.3.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard
changes by more than 30 sec from the last check calibration (12 hr), the
chromatographlc system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the Internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning are necessary.
7.4 GC/MS analysis;
7.4.1 Water samples:
7.4.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be used are: the
headspace sampler (Method 3810) using a gas chromatograph (GC)
equipped with a photo ionization detector (PID) in series with an
electrolytic conductivity detector (ECD); and extraction of the
sample with hexadecane and analysis of the extract on a GC with a
FID and/or an ECD (Method 3820).
8240 - 19
Revision 0
Date September 1986
-------
7.4.1.2 All samples and standard solutions must be allowed to
warm to ambient temperature before analysis.
7.4.1.3 Set up the GC/MS system as outlined 1n Paragraph
7.2.1.
7.4.1.4 BFB tuning criteria and dally GC/MS calibration
criteria must be met (Section 7.3) before analyzing samples.
7.4.1.5 Adjust the purge gas (helium) flow rate to 25-40
mL/m1n on the purge-and-trap device. Optimize the flow rate to
provide the best response for chloromethane and bromoform, 1f these
compounds are analytes. Excessive flow rate reduces chloromethane
response, whereas Insufficient flow reduces bromoform response (see
Section 7.2.8).
7.4.1.6 Remove the plunger from a 5-mL syringe and attach a
closed syringe valve. Open the sample or standard bottle, which has
been allowed to come to ambient temperature, and carefully pour the
sample Into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, 1f
there 1s only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample Integrity.
This second sample 1s maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20-mL syringe would allow the use of only one
syringe. If a second analysis 1s needed from a syringe, 1t must be
analyzed within 24 hr. Care must be taken to prevent air from
leaking into the syringe.
7.4.1.7 The following procedure is appropriate for diluting
purgeable samples. All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.
7.4.1.7.1 Dilutions may be made in volumetric flasks (10-t
o 100-mL). Select the volumetric flask that will allow for the
necessary dilution. Intermediate dilutions may be necessary
for extremely large dilutions.
7.4.1.7.2 Calculate the approximate volume of reagent wate
r to be added to the volumetric flask selected and add slightly
less than this quantity of reagent water to the flask.
7.4.1.7.3 Inject the proper aliquot of samples from the sy
ringe prepared in Paragraph 7.4.1.6 into the flask. AHquots
of less than 1-mL are not recommended. Dilute the sample to
the mark with reagent water. Cap the flask, Invert, and shake
three times. Repeat above procedure for additional dilutions.
8240 - 20
Revision
Date September 1986
-------
7.4.1.7.4 Fill a 5-mL syringe with the diluted sample as 1
n Paragraph 7.4.1.6.
7.4.1.8 Add 10.0 uL of surrogate spiking solution (Paragraph
5.3) and 10 uL of Internal standard spiking solution (Paragraph 5.4)
through the valve bore of the syringe; then close the valve. The
surrogate and Internal standards may be mixed and added as a single
spiking solution. The addition of 10 uL of the surrogate spiking
solution to 5 ml of sample 1s equivalent to a concentration of 50
ug/L of each surrogate standard.
7.4.1.9 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample Into the purging chamber.
7.4.1.10 Close both valves and purge the sample for 11.0 + 0.1
min at ambient temperature.
7.4.1.11 At the conclusion of the purge time, attach the trap
to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and 6C/MS data
acquisition. Concurrently, Introduce the trapped materials to the
gas chromatographic column by rapidly heating the trap to 180*C
while backflushing the trap with Inert gas between 20 and 60 mL/min
for 4 m1n. If this rapid heating requirement cannot be met, the gas
chromatographic column must be used as a secondary trap by cooling
it to 30*C (or subambient, if problems persist) instead of the
recommended Initial program temperature of 45*C.
7.4.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5-mL flushes of reagent water (or methanol followed
by reagent water) to avoid carryover of pollutant compounds into
subsequent analyses.
7.4.1.13 After desorbing the sample for 4 min, recondition the
trap by returning the purge-and-trap device to the purge mode. Wait
15 sec; then close the syringe valve on the purging device to begin
gas flow through the trap. The trap temperature should be
maintained at 180*C. Trap temperatures up to 220*C may be employed;
however, the higher temperature will shorten the useful life of the
trap. After approximately 7 min, turn off the trap heater and open
the syringe valve to stop the gas flow through the trap. When cool,
the trap is ready for the next sample.
7.4.1.14 If the Initial analysis of a sample or a dilution of
the sample has a concentration of analytes that exceeds the Initial
calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantltation 1s allowed only when there are
sample interferences with the primary ion. When a sample 1s
analyzed that has saturated Ions from a compound, this analysis must
be followed by a blank reagent water analysis. If the blank
8240 - 21
Revision
Date September 1986
-------
analysis is not free of interferences, the system must be
decontaminated. Sample analysis may not resume until a blank can be
analyzed that is free of interferences.
7.4.1.15 For matrix spike analysis, add 10 uL of the matrix
spike solution (Paragraph 5.7) to the 5 ml of sample purged.
Disregarding any dilutions, this is equivalent to a concentration of
50 ug/L of each matrix spike standard.
7.4.1.16 All dilutions should keep the response of the major
constituents (previously saturated peaks) in the upper half of the
linear range of the curve. Proceed to Sections 7.5.1 and 7.5.2 for
qualitative and quantitative analysis.
7.4.2 Water-misclble liquids:
7.4.2.1 Water-miscible liquids are analyzed as water samples
after first diluting them at least 50-fold with reagent water.
7.4.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample to a 100-mL volumetric flask and
diluting to volume with reagent water. Transfer immediately to a
5-mL gas-tight syringe.
7.4.2.3 Alternatively, prepare dilutions directly in a 5-mL
syringe filled with reagent water by adding at least 20 uL, but not
more than 100-uL of liquid sample. The sample is ready for addition
of internal and surrogate standards.
7.4.3 Sediment/soil and waste samples: It is highly recommended
that all samples of this type be screened prior to the purge-and-trap
GC/MS analysis. The headspace method (Method 3810) or the hexadecane
extraction and screening method (Method 3820) may used for this purpose.
These samples may contain percent quantities of purgeable organics that
will contaminate the purge-and-trap system, and require extensive cleanup
and instrument downtime. Use the screening data to determine whether to
use the low-level method (0.005-1 mg/kg) or the high-level method
mg/kg).
7.4.3.1 Low-level method; This is designed for samples
containing individualpurgeable compounds of <1 mg/kg. It is
limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-level method is based on
purging a heated sediment/soil sample mixed with reagent water
containing the surrogate and internal standards. Analyze all
reagent blanks and standards under the same conditions as the
samples. See Figure 5 for an illustration of a low soils impinger.
7.4.3.1.1 Use a 5-g sample if the expected concentration
is <0.1 mg/kg or a 1-g sample for expected concentrations
between 0.1 and 1 mg/kg.
8240 - 22
Revision 0
Date September 1986
-------
PURGE INLET FITTING
SAMPLE OUTLET FITTING 11
3" » 6mm 0 D GLASS TUBING
SEPTUM
CAP
40ml VIAL
Figure 5. Low Soils Inpinger
8240 - 23
Revision 0
Date September 1986
-------
7.4.3.1.2 The GC/MS system should be set up as 1n
Paragraphs 7.4.1.2-7.4.1.4. This should be done prior to the
preparation of the sample to avoid loss of volatlles from
standards and samples. A heated purge calibration curve must
be prepared and used for the quantltation of all samples
analyzed with the low-level method. Follow the Initial and
dally calibration Instructions, except for the addition of a
40*C purge temperature.
7.4.3.1.3 Remove the plunger from a 5-mL Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger and
compress the water to vent trapped air. Adjust the volume to
5.0 ml. Add 10 uL each of surrogate spiking solution
(Paragraph 5.3) and internal standard solution (Paragraph 5.4)
to the syringe through the valve. (Surrogate spiking solution
and internal standard solution may be mixed together.) The
addition of 10 uL of the surrogate spiking solution to 5 g of
sediment/soil is equivalent to 50 ug/kg of each surrogate
standard.
7.4.3.1.4 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard
any supernatant liquids. Mix the contents of the sample
container with a narrow metal spatula. Weigh the amount
determined in Paragraph 7.4.3.1.1 into a tared purge device.
Note and record the actual weight to the nearest 0.1 g.
7.4.3.1.5 Determine the percent moisture of the
soil/sediment sample. This includes waste samples that are
amenable to moisture determination. Other wastes should be
reported on a wet-weight basis. Immediately after weighing the
sample, weigh (to 0.1 g) 5-10 g of additional sediment/soil
into a tared crucible. Dry the contents of the crucibles
overnight at 105*C. Allow to cool in a desiccator and reweigh
the dried contents. Concentrations of individual analytes will
be reported relative to the dry weight of sediment.
* mn,-ctiire - grams of sample - grams of dry sample ,nn
* moisture - grams Qf sample x luu
7.4.3.1.6 Add the spiked reagent water to the purge
device, which contains the weighed amount of sample, and
connect the device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device, the
procedures in Paragraphs 7.4.3.1.4 and 7.4.3.1.6 must be
performed rapidly and without interruption to avoid loss
of volatile organics. These steps must be performed in a
laboratory free of solvent fumes.
7.4.3.1.7 Heat the sample to 40*C + 1*C and purge the
sample for 11.0 + 0.1 min.
8240 - 24
Revision 0
Date September 1986
-------
7.4.3.1.8 Proceed with the analysis as outlined in
Paragraphs 7.4.1.11-7.4.1.16. Use 5 mL of the same reagent
water as in the reagent blank. If saturated peaks occurred or
would occur if a 1-g sample were analyzed, the medium-level
method must be followed.
7.4.3.1.9 For low-level sediment/soils add 10 uL of the
matrix spike solution (Paragraph 5.7) to the 5 ml of water
(Paragraph 7.4.3.1.3). The concentration for a 5-g sample
would be equivalent to 50 ug/kg of each matrix spike standard.
7.4.3.2 High-level method; The method is based on extracting
the sediment/soil with methanol. A waste sample is either extracted
or diluted, depending on its solubility in methanol. An aliquot of
the extract is added to reagent water containing surrogate and
internal standards. This is purged at ambient temperature. All
samples with an expected concentration of >1.0 mg/kg should be
analyzed by this method.
7.4.3.2.1 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard
any supernatant liquids. Mix the contents of the sample
container with a narrow metal spatula. For sediment/soil and
waste that are insoluble in methanol weigh 4 g (wet weight) of
sample into a tared 20-mL vial. Use a top-loading balance.
Note and record the actual weight to 0.1 gram and determine the
percent moisture of the sample using the procedure in Paragraph
7.4.3.1.5. For waste that is soluble in methanol, weigh 1 g
(wet weight) into a tared scintillation vial or culture tube or
a 10-mL volumetric flask. (If a vial or tube is used, 1t must
be calibrated prior to use. P1pet 10.0 mL of methanol into the
vial and mark the bottom of the meniscus. Discard this
solvent.)
7.4.3.2.2 Quickly add 9.0 ml of methanol; then add 1.0 ml
of the surrogate spiking solution to the vial. Cap and shake
for 2 min.
NOTE: Steps 7.4.3.2.1 and 7.4.3.2.2 must be performed
rapidly and without interruption to avoid loss of volatile
organics. These steps must be performed in a laboratory
free from solvent fumes.
7.4.3.2.3 Pipet approximately 1 ml of the extract to a GC
vial for storage, using a disposable pipet. The remainder may
be disposed of. Transfer approximately 1 mL of reagent
methanol to a separate GC vial for use as the method blank for
each set of samples. These extracts may be stored at 4'C 1n
the dark, prior to analysis. The addition of a 100-uL aliquot
of each of these extracts 1n Paragraph 7.4.3.2.6 will give a
concentration equivalent to 6,200 ug/kg of each surrogate
standard.
8240 - 25
Revision
Date September 1986
-------
7.4.3.2.4 The GC/MS system should be set up as 1n
Paragraphs 7.4.1.2-7.4.1.4. This should be done prior to the
addition of the methanol extract to reagent water.
7.4.3.2.5 Table 4 can be used to determine the volume of
methanol extract to add to the 5 ml of reagent water for
analysis. If a screening procedure was followed (Method 3810
or 3820), use the estimated concentration to determine the
appropriate volume. Otherwise, estimate the concentration
range of the sample from the low-level analysis to determine
the appropriate volume. If the sample was submitted as a
medium-level sample, start with 100 uL. All dilutions must
keep the response of the major constituents (previously
saturated peaks) in the upper half of the linear range of the
curve.
7.4.3.2.6 Remove the plunger from a 5.0-mL Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with reagent water. Replace the plunger and
compress the water to vent trapped air. Adjust the volume to
4.9 ml. Pull the plunger back to 5.0 ml to allow volume for
the addition of the sample extract and of standards. Add 10
uL of internal standard solution. Also add the volume of
methanol extract determined 1n Paragraph 7.4.3.2.5 and a volume
of methanol solvent to total 100 uL (excluding methanol in
standards).
7.4.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the water/methanol sample into the purging
chamber.
7.4.3.2.8 Proceed with the analysis as outlined in
Paragraphs 7.4.1.11-7.4.1.16. Analyze all reagent blanks on
the same instrument as that use for the samples. The standards
and blanks should also contain 100 uL of methanol to simulate
the sample conditions.
7.4.3.2.9 For a matrix spike 1n the medium-level
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution (Paragraph 5.3), and 1.0 ml of matrix
spike solution (Paragraph 5.7) as in Paragraph 7.4.3.2.2. This
results in a 6,200 ug/kg concentration of each matrix spike
standard when added to a 4-g sample. Add a 100-uL aliquot of
this extract to 5 ml of water for purging (as per Paragraph
7.4.3.2.6).
8240 - 26
Revision
Date September 1986
-------
TABLE 4. QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF MEDIUM-LEVEL
SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract3
500-10,000 ug/kg 100 uL
1,000-20,000 ug/kg 50 uL
5,000-100,000 ug/kg 10 uL
25,000-500,000 ug/kg 100 uL of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this
table.
aThe volume of methanol added to 5 mL of water being purged should be
kept constant. Therefore, add to the 5-mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 uL added to the syringe.
''Dilute an aliquot of the methanol extract and then take 100 uL for
analysis.
8240 - 27
Revision
Date September 1986
-------
7.5 Data Interpretation;
7.5.1 Qualitative analysis:
7.5.1.1 An analyte (e.g., those listed 1n Table 1) 1s
Identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
spectrum). Mass spectra for standard reference should be obtained
on the user's 6C/MS within the same 12 hours as the sample analysis.
These standard reference spectra may be obtained through analysis of
the calibration standards. Two criteria must be satisfied to verify
identification: (1) elutlon of sample component at the same GC
relative retention time (RRT) as those of the standard component;
and (2) correspondence of the sample component and the standard
component mass spectrum.
7.5.1.1.1 The sample component RRT must compare within
+0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hr as
the sample. If coelutlon of Interfering components prohibits
accurate assignment of the sample component. RRT from the total
1on chromatogram, the RRT should be assigned by using extracted
1on current profiles for Ions unique to the component of
Interest.
7.5.1.1.2 (1) All Ions present 1n the standard mass
spectra at a relative Intensity greater than 10% (most abundant
1on 1n the spectrum equals 100% must be present 1n the sample
spectrum). (2) The relative Intensities of Ions specified 1n
(1) must agree within plus or minus 20% between the standard
and sample spectra. (Example: For an 1on with an abundance of
50% 1n the standard spectra, the corresponding sample abundance
must be between 30 and 70 percent.
7.5.1.2 For samples containing components not associated with
the calibration standards, a library search may be made for the
purpose of tentative Identification. The necessity to perform this
type of Identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification
are:
(1) Relative intensities of major ions in the reference spectrum
(ions >10% of the most abundant 1on) should be present 1n the sample
spectrum.
(2) The relative Intensities of the major ions should agree within
+20%. (Example: For an 1on with an abundance of 50% 1n the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present 1n the reference spectrum should be
present 1n the sample spectrum.
8240 - 28
Revision 0
Date September 1986
-------
(4) Ions present 1n the sample spectrum but not 1n the reference
spectrum should be reviewed for possible background contamination or
presence of coelutlng compounds.
(5) Ions present 1n the reference spectrum but not In the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coelutlng peaks.
Data system library reduction programs can sometimes create these
discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample with the nearest library searches will the mass
spectral interpretation specialist assign a tentative
identification.
7.5.2 Quantitative analysis:
7.5.2.1 When a compound has been identified, the quantifi-
cation of that compound will be based on the Integrated abundance
from the EICP of the primary characteristic ion. Quantification
will take place using the internal standard technique. The Internal
standard used shall be the one nearest the retention time of that of
a given analyte (e.g., see Table 5).
7.5.2.2 Calculate the concentration of each identified
analyte 1n the sample as follows:
Water and Water-Mi scible Waste;
(AJ(IS)
concentration (ug/L) = (A )(RF)(V )
where:
Ax = Area of characteristic ion for compound being measured.
Is = Amount of Internal standard injected (ng).
Area of characteristic ion for the Internal standard.
RF = Response factor for compound being measured (Paragraph
7.2.7).
V0 = Volume of water purged (ml), taking Into consideration
any dilutions made.
8240 - 29
Revision
Date September 1986
-------
TABLE 5. VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES ASSIGNED
FOR QUANTITATION
Bromochloromethane
Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulflde
Chloroethane
Chloroform
Chioromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,2-Di chloroethane-d4 (surrogate)
1,1-Dichloroethene
trans-1,2-Di chloroethene
lodomethane
Methylene chloride
Trichlorofluoromethane
Vinyl chloride
1,4-Difluorobenzene
Benzene
Bromodichloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorodibromomethane
2-Chloroethyl vinyl ether
Dibromomethane
1,4-Di chloro-2-butene
1,2-Di chloropropane
ci s-1,3-Di chloropropene
trans-1,3-Di chloropropene
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethene
Vinyl acetate
Chlorobenzene-ds
Bromofluorobenzene (surrogate)
Chlorobenzene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
4-Methyl-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-ds (surrogate)
1,2,3-Trichloropropane
Xylene
8240 - 30
Revision 0
Date September 1986
-------
Sediment/Soil, Sludge, and Waste;
High-level:
(Aj(Is)(Vt)
concentration (ug/kg) = (AIS)(RF)(VI)(WS)
Low-level:
(AX)(IS)
concentration (ug/kg) = (AU)(RF)(WS)
where:
Ax» !s» A1s» RF = same as for water.
Vt = volume of total extract (uL) (use 10,000 uL or a factor
of this when dilutions are made).
Vi = volume of extract added (uL) for purging.
Ws = weight of sample extracted or purged (g). The wet weight
or dry weight may be used, depending upon the specific
applications of the data.
7.5.2.3 Sediment/soil samples are generally reported on a
dry weight basis, while sludges and wastes are reported on a wet
weight basis. The % moisture of the sample (as calculated In
Paragraph 7.4.3.1.5) should be reported along with the data 1n
either Instance.
7.5.2.4 Where applicable, an estimate of concentration for
noncallbrated components 1n the sample should be made. The
formulas given above should be used with the following modifica-
tions: The areas Ax and Ais should be from the total 1on
chromatograms, and the RF for the compound should be assumed to be
1. The concentration obtained should be reported Indicating
(1) that the value 1s an estimate and (2) which Internal standard
was used to determine concentration. Use the nearest internal
standard free of interferences.
7.5.2.5 Report results without correction for recovery data.
When duplicates and spiked samples are analyzed, report all data
obtained with the sample results.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an ongoing
8240 - 31
Revision 0
Date September 1986
-------
analysis of spiked samples to evaluate and document quality data. The
laboratory must maintain records to document the quality of the data
generated. Ongoing data quality checks are compared with established
performance criteria to determine 1f the results of analyses meet the
performance characteristics of the method. When results of sample spikes
Indicate atypical method performance, a quality control check standard must be
analyzed to confirm that the measurements were performed In an 1n-control mode
of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent water blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a set
of samples 1s extracted or there 1s a change 1n reagents, a reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 The experience of the analyst performing GC/MS analyses is
invaluable to the success of the methods. Each day that analysis 1s
performed, the daily calibration standard should be evaluated to determine if
the chromatographic system is operating properly. Questions that should be
asked are: Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations? Careful examination of the standard
chromatogram can Indicate whether the column is still useable, the Injector is
leaking, the Injector septum needs replacing, etc. If any changes are made to
the system (e.g, column changed), recalibration of the system must take place.
8.4 Required instrument QC is found in the following section:
8.4.1 The GC/MS system must be tuned to meet the BFB specifications
in Section 7.2.2.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in 7.2.
8.4.3 The GC/MS system must meet the SPCC criteria specified 1n
7.3.3 and the CCC criteria in 7.3.4, each 12 hr.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality (QC) check sample concentrate is required
containing each analyte at a concentration of 10 ug/mL in methanol. The
QC check sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If prepared by the laboratory, the
QC check sample concentrate must be made using stock standards prepared
independently from those used for calibration.
8.5.2 Prepare a QC check sample to contain 20 ug/L of each analyte
by adding 200 uL of QC check sample concentrate to 100 mL of reagent
water.
8240 - 32
Revision 0
Date September 1986
-------
8.5.3 Four 5-mL allquots of the well-mixed QC check sample are
analyzed according to the method beginning 1n Section 7.4.1.
8.5.4 Calculate the average recovery (7) in ug/L, and the standard
deviation of the recovery (s) in ug/L, for each analyte using the four
results.
8.5.5 For each analyte compare s and 7 with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 6. If s and 7 for all analytes meet the acceptance criteria, the
system performance is acceptable and analysis of actual samples can
begin. .If any individual s exceeds the precision limit or any individual
7 falls outside the range for accuracy, then the system performance is
unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
determined.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Paragraph
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes beginning with Section 8.5.2.
8.5.6.2 Beginning with Section 8.5.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Section
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a reagent blank, a
matrix spike, and a matrix spike duplicate/duplicate for each analytical batch
(up to a maximum of 20 samples/batch) to assess accuracy. For laboratories
analyzing one to ten samples per month, at least one spiked sample per month
is required.
8.6.1 The concentration of
determined as follows:
the spike in the sample should be
8.6.1.1 If, as in compliance monitoring, the concentration of
a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined in
Section 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in the
sample is not being checked against a specific limit, the spike
should be at 20 ug/L or 1 to 5 times higher than the background
concentration determined in Section 8.6.2, whichever concentration
would be larger.
8240 - 33
Revision 0
Date September 1986
-------
TABLE 6. CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
01 bromochl oromethane
1,2-01 chlorobenzene
1,3-01 chlorobenzene
1 , 4-01 chl orobenzene
l,l-D1chloroethane
1,2-Dichloroethane
1,1-01 chl oroethene
trans-1, 2-01 chl oroethene
1 , 2-01 chl oropropane
cis-l,3-Di chl oropropene
trans-1 , 3-01 chl oropropene
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
Toluene
1,1,1-Trlchloroethane
1,1, 2-Tr1 chl oroethane
Trlchloroethene
Tr1 chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(ug/L)
12.8-27.2
13.1-26.9
14.2-25.8
2.8-37.2
14.6-25.4
13.2-26.8
0-44.8
13.5-26.5
0-40.8
13.5-26.5
12.6-27.4
14.6-25.4
12.6-27.4
14.5-25.5
13.6-26,4
10.1-29.9
13.9-26.1
6.8-33.2
4.8-35.2
10.0-30.0
11.8-28.2
12.1-27.9
12.1-27.9
14.7-25.3
14.9-25.1
15.0-25.0
14.2-25.8
13.3-26.7
9.6-30.4
0.8-39.2
Limit
for s
(ug/L)
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
Range
for 7
(ug/L)
15.2-26.0
10.1-28.0
11.4-31.1
0-41.2
17.2-23.5
16.4-27.4
0-50.4
13.7-24.2
0-45.9
13.8-26.6
11.8-34.7
17.0-28.8
11.8-34.7
14.2-28.4
14.3-27.4
3.7-42.3
13.6-28.4
3.8-36.2
1.0-39.0
7.6-32.4
17.4-26.7
0-41.0
13.5-27.2
17.0-26.6
16.6-26.7
13.7-30.1
14.3-27.1
18.5-27.6
8.9-31.5
0-43.5
Range
P, Ps
CO
37-151
35-155
45-169
0-242
70-140
37-160
0-305
51-138
0-273
53-149
18-190
59-156
18-190
59-155
49-155
0-234
54-156
D-210
0-227
17-183
37-162
0-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
0-251
Q = Concentration measured In QC check sample, 1n ug/L.
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, in ug/L.
p, ps = Percent recovery measured.
0 = Detected; result must be greater than zero.
Criteria from 40 CFR Part 136 for Method 624 and were calculated
assuming a QC check sample concentration of 20 ug/L. These criteria are based
directly upon the method performance data 1n Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 7.
8240 - 34
Revision 0
Date September 1986
-------
8.6.2 Analyze one 5-mL sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC check
sample concentrate (Section 8.5.1) appropriate for the background
concentration In the sample. Spike a second 5-mL sample aliquot with 10
uL of the QC check sample concentrate and analyze 1t to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T 1s the known true value of the
spike.
8.6.3 Compare the percent recovery (p) for each analyte with the
corresponding QC acceptance criteria found 1n Table 6. These acceptance
criteria were calculated to Include an allowance for error in measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be acounted for to the extent
that the analyst's spike to background ratio approaches 5:1. If spiking
was performed at a concentration lower than 20 ug/L, the analyst must use
either the QC acceptance criteria presented 1n Table 6, or optional QC
acceptance criteria calculated for the specific spike concentration. To
calculate optional acceptance criteria for the recovery of an analyte:
(1) Calculate accuracy (x1) using the equation found in Table 7,
substituting the spike concentration (T) for ,C; (2) calculate overall
precision (S1) using the equation in Table 7, substituting x1 for 7; (3)
calculate the range for recovery at the spike concentration as (lOOx'/T)
+ 2.44(100S'/T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be
analyzed as described in Section 8.7.
8.7 If any analyte falls the acceptance criteria for recovery 1n Sectln
8.6, a QC check standard containing each analyte that failed must be prepared
and analyzed.
NOTE: The frequency for the required analysis of a QC check standard
will depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the laboratory.
If the entire list of analytes in Table 6 must be measured in the sample
in Section 8.6, the probability that the analysis of a QC check standard
will be required is high. In this case the QC check standard should be
routinely analyzed with the spiked sample.
8.7.1 Prepare the QC check standard by adding 10 uL of the QC check
sample concentrate (Section 8.5.1 or 8.6.2) to 5 ml of reagent water.
The QC check standard needs only to contain the analytes that failed
criteria in the test in Section 8.6.
8.7.2 Analyze the QC check standard to determine the concentration
measured (A) of each analyte. Calculate each precent recovery (ps) as
100 (A/T)%, where T is the true value of the standard concentration.
8240 - 35
Revision
Date September 1986
-------
TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Benzene
Bromodl chl oromethane
Bromoform
Bromomethane
Carbon tetrachlorlde
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether3
Chloroform
Chl oromethane
D1 bromochl oromethane
1 , 2-D1 chl orobenzene*5
1 , 3-D1 chl orobenzene
1 , 4-D1 chl orobenzene'3
1,1-01 chloroethane
1,2-D1 chloroethane
1,1-01 chl oroethene
trans-1 , 2 , -D1 chl oroethene
1 , 2-D1 chl oropropane3
c1s-l,3-D1chloropropene3
trans-1 , 3-D1 chl oropropene3
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
Toluene
1,1, 1-Trl chl oroethane
1,1, 2-Tr1 chl oroethane
Tr1 chl oroethene
Tr1 ch 1 orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(ug/L)
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
1.05C+0.03
l.OOC
l.OOC
l.OOC
0.98C+2.48
0.87C+1.88
0.93C+1.76
1.06C+0.60
0.98C+2.03
1.06C+0.73
0.95C+1.71
1.04C+2.27
0.99C+0.39
l.OOC
Single analyst
precision, sr'
(ug/L)
0.267-1.74
0.157+0.59
0.127+0.34
0.437
0.127+0.25
0.167-0.09
0.147+2.78
0.627
0.167+0.22
0.377+2.14
0.177-0.18
0.227-1.45
0.147-0.48
0.227-1.45
0.137-0.05
0.177-0.32
0.177+1.06
0.147+0.09
0.337
0.387
0.257
0.147+1.00
0.157+1.07
0.167+0.69
0.137-0.18
0.157-0.71
0.127-0.15
0.147+0.02
0.137+0.36
0.337-1.48
0.487
Overall
precision,
S' (ug/L)
0.257-1.33
0.207+1.13
0.177+1.38
0.587
0.117+0.37
0.267-1.92
0.297+1.75
0.847
0.187+0.16
0.587+0.43
0.177+0.49
0.307-1.20
0.187-0.82
0.307-1.20
0.167+0.47
0.217-0.38
0.437-0.22
0.197+0.17
0.457
0.527
0.347
0.267-1.72
0.327+4.00
0.207+0.41
0.167-0.45
0.227-1.71
0.217-0.39
0.187+0.00
0.127+0.59
0.347-0.39
0.657
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at
an average concentration of 7, in ug/L.
S' = Expected Interlaboratory standard deviation of measurements at
an average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
3Est1mates based upon the performance In a single laboratory.
bDue to chromatographic resolution problems, performance statements for
these Isomers are based upon the sums of their concentrations.
8240 - 36
Revision 0
Date September 1986
-------
8.7.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found In Table 6. Only analytes
that failed the test 1n Section 8.6 need to be compared with these
criteria. If the recovery of any such analyte falls outside the
designated range, the laboratory performance for that analyte 1s judged
to be out of control, and the problem must be immediately Identified and
corrected. The result for that analyte 1n the unspiked sample 1s suspect
and may not be reported for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After
the analysis of five spiked samples (of the same matrix) as 1n Section 8.6,
calculate the average percent recovery (J5) and the standard deviation of the
percent recovery (sn). Express the accuracy assessment as a percent recovery
interval from JJ - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the
accuracy interval is expressed as 70-110%. Update the accuracy assessment for
each analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (p) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed 1n Table 8. The limits given 1n Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Paragraph 8.9.3
must fall within those given in Table 8 for these matrices.
8.9.5 If recovery 1s not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
8240 - 37
Revision 0
Date September 1986
-------
TABLE 8. SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/Medium Low/Medium
Surrogate Compound Water Soil/Sediment
4-Bromofluorobenzene 86-115 74-121
l,2-D1chloroethane-d4 76-114 70-121
Toluene-d8 88-110 81-117
8240 - 38
Revision
Date September 1986
-------
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
8.9.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrlx-by-matrix basis, annually.
8.10 It 1s recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column or a different lonization mode using a mass
spectrometer must be used. Whenever possible, the laboratory should analyze
standard reference materials and participate in relevant performance
evaluation studies.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) 1s defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL concentrations listed in
Table 1 were obtained using reagent water. Similar results were achieved
using representative wastewaters. The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
9.2 This method was tested by 15 laboratories using reagent water,
drinking water, surface water, and Industrial wastewaters spiked at six
concentrations over the range 5-600 ug/L. Single operator precision, overall
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially Independent of the sample matrix.
Linear equations to describe these relationships are presented 1n Table 7.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
4. Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.
8240 - 39
Revision 0
Date September 1986
-------
5. Budde, W.L. and J.W. Elchelberger, "Performance Tests for the Evaluation
of Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories," EPA-600/4-79-020, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, April
1980.
6. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.
7. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Elchelberger, Unpublished report, October 1980.
8. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
9. "Interlaboratory Method Study for EPA Method 624-Purgeables," Final Report
for EPA Contract 68-03-3102.
10. "Method Performance Data for Method 624," Memorandum from R. Slater and
T. Pressley, U.S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio/45268, January 17, 1984.
8240 - 40
Revision
Date September 1986
-------
METHOD 8240
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
Direct
inject ion
7. a st
cone
use appr
purge-*
proc
7.2
Purge-an
trap
:t GC/MS
jer-otlng
lltlons;
•oprlate
ind-trap
edure
Calculate
Response
Factors for
5 SPCC's
7.3
f
call
usini
one
erf orm
dally
Dratlon
SPCC ' s
CCC'e
o
8240 - 41
Revision 0
Date September 1986
-------
METHOD 6240
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
ICont Inuea)
Water
mlsclble
1loulos
Sediment/
soil
Select GC/MS
method for the
waste matrix
Dilute at leact
SOX with
reagent water
Screen sample
using Methods
3810 or 382O
IG
concentration
mg/teg?
sample using
Methods 3810 or
3820: dilute
if necessary
7.4.1 Introduce
sample
and standards
into GC by
purge-and-trap
method
and High-level
purge-and-trao
method
response
xceed initial
calibration
Dilute sample
Interference:
decontaminate
system if
necessary
Do ions
saturate?
8240 - 42
Revision p
Date September 1986
-------
METHOD 6240
GAS CHROMATOGHAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
(Continued)
o
7.5 ]
by cc
the
and i
mass
7.S
Ct
concer
of
Ider
ant
Identify
inalytes
loipar ing
; sample
standard
spectra
ilculate
itrat ion
each '
itif ied
ilyte
7.S |
Report results
( Stop J
8240 - 43
Revision 0
Date September 1986
-------
METHOD 8250
GAS CHROMAT06RAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORGANICS;
PACKED COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8250 1s used to determine the concentration of semi volatile
organic compounds In extracts prepared from all types of solid waste
matrices, soils, and ground water. Direct Injection of a sample may be used
in limited applications.
1.2 Method 8250 can be used to quantify most neutral, acidic, and basic
organic compounds that are soluble 1n methylene chloride and capable of being
eluted without derivatlzation as sharp peaks from a gas chromatographic
packed column. Such compounds include polynuclear aromatic hydrocarbons,
chlorinated hydrocarbons and pesticides, phthalate esters, organophosphate
esters, nltrosamlnes, haloethers, aldehydes, ethers, ketones, anilines,
pyridines, quinolines, aromatic nitro compounds, and phenols, including
m'trophenols. See Table 1 for a 11st of compounds and their characteristic
ions that have been evaluated on the specified GC/MS system.
1.3 The following compounds may require special treatment when being
determined by this method. Benzidine can be subject to oxldative losses
during solvent concentration. Also, chromatography is poor. Under the
alkaline conditions of the extraction step, a-BHC, 7-BHC, endosulfan I and
II, and endrln are subject to decomposition. Neutral extraction should be
performed if these compounds are expected and are not being determined by
Method 8080. Hexachlorocyclopentadlene is subject to thermal decomposition
1n the Inlet of the gas chromatograph, chemical reaction in acetone solution,
and photochemical decomposition. N-nltrosodimethyl amine is difficult to
separate from the solvent under the chromatographic conditions described.
N-n1trosod1phenylamine decomposes in the gas chromatographic Inlet and cannot
be separated from diphenylamine. Pentachlorophenol, 2,4-d1nitrophenol,
4-nitrophenol, 4,6-dinitro-2-methylphenol, 4-chloro-3-methylphenol, benzole
acid, 2-nitroaniline, 3-n1troan1line, 4-chloroan1line, and benzyl alcohol are
subject to erratic chromatographic behavior, especially 1f the GC system 1s
contaminated with high boiling material.
1.4 The practical quantltation limit (PQL) of Method 8250 for
determining an individual compound 1s approximately 1 mg/kg (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes (dependent on matrix and method
of preparation), and 10 ug/L for ground water samples (see Table 2). PQLs
will be proportionately higher for sample extracts that require dilution to
avoid saturation of the detector.
1.5 This method 1s restricted to use by or under the supervision of
analysts experienced 1n the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method.
8250 - 1
Revision 0
Date September 1986
-------
TABLE 1. CHROMATOGRAPHIC CONDITIONS, METHOD DETECTION LIMITS, AND
CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
,1
Retention
Compound Time (m1n)
Acenaphthene
Acenaphthene-djo (I.S.)
Acenaphthylene
Acetophenone
Aldrln
Aniline
Anthracene
4-Aminob1 phenyl
Aroclor-1016b
Aroclor-1221b
Aroclor-1232b
Aroclor-1242b
Aroclor-1248b
Aroclor-1254b
Aroclor-1260b
Benzidine3
Benzole add
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo (g , h , 1 ) pery 1 ene
Benzo(a)pyrene
Benzyl alcohol
a-BHCa
£-BHC
5-BHC
7-BHC (Lindane)a
B1 s (2-chl oroethoxy)methane
B1s (2-chl oroethyl) ether
B1 s (2-chl orol sopropy 1 ) ether
B1 s (2-ethyl hexyl ) phthal ate
4-Bromophenyl phenyl ether
Butyl benzyl phthal ate
Chlordaneb
4-Chloroanillne
1-Chloronaphthalene
2-Chl oronaphthal ene
4-Chloro-3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-di2 (I.S.)
4,4'-DDD
4,4'-DDE
17.8
—
17.4
—
24.0
—
22.8
18-30
15-30
15-32
15-32
12-34
22-34
23-32
28.8
—
31.5
34.9
34.9
45.1
36.4
—
21.1
23.4
23.7
22.4
12.2
8.4
9.3
30.6
21.2
29.9
19-30
—
—
15.9
13.2
5.9
19.5
31.5
—
28.6
27.2
Method
detection
limit (ug/L)
1.9
—
3.5
—
1.9
,
1.9
— —
30
«...
»
__
36
44
—
7.8
4.8
2.5
4.1
2.5
—
—
4.2
3.1
—
5.3
5.7
5.7
2.5
1.9
2.5
—
—
1.9
3.0
3.3
4.2
2.5
—
2.8
5.6
Primary
Ion
154
164
152
105
66
93
178
169
222
190
190
222
292
292
360
184
122
228
252
252
276
252
108
183
181
183
183
93
93
45
149
248
149
373
127
162
162
107
128
204
228
240
235
246
Secondary
Ion(s)
153, 152
162, 160
151, 153
77, 51
263, 220
66, 65
176, 179
168, 170
260, 292
224, 260
224, 260
256, 292
362, 326
362, 326
362, 394
92, 185
105, 77
229, 226
253, 125
253, 125
138, 277
253, 125
79, 77
181, 109
183, 109
181, 109
181, 109
95, 123
63, 95
77, 121
167, 279
250, 141
91, 206
375, 377
129
127, 164
127, 164
144, 142
64, 130
206, 141
226, 229
120, 236
237, 165
248, 176
8250 - 2
Revision 0
Date September 1986
-------
TABLE 1. - Continued
Retention
Compound Time (m1n)
4,4'-DDT
D1benz(a,j)acridine
D1 benz (a, h) anthracene
Dlbenzofuran
D1-n-butylphthalate
1 , 3-D1 chl orobenzene
1 , 4-Di chl orobenzene
l,4-D1chlorobenzene-d4 (I.S.)
1 , 2-D1 chl orobenzene
3,3'-D1chlorobenz1d1ne
2 , 4-D1 chl orophenol
2,6-Dichlorophenol
D1eldr1n
Diethylphthalate
p-Di methyl ami noazobenzene
7 , 12-Di methyl benz (a) anthracene
a- , a-D1 methyl phenethy 1 ami ne
2,4-D1methylphenol
Dimethylphthalate
4 , 6-Di ni tro-2-methy 1 phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
1 , 2-D1 pheny 1 hydrazl ne
Di-n-octylphthalate
Endosulfan Ia
Endosulfan IIa
Endosulfan sulfate
Endrin*
Endrln aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorobi pheny 1 (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocycl opentadi ene*
Hexachl oroethane
Indeno (1 , 2 , 3-cd) pyrene
29.3
—
43.2
—
24.7
7.4
7.8
—
8.4
32.2
9.8
—
27.2
20.1
—
—
—
9.4
18.3
16.2
15.9
19.8
18.7
—
—
32.5
26.4
28.6
29.8
27.9
—
—
—
26.5
19.5
—
—
23.4
25.6
21.0
11.4
13.9
8.4
42.7
Method
detection
limit (ug/L)
4.7
—
2.5
—
2.5
1.9
4.4
—
1.9
16.5
2.7
—
2.5
1.9
—
—
—
2.7
1.6
24
42
5.7
1.9
—
—
2.5
—
—
5.6
—
—
—
—
2.2
1.9
—
—
1.9
2.2
1.9
0.9
—
1.6
3.7
Primary
Ion
235
279
278
168
149
146
146
152
146
252
162
162
79
149
120
256
58
122
163
198
184
165
165
169
77
149
195
337
272
263
67
317
79
202
166
172
112
100
353
284
225
237
117
276
Secondary
Ion(s)
237, 165
280, 277
139, 279
139
150, 104
148, 111
148, 111
150, 115
148, 111
254, 126
164, 98
164, 98
263, 279
177, 150
225, 77
241, 257
91, 42
107, 121
194, 164
51, 105
63, 154
63, 89
63, 89
168, 167
105, 182
167, 43
339, 341
339, 341
387, 422
82, 81
345, 250
67, 319
109, 97
101, 203
165, 167
171
64
272, 274
355, 351
142, 249
223, 227
235, 272
201, 199
138, 227
8250 - 3
Revision 0
Date September 1986
-------
TABLE 1. - Continued
Retention
Compound Time (m1n)
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphthal ene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthal ene-ds (I.S.)
1-Naphthylamlne
2-Naphthylamine
2-Nitroan1l1ne
3-N1troan11ine
4-Nitroaniline
Nitrobenzene
Nitrobenzene-ds (surr.)
2-Nitrophenol
4-Nitrophenol
N-N1 troso-di -n-butyl ami ne
N-Ni trosodimethyl ami nea
N-Ni trosodi phenyl ami nea
N-Ni troso-di -N-propyl ami ne
N-Ni trosopi peri dine
Pentachl orobenzene
Pentachl oroni trobenzene
Pentachl orophenol
Perylene-di2 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-djo (I.S.)
Phenol
Phenol -ds (surr.)
2-P1coline
Pronamide
Pyrene
Terphenyl-dj4 (surr.)
1, 2, 4, 5-Tetrachl orobenzene
2,3,4, 6-Tetrachl orophenol
2,4,6-Tribromophenol (surr.)
1,2, 4-Tri chl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Tri chl orophenol
Toxaphene"
11.9
—
—
—
—
—
—
12.1
—
—
—
—
—
—
11.1
—
6.5
20.3
—
—
20.5
—
—
—
—
17.5
—
—
22.8
—
8.0
—
—
—
27.3
—
—
—
—
11.6
—
11.8
25-34 ,
Method
detection
limit (ug/L)
2.2
—
—
—
—
—
—
1.6
—
—
—
—
—
—
1.9
—
3.6
2.4
—
—
1.9
—
—
—
—
3.6
—
—
5.4
—
1.5
—
—
• —
1.9
—
—
—
—
1.9
—
2.7
Primary
Ion
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
330
180
196
196
159
Secondary
Ion(s)
95, 138
228
253, 267
79, 65
141
107, 79
107, 79
129, 127
68
115, 116
115, 116
92, 138
108, 92
108, 92
123, 65
128, 54
109, 65
109, 65
57, 41
74, 44
168, 167
130, 42
114, 55
252, 248
237, 142
264, 268
260, 265
109, 179
179, 176
94, 80
65, 66
42, 71
66, 92
175, 145
200, 203
122, 212
214, 218
230, 131
332, 141
182, 145
198, 200
198, 200
231, 233
aSee Section 1.3
^These compounds are mixtures of various Isomers.
8250 - 4
Revision 0
Date September 1986
-------
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix Factor^
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste 100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
8250 - 5
Revision
Date September 1986
-------
2.0 SUMMARY OF METHOD
2.1 Prior to using this method, the samples should be prepared for
chromatography using the appropriate sample preparation and cleanup methods.
This method describes chromatographic conditions that will allow for the
separation of the compounds in the extract.
3.0 INTERFERENCES
3.1 Raw GC/MS data from all blanks, samples, and spikes must be
evaluated for interferences. Determine if the source of interference is in
the preparation and/or cleanup of the samples and take corrective action to
eliminate the problem.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph/mass spectrometer system;
4.1.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection and all required accessories, including syringes, analytical
columns, and gases.
4.1.2 Columns:
4.1.2.1 For base/neutral compound detection; 2-m x 2-mm I.D.
stainless or glass,packedwith 3%SP-2250-DB on 100/120 mesh
Supelcoport or equivalent.
4.1.2.2 For acid compound detection; 2-m x 2-mm I.D. glass,
packed with 1%SP-1240-DAon100/120 mesh Supelcoport or
equivalent.
4.1.3 Mass spectrometer: Capable of scanning from 35 to 500 amu
every 1 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable
of producing a mass spectrum for decafluorotriphenylphosphine (DFTPP)
which meets all of the criteria in Table 3 when 1 uL of the GC/MS tuning
standard is injected through the GC (50 ng of DFTPP).
4.1.4 GC/MS interface: Any GC-to-MS interface that gives
acceptable calibration points at 50 ng per injection for each compound
of interest and achieves acceptable tuning performance criteria may be
8250 - 6
Revision 0
Date September 1986
-------
TABLE 3. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA a
Mass Ion Abundance Criteria
51 30-60% of mass 198
68 <2% of mass 69
70 <2% of mass 69
127 40-60% of mass 198
197 <1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 >1% of mass 198
441 Present but less than mass 443
442 >40% of mass 198
443 17-23% of mass 442
a J.W. Elchelberger, I.E. Harris, and W.L. Budde. "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry",
Analytical Chemistry, 47, 995 (1975).
8250 - 7
Revision
Date September 1986
-------
used. GC-to-MS Interfaces constructed entirely of glass oY* glass-lined
materials are recommended. Glass may be deactivated by silanlzlng with
d1chlorodimethyls1lane.
4.1.5 Data system: A computer system must be Interfaced to the
mass spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained
throughout the duration of the chromatographic program. The computer
must have software that can search any GC/MS data file for Ions of a
specific mass and that can plot such 1on abundances versus time or scan
number. This type of plot 1s defined as an Extracted Ion Current
Profile (EICP). Software must also be available that allows integrating
the abundances in any EICP between specified time or scan-number limits.
The most recent version of the EPA/NIH Mass Spectral Library should also
be available.
4.2 Syringe; 10-uL.
5.0 REAGENTS
5.1 Stock standard solutions (1.00 ug/uL): Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.
5.1.1 Prepare stock standard solutions by accurately weighing
about 0.0100 g of pure material. Dissolve the material in pesticide
quality acetone or other suitable solvent and dilute to volume in a
10-mL volumetric flask. Larger volumes can be used at the convenience
of the analyst. When compound purity 1s assayed to be 96% or greater,
the weight may be used without correction to calculate the concentration
of the stock standard. Commercially prepared stock standards may be
used at any concentration if they are certified by the manufacturer or
by an Independent source.
5.1.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them. ',
5.1.3 Stock standard solutions must be replaced after 1 yr or
sooner if comparison with quality control check samples Indicates a
problem.
5.2 Internal standard solutions; The internal standards recommended
are 1,4-d1chlorobenzene-d4,naphthalene-dg, acenaphthene-diQi phenanthrene-
dio. chrysene-di2, and perylene-di2. Other compounds may be used as internal
standards as long as the requirements given 1n Paragraph 7.3.2 are met.
Dissolve 200 mg of each compound with a small volume of carbon disulfide.
Transfer to a 50-mL volumetric flask and dilute to volume with methylene
chloride so that the final solvent Is approximately 20% carbon disulfide.
8250 - 8
Revision 0
Date September 1986
-------
Most of the compounds are also soluble 1n small volumes of methanol, acetone,
or toluene, except for perylene-dj2« The resulting solution will contain
each standard at a concentration of 4,000 ng/ul. Each 1-mL sample extract
undergoing analysis should be spiked with 10 uL of the Internal standard
solution, resulting in a concentration of 40 ng/uL of each internal standard.
Store at 4*C or less when not being used.
5.3 GC/MS tuning standard; A methylene chloride solution containing
50 ng/uL oT decaf1uorotriphenylphosphine (DFTPP) should be prepared. The
standard should also contain 50 ng/uL each of 4,4'-DDT, pentachlorophenol,
and benzidine to verify injection port Inertness and GC column performance.
Store at 4'C or less when not being used.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels should be prepared. One of the calibration standards
should be at a concentration near, but above, the method detection limit; the
others should correspond to the range of concentrations found 1n real samples
but should not exceed the working range of the GC/MS system. Each standard
should contain each analyte for detection by this method (e.g., some or all
of the compounds listed 1n Table 1 may be included). Each 1-mL aliquot of
calibration standard should be spiked with 10 uL of the Internal standard
solution prior to analysis. All standards should be stored at -10*C to -20°C
and should be freshly prepared once a year, or sooner if check standards
indicate a problem. The dally calibration standard should be prepared weekly
and stored at 4*C.
5.5 Surrogate standards; The recommended surrogate standards are
phenol-ds, 2-f1uorophenol,274,6-tribromophenol, nitrobenzene-ds, 2-fluoro-
biphenyl, and p-terphenyl-dj4. See Method 3500 for the instructions on
preparing the surrogate standards. Determine what concentration should be 1n
the blank extracts after all extraction, cleanup, and concentration steps.
Inject this concentration Into the GC/MS to determine recovery of surrogate
standards in all blanks, spikes, and sample extracts. Take Into account all
dilutions of sample extracts.
5.6 Matrix spike standards; See Method 3500 for instructions on
preparing the matrix spike standard. Determine what concentration should be
1n the blank extracts after all extraction, cleanup, and concentration steps.
Inject this concentration into the GC/MS to determine recovery of surrogate
standards in all blanks, spikes, and sample extracts. Take Into account all
dilutions of sample extracts.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material to this chapter, Organic Analytes,
Section 4.1.
8250 - 9
Revision 0
Date September 1986
-------
7.0 PROCEDURE
7.1 Sample preparation; Samples must be prepared by one of the
following methods prior to GC/MS analysis.
Matrix Methods
Water 3510, 3520
Soil/sediment 3540, 3550
Waste 3540, 3550, 3580
7.1.1 Direct Injection: In very limited applications direct
injection of the sample into the GC/MS system with a 10 uL syringe may
be appropriate. The detection limit is very high (approximately 10,000
ug/L); therefore, it is only permitted where concentrations in excess of
10,000 ug/L are expected. The system must be calibrated by direct
injection.
7.2 Extract cleanup; Extracts may be cleaned up by any of the
following methods prior to GC/MS analysis.
Compounds Methods
Phenols 3630, 3640, 8040a
Phthalate esters 3610, 3620, 3640
Nitrosamines 3610, 3620, 3640
Organochlorine pesticides & PCBs 3620, 3640, 3660
Nitroaromatics and cyclic ketones 3620, 3640
Polynuclear aromatic hydrocarbons 3611, 3630, 3640
Haloethers 3620, 3640
Chlorinated hydrocarbons 3620, 3640
Organophosphorous pesticides 3620, 3640
Petroleum waste 3611, 3650
All priority pollutant base,
neutral, and acids 3640
aMethod 8040 includes a derivatization technique followed by GC/ECD
analysis, if interferences are encountered on GC/FID.
7.3 Initial calibration; The recommended GC/MS operating conditions;
Electron energy: 70 volts (nominal)
Mass range: 35-500 amu
Scan time: 1 sec/scan
Injector temperature: 250-300*C
Transfer line temperature: 250-300°C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
Sample volume: 1-2 uL
Carrier gas: Helium at 30 mL/min
8250 - 10
Revision
Date September 1986
-------
Conditions for base/neutral analysis (3% SP-2250-DB):
Initial column temperature and hold time: 50*C for 4 m1n
Column temperature program: 50-300*C at 8*C/m1n
Final column temperature hold: 300*C for 20 m1n
Conditions for add analysis (1% SP-1240-DA):
Initial column temperature and hold time: 70*C for 2 m1n
Column temperature program: 70-200*C at 8*C/m1n
Final column temperature hold: 200*C for 20 m1n
7.3.1 Each GC/MS system must be hardware-tuned to meet the
criteria 1n Table 3 for a 50-ng Injection of DFTPP. Analyses should not
begin until all these criteria are met. Background subtraction should
be straightforward and designed only to eliminate column bleed or
Instrument background Ions. The GC/MS tuning standard should also be
used to assess GC column performance and Injection port Inertness.
Degradation of DDT to DDE and DDD should not exceed 20%. Benz1d1ne and
pentachlorophenol should be present at their normal responses, and no
peak tailing should be visible. If degradation 1s excessive and/or poor
chromatography Is noted, the Injection port may require cleaning.
7.3.2 The Internal standards selected In Paragraph 5.1 should
permit most of the components of Interest 1n a chromatogram to have
retention times of 0.80-1.20 relative to one of the Internal standards.
Use the base peak 1on from the specific Internal standard as the primary
1on for quantltatlon (see Table 1). If Interferences are noted, use the
next most Intense 1on as the quantltatlon 1on, I.e., for 1,4-
d1chlorobenzene-d4 use m/z 152 for quantltatlon.
7.3.3 Analyze 1 uL of each calibration standard (containing
Internal standards) and tabulate the area of the primary characteristic
Ion against concentration for each compound (as Indicated 1n Table 1).
Calculate response factors (RFs) for each compound as follows:
RF = (AxC1s)/(A1sCx)
where:
Ax = Area of the characteristic Ion for the compound being
measured.
Ais = Area of the characteristic 1on for the specific Internal
standard.
Cx = Concentration of the compound being measured (ng/uL).
Cjs = Concentration of the specific Internal standard (ng/uL).
8250 - 11
Revision
Date September 1986
-------
7.3.4 The average RF should be calculated for each compound. The
percent relative standard deviation (%RSD = 100[SD7RF]) should also be
calculated for each compound. The %RSD should be less than 30% for each
compound. However, the %RSD for each individual Calibration Check
Compound (CCC) (see Table 4) must be less than 30%. The relative
retention times of each compound in each calibration run should agree
within 0.06 relative retention time units. Late-eluting compounds
usually have much better agreement.
7.3.5 A system performance check must be performed to ensure that
minimum average response factors are met before the calibration curve is
used. For semivolatiles, the System Performance Check Compounds (SPCCs)
are: N-nitroso-di-n-propylamine; hexachlorocyclopentadiene; 2^4-
dinitrophenol; and 4-nitrophenol. The minimum acceptable average RF for
these is 0.050. These SPCCs typically have very low RFs (0.1-0.2) and
tend to decrease in response as the chromatographic system begins to
deteriorate or the standard material begins to deteriorate. They are
usually the first to show poor performance. Therefore, they must meet
the minimum requirement when the system is calibrated.
7.4 Daily GC/MS calibration;
7.4.1 Prior to analysis of samples, the GC/MS tuning standard must
be analyzed. A 50-ng injection of DFTPP must result in a mass spectrum
for DFTPP which meets the criteria given in Table 3. These criteria
must be demonstrated during each 12-hr shift.
7.4.2 A calibration standard(s) at mid-level concentration
containing all semi volatile analytes, including all required surrogates,
must be performed every 12-hr during analysis. Compare the response
factor data from the standards every 12-hr with the average response
factor from the initial calibration for a specific Instrument as per
SPCC (Paragraph 7.4.3) and CCC (Paragraph 7.4.4) criteria.
7.4.3 System Performance Check Compounds (SPCCs): A system
performance check must be made during every 12 hr shift. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the Initial
calibration. If the minimum response factors are not met, the system
must be evaluated, and corrective action must be taken before sample
analysis begins. The minimum RF for semivolatile SPCCs is 0.050. Some
possible problems are standard mixture degradation, injection port inlet
contamination, contamination at the front end of the analytical column,
and active sites in the column or chromatographic system. This check
must be met before analysis begins.
7.4.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed 1n Table 4 are used to check the
validity of the initial calibration. Calculate the percent difference
using:
8250 - 12
Revision 0
Date September 1986
-------
TABLE 4. CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction Add Fraction
Acenaphthene 4-Chloro-3-methylphenol
1,4-D1chlorobenzene 2,4-D1chlorophenol
Hexachlorobutadi ene 2-N1trophenol
N-Ni troso-d1-n-phenylamine Phenol
D1-n-Octy1phthalate Pentachlorophenol
Fluoranthene 2,4,6-Trlchlorophenol
Benzo(a)pyrene
8250 - 13
Revision
Date September 1986
-------
RFj - RF
% Difference = — — - x 100
where:
RFj = average response factor from Initial calibration.
RFC = response factor from current verification check standard.
If the percent difference for any compound 1s greater than 20, the
laboratory should consider this a warning limit. If the percent
difference for each CCC 1s less than 30%, the Initial calibration 1s
assumed to be valid. If the criterion 1s not met (>30% difference) for
any one CCC, corrective action MUST be taken. Problems similar to those
listed under SPCCs could affect these criterion. If no source of the
problem can be determined after corrective action has been taken, a new
five-point calibration MUST be generated. This criterion MUST be met
before sample analysis begins.
7.4.5 The Internal standard responses and retention times 1n the
calibration check standard must be evaluated Immediately after or during
data acquisition. If the retention time for any Internal standard
changes by more than 30 sec from the last check calibration (12 hr), the
chromatographlc system must be Inspected for malfunctions and correc-
tions must be made, as required. If the EICP area for any of the
Internal standards changes by a factor of two (-50% to +100%) from the
last dally calibration standard check, the mass spectrometer must be
Inspected for malfunctions and corrections must be made,, as appropriate.
7.5 GC/MS analysis;
7.5.1 It 1s highly recommended that the extract be screened on a
GC/FID or GC/PID using the same type of column. This will minimize
contamination of the GC/MS system from unexpectedly high concentrations
of organic compounds.
7.5.2 Spike the 1-mL extract obtained from sample preparation with
10 uL of the Internal standard solution just prior to analysis.
7.5.3 Analyze the 1-mL extract by GC/MS using the appropriate
column (as specified in Paragraph 4.1.2). The recommended GC/MS
operating conditions to be used are specified in Paragraph 7.3.
7.5.4 If the response for any quantltatlon 1on exceeds the Initial
calibration curve, range of the GC/MS system, extract dilution must take
place. Additional internal standard must be added to the diluted
extract to maintain the required 40 ng/uL of each Internal standard 1n
the extracted volume.. The diluted extract must be reanalyzed.
8250 - 14
Revision 0
Date September 1986
-------
7.5.5 Perform all qualitative and quantitative measurements as
described 1n Paragraph 7.6. Store the extracts at 4*C, protected from
light 1n screw-cap vials equipped with unplerced Teflon-lined septa.
7.6 Data Interpretation:
7.6.1 Qualitative analysis:
7.6.1.1 An analyte (e.g., those listed 1n Table 1) 1s
Identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
spectrum). Mass spectra for standard reference compounds should be
obtained on the user's GC/MS within the same 12 hours as the sample
analysis. These standard reference spectra may be obtained through
analysis of the calibration standards. Two criteria must be
satisfied to verify Identification: (1) elutlon of sample component
at the same GC relative retention time (RRT) as the standard
component; and (2) correspondence of the sample component and the
standard component mass spectrum.
7.6.1.1.1 The sample component RRT must compare within
+0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hrs as
the sample. If coelutlon of Interfering components prohibits
accurate assignment of the sample component RRT from the total
1on chromatogram, the RRT should be assigned by using extracted
1on current profiles for ions unique to the component of
interest.
7.6.1.1.2 All ions present 1n the standard mass spectra
at a relative intensity greater than 10% (most abundant ion 1n
the spectrum equals 100% must be present in the sample
spectrum.
7.6.1.1.3 The relative intensities of Ions specified in
Paragraph 7.6.1.1.2 must agree within plus or minus 20% between
the standard and sample spectra. (Example: For an ion with an
abundance of 50% in the standard spectra, the corresponding
sample abundance must be between 30 and 70 percent.
7.6.1.2 For samples containing components not associated with
the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted (e.g., for EPA Contract Laboratory Program
requirements, up to 20 substances of greatest apparent concentration
not listed in the Hazardous Substance List must be tentatively
identified). Computer generated library search routines should not
use normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample spectra with the nearest library searches will
8250 - 15
Revision 0
Date September 1986
-------
the mass spectral Interpretation specialist assign a tentative
identification. Guidelines for making tentative Identification are:
(1) Relative Intensities of major ions in the reference spectrum
(ions >10% of the most abundant ion) should be present in the sample
spectrum.
(2) The relative intensities of the major ions should agree within
+20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ,ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should be
present 1n sample the spectrum.
(4) Ions present 1n the sample spectrum but not 1n the reference
spectrum should be reviewed for possible background contamination or
presence of coelutlng compounds.
(5) Ions present 1n the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coelutlng peaks.
Data system library reduction programs can sometimes create these
discrepancies.
7.6.2 Quantitative analysis:
7.6.2.1 When a compound has been identified, the quantltatlon
of that compound will be based on the Integrated abundance from the
EICP of the primary characteristic 1on. Quantltatlon will take
place using the internal standard technique. The internal standard
used shall be the one nearest the retention time of that of a given
analyte (e.g., see Table 5).
7.6.2.2 Calculate the concentration of each identified analyte
in the sample as follows:
Water;
(Ax)(IJ(Vt)
concentration (ug/L) = -TT—WRF\ /v
o
where:
Ax = Area of characteristic ion for compound being
measured.
Is = Amount of Internal standard Injected (ng).
8250 - 16
Revision
Date September 1986
-------
TABLE 5. SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
1,4-Di chlorobenzene-d4
Naphtha!ene-dg
Acenaphthene-dio
Aniline
Benzyl alcohol
Bi s(2-chloroethyl)ether
Bi s(2-chl oroi sopropyl)ether
2-Chlorophenol
1,3-Di chlorobenzene
1,4-Di chlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Ni trosodlmethylami ne
N-Ni troso-di-n-propy1 ami ne
Phenol
Phenol-de (surr.)
2-P1coline
Acetophenone
Benzoic acid
Bi s(2-chloroethoxy)methane
4-Chloroaniline
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl -
phenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-dg (surr.)
2-Nitrophenol
N-Ni troso-di-n-butylami ne
N-Nitrosopiperidine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Di ni trotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
(surr.)
Hexachlorocyclo-
pentadiene
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetra-
chlorobenzene
2,3,4,6-Tetra-
chlorophenol
2,4,6-Tribromo-
phenol (surr.)
2,4,6-Trichloro-
phenol
2,4,5-Trichloro-
phenol
(surr.) = surrogate
8250 - 17
Revision 0
Date September 1986
-------
TABLE 5. SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION (Continued)
Phenanthrene-dio
Chrysene-di2
Perylene-dj2
4-Am1nob1phenyl
Anthracene
4-Bromophenyl phenyl ether
D1-n-butyl phthalate
4,6-Din1tro-2-methylphenol
D1phenylamine
1,2-D1phenylhydrazlne
Fluoranthene
Hexachlorobenzene
N-N1trosodlphenylamine
Pentachlorophenol
Pentachloronltrobenzene
Phenacetln
Phenanthrene
Pronamlde
Benz1d1ne
Benzo(a)anthracene
B1s(2-ethy1hexyl)phthalate
Butyl benzylphthalate
Chrysene
3,3'-D1chlorobenzld1ne
p-D1methyl aminoazobenzene
Pyrene
Terphenyl-dj4 (surr.)
Benzo(b)fluor-
anthene
Benzo(k)fluor-
anthene
Benzo(g,h,1)
perylene
Benzo(a)pyrene
D1benz(a,j)acr1d1ne
D1benz(a,h)
anthracene
7,l2-D1methylbenz-
(a)anthracene
D1-n-octylphthalate
Indeno(l,2,3-cd)
pyrene
3-Methylchol-
anthrene
(surr.) = surrogate
8250 - 18
Revision 0
Date September 1986
-------
Vt = Volume of total extract, taking Into account dilutions
(I.e., a l-to-10 dilution of a 1-mL extract will mean
Vt = 10,000 uL. If half the base/neutral extract and
half the add extract are combined, Vt = 2,000.
AJS = Area of characteristic Ion for the Internal standard.
RF = Response factor for compound being measured (Paragraph
7.3.3).
V0 = Volume of water extracted (ml_).
Vj = Volume of extract Injected (uL).
Sediment/Soil Sludge (on a dry-weight basis) and Waste (normally on
a wet-weight basis;
(AJU.MVJ
concentration (ug/kg) = (AIS)(RF)(VI)(WS)(D)
where:
Ax» Is* Vt! Ais, RF, V^ = same as for water.
Ws = weight of sample extracted or diluted 1n grams.
D = (100 - % moisture 1n sample)/100, or 1 for a wet-weight
basis.
7.6.2.3 Where applicable, an estimate of concentration for
noncallbrated components 1n the sample should be made. The
formulas given above should be used with the following modifica-
tions: The areas Ax and Ajs should be from the total 1on chromato-
grams and the RF for the compound should be assumed to be 1. The
concentration obtained should be reported Indicating (1) that the
value 1s an estimate and (2) which Internal standard was used to
determine concentration. Use the nearest Internal standard free of
Interferences.
7.6.2.4 Report results without correction for recovery data.
When duplicates and spiked samples are analyzed, report all data
obtained with the sample results.
7.6.2.5 Quantisation of multlcomponent compounds (e.g.,
Aroclors) is beyond the scope of Method 8270. Normally,
quantltatlon is performed using a GC/ECD by Method 8080.
8250 - 19
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 Each laboratory.that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an ongoing
analysis of spiked samples to evaluate and document quality data. The
laboratory must maintain records to document the quality of the data
generated. Ongoing data quality checks are compared with established
performance criteria to determine if ', the results of analyses meet the
performance characteristics of the method. When results of sample spikes
indicate atypical method performance, a quality control check standard must
be analyzed to confirm that the measurements were performed in an 1n-control
mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent water blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a
set of samples is extracted or there is a change in reagents, a reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 The experience of the analyst performing GC/MS analyses 1s
invaluable to the success of the methods.' Each day that analysis is
performed, the daily calibration standard should be evaluated to determine if
the chromatographic system is operating properly. Questions that should be
asked are: Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations? Careful examination of the standard
chromatogram can Indicate whether the column is still good, the Injector 1s
leaking, the injector septum needs replacing, etc. If any changes are made
to the system (e.g, column changed), recalibration of the system must take
place.
8.4 Required instrument QC is found 1n the following section:
8.4.1 The GC/MS system must be tuned to meet the DFTPP
specifications in Section 7.3.1 and 7.4.1.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in 7.3.
8.4.3 The GC/MS system must meet the SPCC criteria specified 1n
7.4.3 and the CCC criteria in 7.4.4, each 12 hr.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the; following operations.
8.5.1 A quality (QC) check sample concentrate is required
containing each analyte at a concentration of 100 ug/mL in acetone. The
QC check sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If prepared by the laboratory, the
8250 - 20
Revision 0
Date September 1986
-------
QC check sample concentrate must be made using stock standards prepared
independently from those used for calibration.
8.5.2 Using a pipet, prepare QC check samples at a concentration of
100 ug/L by adding 1.00 ml of QC check sample concentrate to each of four
1-L aliquots of reagent water.
8.5.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 7.1 with extraction of the samples.
8.5.4 Calculate the average recovery (7) in ug/L, and the standard
deviation of the recovery (s) in ug/L, for each analyte of interest using
the four results.
8.5.5 For each analyte compare s and 7 with the corresponding
acceptance criteria for precision and accuracy, respectively, found in
Table 6. If s and 7 for all analytes of interest meet the acceptance
criteria, the system performance is acceptable and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual 7 falls outside the range for accuracy, then the system
performance is unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
analyzed.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Section
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with Section
8.5.2.
8.5.6.2 Beginning with Section 8.5.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Section
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a reagent blank, a
matrix spike, and a matrix spike/duplicate for each analytical batch (up to a
maximum of 20 samples/batch) to assess accuracy. For laboratories analyzing
one to ten samples per month, at least one spiked sample per month is
required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration of
a specific analyte in the sample is being checked against a
regulatory concentration limit, the spike should be at that limit or
8250 - 21
Revision 0
Date September 1986
-------
TABLE 6. QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
AldHn
Anthracene
Benzo a) anthracene
Benzo bjfluoranthene
Benzo kjfluoranthene
Benzo ajpyrene
Benzo (ghl)perylene
Benzyl butyl phthalate
/7-BHC
5-BHC
B1s 2-chloroethyl) ether
Bis 2-chloroethoxy)methane
B1s 2-chloro1sopropyl) ether
B1 s (2-ethy 1 hexyl ) phthal ate
4-Bromophenyl phenyl ether
2-Chl oronaphthal ene
4-Chlorophenyl phenyl ether
Chrysene
4, 4 '-ODD
4,4'-DDE
4, 4 '-DDT
Dlbenzo (a, h) anthracene
Dl-n-butyl phthalate
1 , 2-D1 chl orobenzene
1 , 3-D1 chl orobenzene
1,4-01 chl orobenzene
3,3'-D1chlorobenz1d1ne
Dleldrln
D1 ethyl phthalate
Dimethyl phthalate
2,4-D1n1trotoluene
2,6-D1n1trotoluene
01 -n-octyl phthal ate
Endosulfan sulfate
Endrln aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxlde
Hexachl orobenzene
Hexach 1 orobutadl ene
Hexachl oroethane
Test
cone.
(ug/L)
100 ;
100
100
100
100
100 ,
100
100
100
100
100
100
100 .
100
100
100
100 :
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9 .
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
24.5
Range
for X
(ug/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
55.2-100.0
Range
P, Ps
(%)
47-145
33-145
D-166
27.133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
40-113
8250 - 22
Revision 0
Date September 1986
-------
TABLE 6. QC ACCEPTANCE CRITERIA3 - Continued
Parameter
Indeno (1, 2 ,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-N1 troso-d1 -n-propyl ami ne
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trlchlorobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-01 methyl phenol
2,4-D1n1trophenol
2-Methyl -4, 6-d1 n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
Range
for 7.
(ug/L)
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
Range
P, Ps
(%)
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
p, ps = Percent recovery measured.
D = Detected; result must be greater than zero.
aCn'ter1a from 40 CFR Part 136 for Method 625. These criteria are based
directly on the method performance data In Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 7.
8250 - 23
Revision
Date September 1986
-------
1 to 5 times higher than the background concentration determined 1n
Section 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in the
sample is not being checked against a limit specific to that
analyte, the spike should be at 100 ug/L or 1 to 5 times higher than
the background concentration determined in Section 8.6.2, whichever
concentration would be larger.
8.6.1.3 If it 1s impractical to determine background levels
before spiking (e.g., maximum holding times will be exceeded), the
spike concentration should be at (1) the regulatory concentration
limit, if any; or, if none (2) the larger of either 5 times higher
than the expected background concentration or 100 ug/L.
8.6.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC check
sample concentrate (Section 8.5.1) appropriate for the background
concentration in the sample. Spike a second sample aliquot with 1.00 mL
of the QC check sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T is the known true value of the
spike.
8.6.3 Compare the percent recovery (p) for each analyte with the
corresponding QC acceptance criteria found In Table 6. These acceptance
criteria were calculated to include an allowance for error 1n measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1. If spiking
was performed at a concentration lower than 100 ug/L, the analyst must
use either the QC acceptance criteria presented in Table 6, or optional
QC acceptance criteria calculated for the specific spike concentration.
To calculate optional acceptance criteria for the recovery of an analyte:
(1) Calculate accuracy (x1) using the equation found in Table 7,
substituting the spike concentration (T) for C; (2) calculate overall
precision (S1) using the equation in Table 7, substituting x1 for 7; (3
calculate the range for recovery at the spike concentration as (lOOx'/T
+ 2.44(100S'/T)%.
8.6.4 If any individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be
analyzed as described 1n Section 8.7.
8.7 If any analyte fails the acceptance criteria for recovery 1n Section
8.6, a QC check standard containing each analyte that failed must be prepared
and analyzed.
NOTE: The frequency for the required analysis of a QC check standard
will depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the laboratory.
8250 - 24
Revision 0
Date September 1986
-------
TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo (a) anthracene
Chloroethane
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Benzo (ghi ) pery 1 ene
Benzyl butyl phthalate
0-BHC
5-BHC
Bi s (2-chl oroethyl ) ether
Bi s (2-chl oroethoxy) methane
Bi s (2-chl orol sopropyl ) ether
B1 s (2-ethyl hexyl )phthal ate
4-Bromophenyl phenyl ether
2-Chl oronaphthal ene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo(a,h)anthracene
Di-n-butyl phthalate
l,2-D1chlorobenzene
1 , 3-Di chl orobenzene
1 , 4-D1 chl orobenzene
3 , 3 ' -Di chl orobenzi d1 ne
Dieldrin
Di ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl oroethane
Accuracy, as
recovery, x1
(ug/L)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
Single analyst
precision, sr'
(ug/L)
0.157-0.12
0.247-1.06
0.277-1.28
0.217-0.32
0.157+0.93
0.147-0.13
0.227+0.43
0.197+1.03
0.227+0.48
0.297+2.40
0.187+0.94
0.207-0.58
0.347+0.86
0.357-0.99
0.167+1.34
0.247+0.28
0.267+0.73
0.137+0.66
0.077+0.52
0.207-0.94
0.287+0.13
0.297-0.32
0.267-1.17
0.427+0.19
0.307+8.51
0.137+1.16
0.207+0.47
0.257+0.68
0.247+0.23
0.287+7.33
0.207-0.16
0.287+1.44
0.547+0.19
0.127+1.06
0.147+1.26
0.217+1.19
0.127+2.47
0.187+3.91
0.227-0.73
0.127+0.26
0.247-0.56
0.337-0.46
0.187-0.10
0.197+0.92
0.177+0.67
Overall
precision,
S1 (ug/L)
0.217-0.67
0.267-0.54
0.437+1.13
0.277-0.64
0.267-0.21
0.177-0.28
0.297+0.96
0.357+0.40
0.327+1.35
0.517-0.44
0.537+0.92
0.307+1.94
0.937-0.17
0.357+0.10
0.267+2.01
0.257+1.04
0.367+0.67
0.167+0.66
0.137+0.34
0.307-0.46
0.337-0.09
0.667-0.96
0.397-1.04
0.657-0.58
0.597+0.25
0.397+0.60
0.247+0.39
0.417+0.11
0.297+0.36
0.477+3.45
0.267-0.07
0.527+0.22
1.057-0.92
0.217+1.50
0.197+0.35
0.377+1.19
0.637-1.03
0.737-0.62
0.287-0.60
0.137+0.61
0.507-0.23
0.287+0.64
0.437-0.52
0.267+0.49
0.177+0.80
8250 - 25
Revision 0
Date September 1986
-------
TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3 -
Continued
Parameter
Indeno (1 , 2 , 3-cd) py rene
Isophorone
Naphthalene
Nitrobenzene
N-N1 troso-d1 -n-propy 1 ami ne
PCB-1260
Phenanthrene
Pyrene
1,2, 4-Tr1 chl orobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2, 4-D1methyl phenol
2,4-D1n1trophenol
2-Methyl -4, 6-d1 n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x'
(ug/L)
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22:
0.81C-10.86
0.87C+0.06'
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, sr'
(ug/L)
0.297+1.46
0.277+0.77
0.217-0.41
0.197+0.92
0.277+0.68
0.357+3.61
0.127+0.57
0.167+0.06
0.157+0.85
0.237+0.75
0.187+1.46
0.157+1.25
0.167+1.21
0.387+2.36
0.107+42.29
0.167+1.94
0.387+2.57
0.247+3.03
0.267+0.73
0.167+2.22
Overal 1
precision,
S' (ug/L)
0.507-0.44
0.337+0.26
0.307-0.68
0.277+0.21
0.447+0.47
0.437+1.82
0.157+0.25
0.157+0.31
0.217+0.39
0.297+1.31
0.287+0.97
0.217+1.28
0.227+1.31
0.427+26.29
0.267+23.10
0.277+2.60
0.447+3.24
0.307+4.33
0.357+0.58
0.227+1.81
x1 = Expected recovery for one or • more measurements of a sample
containing a concentration of C, 1n ug/L.
-i- '
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, 1n ug/L.
S1 = Expected Interlaboratory standard deviation of measurements at an
average concentration found of 7, 1n ug/L.
C = True value for the concentration, 1n ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8250 - 26
Revision 0
Date September 1986
-------
If the entire 11st of analytes 1n Table 6 must be measured 1n the sample
1n Section 8.6, the probability that the analysis of a QC check standard
will be required 1s high. In this case the QC check standard should be
routinely analyzed with the spiked sample.
8.7.1 Prepare the QC check standard by adding 1.0 ml of the QC
check sample concentrate (Section 8.5.1 or 8.6.2) to 1 L of reagent
water. The QC check standard needs only to contain the analytes that
failed criteria in the test 1n Section 8.6.
8.7.2 Analyzed the QC check standard to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (Ps) as
100 (A/T)%, where T 1s the true value of the standard concentration.
8.7.3 Compare the percent recovery (Ps) for each analyte with the
corresponding QC acceptance criteria found In Table 6. Only analytes
that failed the test 1n Section 8.6 need to be compared with these
criteria. If the recovery of any such analyte falls outside the
designated range, the laboratory performance for that analyte 1s judged
to be out of control, and the problem must be Immediately Identified and
corrected. The result for that analyte in the unspiked sample 1s suspect
and may not be reported for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After
the analysis of five spiked samples (of the same matrix) as in Section 8.6,
calculate the average percent recovery (p) and the standard deviation of the
percent recovery (sp). Express the accuracy assessment as a percent recovery
Interval from p - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the
accuracy Interval is expressed as 70-110%. Update the accuracy assessment for
each analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate 1n the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (P) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = P + 3s
Lower Control Limit (LCL) = P - 3s
8250 - 27
Revision
Date September 1986
-------
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 8. The limits given in Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Paragraph 8.9.3
must fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.9.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrlx-by-matrix basis, annually.
8.10 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column or mass spectrometry using other ionization modes
must be used. Whenever possible, the laboratory should analyze standard
reference materials and participate in relevant performance evaluation
studies.
9.0 METHOD PERFORMANCE
9.1 Method 8250 was tested by 15 laboratories using reagent water,
drinking water, surface water, and Industrial wastewaters spiked at six
concentrations over the range 5-1,300 ug/L. Single operator accuracy and
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially independent of the sample
matrix. Linear equations to describe these relationships are presented in
Table 7.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 625," October 26,
1984.
8250 - 28
Revision 0
Date September 1986
-------
TABLE 8. SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/Medium Low/Medium
Surrogate Compound Water Soil/Sediment
Nitrobenzene-ds 35-114 23-120
2-Fluorobiphenyl 43-116 30-115
p-Terphenyl-di4 33-141 18-137
Phenol-d6 10-94 24-113
2-Fluorophenol 21-100 25-121
2,4,6-Tribromophenol 10-123 19-122
8250 - 29
Revision
Date September 1986
-------
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, 58-63, 1983.
4. Elchelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.
5. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Elchelberger, Unpublished report, October 1980.
6. "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Adds, and
Pesticides," Final Report for EPA. Contract 68-03-3102 (1n preparation).
7. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8250 - 30
Revision
Date September 1986
-------
METHOD easo
GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORGANICS:
PACKED COLUMN TECHNIQUE
7. t
Prepare ••tuple
using Method
3540 or 3SSO
7. 1
Prepare sample
using Method
3510 or 3520
7.1 |
Prepare
•ample using
Method 3540.
3SSO or 3580
7.2
Cleanup extract
7.3
Set GC/MS
operating
conditions ana
perform initial
calibration
7.4
Perform daily GC/MS
calibration -1th
SPCCs ana CCC» prior
to analysis of
samples
o
8250 - 31
Revision 0
Date September 1986
-------
METHOD 8250
GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORCANICS:
PACKED COLUMN TECHNIQUE
(Continued)
o
7.5.1
0
Screen
extract
on GC/FID or
GC/PIO to elim-
inate too-high
concentration
7.5
7.6. 1
Identify
analyte
by comparing
the sample and
standard mass
spectra
Analyze extract by
GC/MS using
silicone-coated
fused—s ilica
capillary column
7.6.2
Calculate
concentration
of each
identified
analyte
Does response
exceed initial
calibration
curve
range
7.6.2.4
Report results
f Stop J
8250 - 32
Revision o
Date September 1986
-------
METHOD 8260
&
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE
* CAPILLARY COLUMN TECHNIQUE
S'v^
l!o- SCOPE AND APPLICATION
1.1 Method 8260 is used to determine volatile organic compounds.in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous
sludges, caustic liquors, acid liquors, waste solvents, oily wastes, mousses,
tars, fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments. The following compounds can be determined by
this method:
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
Di bromochloromethane
1,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
8260 - 1
CAS No.
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
124-48-1
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-69-4
156-60-5
78-87-5
142-28-9
594-20-7
563-58-6
100-41-4
87-68-3
Revision 1
December 1988
-------
Analyte CAS No.a
Isopropylbenzene 98-82-8
p-Isopropyltoluene 99-87-6
Methylene chloride 75-09-2
Naphthalene 91-20-3
n-Propylbenzene 103-65-1
Styrene 100-42-5
1,1,1,2-Tetrachloroethane 630-20-6
1,1,2,2,-Tetrachloroethane 79-34-5
Tetrachloroethene 127-18-4
Toluene 108-88-3
T,2.3-Trichlorobenzene 87-61-6
1,2,4-Trichlorobenzene 120-82-1
1,1,1-Trichloroethane 71-55-6
1,f,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
1,2,3-Trichloropopane • 96-18-4
1,2,4-Trimethylbenzene 95-63-6
1,3,5-Trimethylbenzene 108-67-8
Vinyl chloride 75-01-4
o-Xylene 95-47-6
m-Xylene 108-38-3
p-Xylene 106-42-3
aChemical Abstract Services Registry Number.
1.2 Method 8260 can be used to quantify most volatile organic compounds
that have boiling points below 200°C and that are insoluble or slightly
soluble in water. Volatile water-soluble compounds can be included in this
analytical technique; however, for the more soluble compounds, quantitation
limits are approximately ten times higher because of poor purging efficiency.
Such compounds include low-molecular-weight halogenated hydrocarbons,
aromatics, ketones, nitriles, acetates, acrylates, ethers, and sulfides. See
Tables 1 and 2 for lists of analytes and retention times that have been
evaluated on a purge-and-trap GC/MS system. Also, the method detection limits
for 25-mL sample volumes are presented.
1.3 The practical quantitation limit (PQL) of Method 8260 for an
individual compound is approximately 5 ug/kg (wet weight) for soil/sediment
samples, 0.5 mg/kg (wet weight) for wastes, and 5 ug/L for ground water (see
Table 3). PQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the
detector.
1.4 Method 8260 is based upon a purge-and-trap, gas chromatographic/ mass
spectrometric (GC/MS) procedure. This method is restricted to use by, or under
the supervision of, analysts experienced in the use of purge-and-trap systems
and gas chromatograph/mass spectrometers, and skilled in the interpretation of
mass spectra and their use as a quantitative tool.
8260 - 2 Revision 1
December 1988
-------
2.0 SUMMARY OF METHOD
2.1 The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications).
Purged sample components are trapped in a tube containing suitable sorbent
materials. When purging is complete, the sorbent tube is heated and
backflushed with .helium to desorb trapped sample components. The analytes are
desorbed diretly to a large bore capillary or cryofocussed on a capillary
precolumn before being flash evaporated to a narrow bore capillary for
anaylsis. The column is temperature programmed to separate the analytes which
are then detected with a mass spectrometer (MS) interfaced to the gas
chromatograph. Wide bore capillary columns require a jet separator, whereas
narrow bore capillary columns can be directly interfaced to the ion source.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in solvent to dissolve the.volatile organic
constituents. A portion of the solution is combined with water in the purge
chamber. It is then analyzed by purge-and-trap GC/MS following the normal
water method.
2.3 Qualitative identifications are confirmed by analyzing standards
under the same conditions used for samples and comparing resultant mass
spectra and GC retention times. Each identified component is quantified by
relating the MS response for an appropriate selected ion produced by that
compound to the MS response for another ion produced by an internal standard.
3.0 INTERFERENCES
3.1 Major contaminant sources are volatile materials in the laboratory
and impurities in the inert purging gas and in the sorbent trap. The use of
non-polytetrafluoroethylene (PTFE) thread sealants, plastic tubing, or flow
controllers with rubber components should be avoided since such materials out-
gas organic compounds which will be concentrated in the trap during the purge
operation. Analyse? of calibration and reagent blanks provide information
about the presence of contaminants. When potential interfering peaks are noted
in blanks, the analyst should change the purge gas source and regenerate the
molecular sieve purge gas filter (Figure 1). Subtracting blank values from
sample results is not permitted. If reporting values not corrected for blanks
result in what the laboratory feels is a false positive for a sample, this
should be fully explained in text accompanying the uncorrected data.
3.2 Interfering contamination may occur when a sample containing low
concentrations of volatile organic compounds is analyzed immediately after a
sample containing high concentrations of volatile organic compounds. The
preventive technique is rinsing of the purging apparatus and sample syringes
with two portions of water between samples. After analysis of a sample
containing high concentrations of volatile organic compounds, one or more
calibration blanks should be analyzed to check for cross contamination. For
samples containing large amounts of water soluble materials, suspended solids,
high boiling compounds or high levels of compounds being determined, it may be
necessary to .wash the purging device with a soap solution, rinse it with
water, and then dry the purging device in an oven at 105°C. In extreme
situations, the whole purge and trap device may require dismantling and
8260 - 3 Revision 1
December 1988
-------
cleaning. Screening of the samples prior to purge and trap GC/MS analysis is
highly recommended to prevent contamination of the system. This is especially
true for soil and waste samples. Screening may be accomplished with an
automated headspace technique or by Method 3820 (Hexadecane Extraction and
Screening of Purgeable Organics).
3.3 Special precautions must be taken to analyze for methylene chloride.
The analytical and sample storage area should be isolated from all atmospheric
sources of methylene chloride, otherwise random background levels will result.
Since methylene chloride will permeate through PTFE tubing, all gas
chromatography carrier gas lines and purge gas plumbing should be constructed
from stainless steel or copper tubing. Laboratory clothing worn by the analyst
should be clean since clothing previously exposed to methylene chloride fumes
during liquid/liquid extraction procedures can contribute to sample
contamination.
3.4 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal
into the sample during shipment and storage. 'A trip blank prepared from water
and carried through the sampling and handling protocol can serve as a check on
such contamination.
4.0 APPARATUS AND MATERIALS
4.1 Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
4.1.1 The recommended purging chamber is designed to accept 5 'mL
(and 25 mL if the lowest detection limit is required) samples with a water
column at least 3 cm deep. The gaseous headspace between the water column
and the trap must have a total volume of less than 15 mL. The purge gas
must pass through the water column as finely divided bubbles with a
diameter of less than 3 mm at the origin. The purge gas must be introduced
no more than 5 mm from the base of the water column. The sample purger,
illustrated in Figure 1, meets these design criteria. Alternate sample
purge devices (i.e. needle spargers), may be utilized, provided equivalent
performance is demonstrated.
4.1.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of absorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is recommended
that 1.0 cm of methyl silicone-coated packing be inserted at the inlet to
extend the life of the trap (see Figure 2). If it is not necessary to
analyze for dichlorodifluoromethane or other fluorocarbons of similar
volatility, the charcoal can be eliminated and the polymer increased to
fill 2/3 of the trap. If only compounds boiling above 35°C are to be
analyzed, both the silica gel and charcoal can be eliminated and the
polymer increased to fill the entire trap. Before initial use, the trap
should be conditioned overnight at 180°C by backflushing with an inert gas
flow of at least 20 mL/min. Vent the trap effluent to the room, not to the
analytical column. Prior to daily use, the trap should be conditioned for
8260 - 4 Revision 1
December 1988
-------
10 minutes at 180'C with backflushing. The trap may be vented to the
analytical column during daily conditioning; however, the column must be
run through the temperature program prior to analysis of samples. Traps
normally last 2-3 months when used daily. Some signs of a deteriorating
trap are: uncharaceristic recoveries of surrogates, especially toluene-ds;
a loss of the response of the internal standards during a 12 hour shift;
and/or a rise in the baseline in the early portion of the scan-.
4.1.3 The desorber should be capable of rapidly heating the trap to
180°C for desorption. The trap bake-out temperature should not exceed
220°C. The desorber design illustrated in Figure 2 meets these criteria.
4.1.4 The purge-and-trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph, as shown in Figures 3 and 4.
4.1.5 Trap Packing Materials
4.1.5.1 2,6-Di phenyl ene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.1.5.2 Methyl silicone packing - OV-1 (3%) on Chromosorb-W,
60/80 mesh or equivalent.
4.1.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.1.5.4 Coconut charcoal - Prepare from Barnebey Cheney, CA-
580-26 lot #M-2649 by crushing through a 26 mesh screen.
4.2 Heater or heated oil bath - Should be capable of maintaining the
purging chamber to within laC over the temperature range of ambient to 100°C.
4.3 Gas chromatography/mass spectrometer/data system
4.3.1 The GC must be capable of temperature programming and should
be equipped with variable constant differential flow controllers so that
the column flow rate will remain constant throughout desorption and
temperature program operation!. For some column configuration, the column
oven must be cooled to < 30°C,; therefore, a subambient oven controller may
be required. The GC is interfaced to the MS with an all glass enrichment
device and an all glass transfer line, but any enrichment device or
transfer line can be used if the performance specifications described in
Step 8.2.4 can be achieved.
4.3.2 Gas chromatographic column 1 - 60 m x 0.75 mm i.d. VOCOL
(Supelco) wide bore capillary column with 1.5 urn film thickness. The flow
rate of helium carrier gas is established at 15 mL/min. The column
temperature is held for 5 minutes at 10"C, then programmed to 160°C at
6°C/min, and held until all expected compounds have eluted. A sample
chromatogram obtained with this column is presented in Figure 5.
4.3.3 Gas chromatographic column 2 - 30 m x 0.53 mm i.d. DB-624
wide-bore (J&W Scientific) column with 3 urn film thickness.
8260 - 5 Revision 1
December 1988
-------
4.3.3.1 Cryogenic cooling - Helium carrier gas flow is
15 mL/min. The column temperature is held for 5 minutes at 10°C, then
programmed to 1608C at 6"C/min. A sample chromatogram obtained with
this column is presented in Figure 6.
4.3.3.2 Non-cryogenic cooling - It is recommended that carrier
gas flow and split and make-up gases be set using performance of
standards as guidance. Set the carrier gas head pressure to 10 psi
and the split to 30 mL/min. Optimize the make-up gas flow for the
separator (approximately 30 mL/min) by injecting BFB and determining
the optimum response when varying the make-up gas. This will require
several injections of BFB. Next, make several injections of the
volatile working standard with all analytes of interst. Adjust the
carrier and split to provide optimum chromatography and response.
This is an especially critical adjustment for the volatile gas
analytes. The head pressure should optimize between 8-12 psi and the
split between 20-60 mL/min. The use of the splitter is important to
minimize the effect of water on analyte response; to allow the use of
a larger volume of helium during trap desorption; and to slow column
flow. The column temperature is held for 2 minutes at 458C, then
programmed to 200°C at 8°C/min, and held for 6 minutes. A sample
chromatogram is presented in Figure 7. A trap preheated to 1508C
prior to trap desorption is required to provide adequate
chromatography of the gas analytes.
4.3.4 Gas chromatographic column 3 - 30 m x 0.32 mm i.d. fused
silica capillary column coated with Durabond DB-5 (J&W Scientific) with a
1 urn film thickness. Helium carrier gas flow is 4 mL/min. The column is
maintained at 10°C for 5 minutes, then programmed at 6°C/min for
10 minutes then 15°C/min for 5 minutes to 1458C. A sample chromatogram
obtained with this column is presented in Figure 8.
4.3.5 Mass spectrometer - Mass spectral data are obtained with
electron impact ionization at a nominal electron energy of 70 eV. The mass
spectrometer must be capable of scanning from 35 to 300 amu every
2 seconds or less and must produce a mass spectrum that meets all criteria
in Table 4 when 50 ng of 4-bromofluorobenzene is introduced into the GC.
To ensure sufficient precision of mass spectral data, the desirable MS
scan rate allows acquisition of at least five spectra while a sample
component elutes from the GC. Injector temperature should be 200-225°C and
transfer line temperature, 250-3008C. This includes, but is not limited
to quadrupole, magnetic, ion trap, time of fight, and mixed analyzer (i.e.
combined analyzers such as magnetic and quadrupole) mass spectrometers.
4.3.6 GC/MS interface - Any GC-to-MS interface that gives acceptable
calibration points at 50 ng or less per injection for each of the analytes
and achieves all acceptable performance criteria (see Table 4) may be
used. GC-to-MS interfaces constructed entirely of glass or of glass-lined
materials are recommended. Glass can be deactivated by silanizing with
dichlorodimethylsilane. This interface is only needed for the wide bore
columns (> 0.53 mm i.d.).
8260 - 6 Revision 1
December 1988
-------
4.3.7 Data system - A computer system that allows the continuous
acquisition and storage on machine-readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have ..software that
allows searching any GC/MS data file for ions of a specified mass and
plotting such ion abundances versus time or scan number. This type of plot
is defined as an Extracted Ion Current Profile (EICP). Software must also
be available that allows integrating the abundances in any EICP between
specified time or scan-number limits. The most recent version of the
NBS/EPA Mass Spectral Library should also be available.
4.4 Capillary precolumn interface when using cryogenic cooling - This
device interfaces the purge and trap concentrator to the capillary gas
chromatograph. The interface condenses the desorbed sample components and
focuses them into a narrow band on an uncoated fused silica capillary
precolumn. When the interface is flash heated, the sample is transferred to
the analytical capillary column.
4.4.1 Under a stream of liquid nitgrogen, the temperature of the
fused silica in the interface is maintained at -1508C during the
cryofocussing step. After the desorption period, the interface must be
capable of rapid heating to 250"C in 15 seconds or less to complete the
transfer of analytes.
4.5 Microsyringes - 10, 25, 100, 250, 500, and 1,000-uL.
4.6 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.7 Syringes - 5, 10, or 25-mL, gas-tight with shutoff valve.
4.8 Balance - Analytical, capable of accurately weighing 0.0001 g, and a
top-loading balance capable of weighing 0.1 g.
4.9 Glass scintillation vials - 20-mL, with Teflon, lined screw-caps or
glass culture tubes with Teflon lined screw-caps.
4.10 Vials - 2-mL, for GC autosampler.
4.11 Disposable pipets - Pasteur.
5.0 REAGENTS
5.1 Methanol, CHsOH. Pesticide quality or equivalent, demonstrated to be
free of analytes. Store apart from other solvents.
5.2 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of compounds
of interest.
CAUTION: Glycolethers are suspected carcinogens. All solvent handling
should be done in a hood while using proper protective equipment
to minimize exposure to liquid and vapor.
8260 - 7 Revision 1
December 1988
-------
5.2.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
240-5 or equivalent), CsHisOs. Purify by treatment at reduced pressure in
a rotary evaporator. The tetraglyme should have a peroxide content of less
than 5 ppm as indicated by EM Quant Test Strips (available from Scientific
Products Co., Catalog No. P1126-8 or equivalent).
Peroxides may be removed by passing the tetraglyme through a column of
activated alumina. The tetraglyme is placed in a round bottom flask
equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed in a water bath at 90-100°C and a vacuum
is maintained at < 10 mm Hg for at least two hours using a two-stage
mechanical pump. The vacuum system is equipped with an all-glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 0.1 mg/mL of 2,6-di-tert-butyl-4-methyl-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw-cap bottle in an area that is not contaminated by solvent vapors.
5.2.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, a water/tetraglyme blank must be
analyzed.
5.3 Polyethylene glycol, reagent grade. Free of interferences at the
detection limit of the analytes.
5.4 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall conform
to the specifications of the Committee on'Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.5 Hydrochloric acid (1:1), HCL. Carefully add a measured volume of
concentrated HCL to an equal volume of water.
5.6 ASTM Type II Water (ASTM Dll93-77 (1983)). All references to water in
the method refer to ASTM Type II unless otherwise specified. Must be free of
interferents at the method detection limit (MDL) of the analytes of interest.
ASTM Type II water is further purified by any of the following techniques:
5.6.1 Water may be generated by passing tap water through a carbon
filter bed containing about 450 g of activated carbon (Calgon Corp.,
Filtrasorb-300 or equivalent).
5.6.2 A water purification system (Millipore Milli-Q Plus with the
Organex-Q cartridge or equivalent) may be used to generate water.
5.6.3 Water may also be prepared by boiling water for 15 minutes.
Subsequently, while maintaining the temperature at 90°C, bubble a
contaminant-free inert gas through the water for 1 hour. While it is still
hot, transfer the water to a narrow-mouth screw-cap bottle and seal with a
Teflon lined septum and cap.
8260 - 8 Revision 1
December 1988
-------
5.7 Stock solutions - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standard
solutions in methanol, using assayed liquids or gases, as appropriate.
. 5.7.1 Place about 9.8 ml of methanol in a 10-mL tared ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
5.7.2 Add the assayed reference material, as described below.
5.7.2.1 Liquids - Using a 100-uL syringe, immediately add two
or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5.7.2.2 Gasses - To prepare standards for any compounds that
boil below 308C (e.g. bromomethane, chloroethane, chloromethane, or
vinyl chloride), fill a 5-mL valved gas-tight syringe with the
reference standard to the 5.0-mL mark. Lower the needle to 5 mm above
the methanol meniscus. Slowly introduce the reference standard above
the surface of the liquid. The heavy gas will rapidly dissolve in the
methanol. Standards may also be prepared by using a lecture bottle
equipped with a Hamilton Lecture Bottle Septum (#86600). Attach
Teflon tubing to the side arm relief valve and direct a gentle stream
of gas into the methanol meniscus.
5.7.3 Reweigh, dilute to Volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in micrograms per
micro!iter (ug/uL) from the net gain in weight. When compound purity is
assayed to be 90% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.7.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light. I
5.7.5 Prepare fresh standards for gases every two months or sooner
if comparison with check standards indicates a problem. Reactive compounds
such as 2-chloroethylvinyl ether and styrene may need to be prepared more
frequently. All other standards must be replaced after six months, or
sooner if comparison with check standards indicates a problem. Both gas
and liquid standards must be monitored closely by comparison to the
initial calibration curve and by comparison to QC reference samples. It
may be necessary to replace the standards more frequently if either check
exceeds a 25% difference.
5.8 Secondary dilution standards - Using stock standard solutions,.
prepare in methanol, secondary dilution standards containing the compounds of
interest, either singly or mixed together. Secondary dilution standards must
be stored with minimal headspace and should be checked frequently for signs of
8260 - 9 Revision 1
December 1988
-------
degradation or evaporation, especially just prior to preparing calibration
standards from them. Store in a vial with no headspace for one week only.
5.9 Surrogate standards - The surrogates recommended are toluene-ds,
4-bromofluorobenzene, and dibromofluoromethane. Other compounds may be used as
surrogates, depending upon the analysis requirements. A stock surrogate
solution in methanol should be prepared as described in Step 5.7, and a
surrogate standard spiking solution should be prepared from the stock at a
concentration of 50-250 ug/10 ml in methanol. Each sample undergoing GC/MS
analysis must be spiked with 10 uL of the surrogate spiking solution prior to
analysis.
5.10 Internal standards - The recommended internal standards are
chlorobenzene-ds, 1, 4-dif1uorobenzene, 1, 4-dichlorobenzene-d4, and
pentafluorobenzene. Other compounds may be used as internal standards as long
as they have^retention times similar to the compounds being detected by GC/MS.
Prepare internal standard stock and secondary dilution standards in methanol
using the procedures described in Steps 5.7 and 5.8. It is recommended that
the secondary, dilution standard should be prepared at a concentration of
25 ug/mL of each internal standard compound. Addition of 10 uL of this
standard to 5.0 ml of sample or calibration standard would be the equivalent
of 50 ug/L.
5.11 4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng/uL of BFB in methanol should be prepared.
5.12 Calibration standards - Calibration standards at a minimum of five
concentration levels should be prepared from the secondary dilution of stock
standards (see Steps 5.7 and 5.8). Prepare these solutions in water. One of
the concentration levels should be at a concentration near, but above, the
method detection limit. The remaining concentration levels should correspond
to the expected range of concentrations found in real samples but should not
exceed the working range of the GC/MS system. Each standard should contain
each analyte for detection by this method (e.g. some or all of the compounds
listed in Table 1 may be included). Calibration standards must be prepared
daily.
5.13 Matrix spiking standards - Matrix spiking standards should be
prepared from volatile organic compounds which will be representative of the
compounds being investigated. At a minimum, the matrix spike should include
1,1-dichloroethene, trichloroethene, chlorobenzene, toluene, and benzene. It
is desirable to perform a matrix spike using compounds found in samples. Some
permits may require spiking 'specific compounds of interest, especially if they
are polar and would not be represented by the above listed compounds. The
standard should be prepared in methanol, with each compound present at a
concentration of 250 ug/10.0 ml.
5.14 Great care must be taken to maintain the integrity of all standard
solutions. It is recommended all standards in methanol be stored at -10°C to
-20°C in amber bottles with Teflon lined screw-caps.
8260 - 10 . Revision 1
December 1988
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Step
4.1.
7.0 PROCEDURE
7.1 Direct injection - In very limited appliations (e.g. aqueous process
wastes) direct injection of the sample into the GC/MS system with a 10 uL
syringe may be appropriate. One such application is for verification of the
alcohol content of an aqueous sample prior to determining if the sample is
ignitable (Methods 1010 or 1020). In this case, it is suggested that direct
injection be used. The detection limit is very high (approximately
10,000 ug/L); therefore, it is only permitted when concentrations in excess of
10,000 ug/L are expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection using the same solvent (e.g.
water) for standards as the sample matrix (bypassing the purge-and-trap
device).
7.2 Initial calibration for purge-and-trap procedure
t
7.2.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 4 for a 50 ng injection or purging of 4-bromofluorobenzene (2 uL
injection of the BFB standard). Analyses must not begin until these
criteria are met.
7.2.2 Assemble a purge-and-trap device that meets the specification
in Step 4.1. Condition the trap overnight at 180°C in the purge mode with
an inert gas flow of at least 20 mL/min. Prior to use, condition the trap
daily for 10 minutes while backflushing at 180'C with the column at 220°C.
7.2.3 Connect the purge-and-trap device to a gas chromatograph.
7.2.4 A set of at least five calibration standards containing the
method analytes is needed. One calibration standard should contain each
analyte at a concentration approaching but greater than the method
detection limit (Table 1) for that compound; the other calibration
standards should contain analytes at concentrations that define the range
of the method. The purging efficiency for 5 mL of water is greater than
for 25 mL, therefore, develop the standard curve with whichever volume of
sample that will be analyzed. To prepare a calibration standard, add an
appropriate volume of a secondary dilution standard solution to an aliquot
of water in a volumetric flask. Use a microsyringe and rapidly inject the
alcoholic standard into the expanded area of the filled volumetric flask.
Remove the needle as quickly as possible after injection. Mix by inverting
the flask three times only. Discard the contents contained in the neck of
the flask. Aqueous standards are not stable and should be prepared daily.
Transfer 5.0 mL (or 25 mL if lower detection limits are required) of each
standard to a gas tight syringe along with 10 uL of internal standard.
Then transfer the contents to a purging device.
7.2.5 Carry out the purge-and-trap analysis procedure as described
in Step 7.4.1.
8260 - 11 Revision 1
December 1988
-------
7.2.6 Tabulate the area response of the characteristic ions (see
Table 5) against concentration for each compound and each internal
standard. Calculate response factors (RF) for each compound relative to
one of the internal standards. The internal standard selected for the
calculation of the RF for a compound should be the internal standard that
has a retention time closest to the compound being measured (Step 7.5.2).
The RF is calculated as follows:
RF = (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
Ais = Area of the characteristic ion for the specific internal
standard.
Cis = Concentration of the specific internal standard.
Cx = Concentration of the compound being measured.
7.2.7 The average RF must be calculated for each compound and
recorded on Form VI (see Chapter One). A system performance check should
be made before this calibration curve is used. Five compounds (the System
Performance Check Compounds, or SPCCs) are checked for a minimum average
response factor. These compounds are chloromethane, 1,1-dichloroethane,
bromoform, 1,1,2,2-tetrachlor.oethane, and chlorobenzene. The minimum
acceptable average RF for these compounds should be 0.300 (0.250 for
bromoform). These compounds typically have RFs of 0.4-0.6 and are used to
check compound instability and check for degradation caused by
contaminated lines or active sites in the system. Examples of these
occurences are:
7.2.7.1 Chloromethane - This compound is the most likely
compound to be lost if the purge flow is too fast.
7.2.7.2 Bromoform - This compound is one of the compounds most
likely to be purged very poorly if the purge flow is too slow. Cold
spots and/or active sites in the transfer lines may adversely affect
response. Response of the quantitation ion (m/z 173) is directly
affected by the tuning of BFB at ions m/z 174/176. Increasing the m/z
174/176 ratio relative to m/z 95 may improve bromoform response.
7.2.7.3 Tetrachloroethane and 1,1-dichloroethane - These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2.8 Using the RFs from the initial calibration, calculate the
percent relative standard deviation (%RSD) for Calibration Check Compounds
(CCCs). Record the %RSDs for all compounds on Form VI (see Chapter One).
The percent RSD is calculated as follows:
8260 - 12 Revision 1
December 1988
-------
%RSD = SD 13 x 100
where:
RSD = Relative standard deviation.
x = Mean of 5 initial RFs for a compound.
SD = Standard deviation of average RFs for a compound.
N - 2
SD = (x - x)*
1-1 -R-T-T-
•
The %RSD for each individual CCC must be less than 30 percent. This criterion
must be met for the individual calibration to be valid. The CCCs are:
1,1-Dichloroethene,
Chloroform,
1,2-Dichloropropane,
Toluene,
Ethyl benzene, and
Vinyl chloride.
If the CCCs are not required analytes by the permit, then all required
analytes must meet the 30% RSD criterion.
7.3 Daily GC/MS calibration
7.3.1 Prior to the analysis of samples, inject or purge 50-ng of the
4-bromofluorobenzene standard. The resultant mass spectra for the BFB must
meet all 'of the criteria given in Table 4 before sample analysis begins.
These criteria must be demonstrated each 12-hour shift.
7.3.2 The initial calibration curve (Step 7.2) for each compound of
interest must be checked and verified once every 12 hours of analysis
time. This is accomplished by analyzing a calibration standard that is at
a concentration near the midpoint concentration for the working range of
the GC/MS by checking the SPCC (Step 7.3.3) and CCC (Step 7.3.4).
7.3.3 System Performance Check Compounds (SPCCs) - A system
performance check must be made each 12 hours. If the SPCC criteria are
met, a comparison of response factors is made for all compounds. This is
the same check that is applied during the initial calibration. If the
minimum response factors are not met, the system must be evaluated, and
corrective action must be taken before sample analysis begins. The minimum
response factor for volatile SPCCs is 0.300 (0.250 for Bromoform). Some
possible problems are standard mixture degration, injection port inlet
contamination, contamination at the front end of the analytical column,
and active sites in the column or chromatographic system.
8260 - 13 Revision 1
December 1988
-------
7.3.4 Calibration Check Compounds (CCCs) - After the system
performance check is met, CCCs listed in Step 7.2.8 are used to check the
validity of the initial calibration. Calculate the percent difference
using the following equation:
% Difference = -— ----- - x 100
- RF
RF
,
where:
RFj = Average response factor from initial calibration.
RFC = Response factor from current verification check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent difference
for each CCC is less than 25%, the initial calibration is assumed to be
valid. If the criterion is not met (> 25% difference), for any one CCC,
corrective action must be taken. Problems similar to those listed under
SPCCs could affect this criterion. If no source of the problem can be
determined after corrective action has been taken, a new five-point
calibration must be generated. This criterion must be met before
quantitative sample analysis begins. If the CCCs are not required analytes
by the permit, then all required analytes must meet the 25% difference
criterion.
7.3.5 The internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last check calibration (12 hours), the
chromatograhic system must be inspected for malfunctions and corections
must be made, as required. If the EICP area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate. When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning are necessary.
7.4 GC/MS analysis
7.4.1 Water samples
7.4.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be used are the headspace
sampler (Method 3810) using a gas chromatograph (GC) equipped with a
photo ionization detector (PID) in series with an electrolytic
conductivity detector (BCD), and extraction of the sample with
8260 - 14 Revision 1
December 1988
-------
hexadecane and analysis of the extract on a GC with a FID and/or an
ECD (Method 3820).
7.4.1.2 All samples and standard solutions must be allowed to
warm to ambient temperature before analyses.
7.4.1.3 Set up the GC/MS system as outlined in Step 4.3.
7.4.1.4 BFB tuning criteria and daily GC/MS calibration
criteria must be met (Step 7.3) before analyzing samples..
7.4.1.5 Adjust the purge gas (helium) flow rate to 25-40 mL/min
on the purge-and-trap device. Optimize the flow rate to provide the
best response for chloromethane and bromoform, if these compounds are
analytes. Excessive flow rate reduces chloromethane response, whereas
insufficient flow reduces bromoform response (see Step 7.2.7)-.
7.4.1.6 Remove the plunger from a 5-mL syringe and attach a
closed syringe valve. If lower detection limits are required, use a
25-mL syringe. Open the sample or standard bottle, which has been
allowed to come to ambient temperature, and carefully pour the sample
into the syringe "barrel to just short of overflowing. Replace the
syringe plunger and compress the sample. Open the syringe valve and
vent any residual air while adjusting the sample volume to 5.0 mL.
This process of taking an aliquot destroys the validity of the liquid
sample for future analysis;'therefore, if there is only one VGA vial,
the analyst should fill a second syringe at this time to protect
against possible loss of sample integrity. This second sample is
maintained only until such time when the analyst has determined that
the first sample has been analyzed properly. Filling one 20-mL
syringe would allow the use of only one syringe. If a second analysis
is needed from a syringe, it must be analyzed within 24 hours. Care
must be taken to prevent air from leaking into the syringe.
7.4.1.7 The following procedure is appropriate for diluting
purgeable samples. All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.
7.4.1.7.1 Dilutions may be made in volumetric flasks (10
to 100-mL). Select the volumetric flask that will allow for the
necessary dilution. Intermediate dilutions may be necessary for
extremely large dilutions.
7.4.1.7.2 Calculate the approximate volume of water to be
added to the volumetric flask selected and add slightly less
than this quantity of water to the flask.
7.4.1.7.3 Inject the proper aliquot of samples from the
syringe prepared in Step 7.4.1.6 into the flask. Aliquots of
less than 1 ml are not recommended. Dilute the sample to the
mark with water. Cap the flask, invert, and shake three times.
Repeat above procedure for additional dilutions.
8260 - 15 Revision 1
December 1988
-------
7.4.1.7.4 Fill a 5-mL syringe with the diluted sample as
in Step 7.4.1.6.
7.4.1.8. Compositing samples prior to GC/MS analysis
7.4.1.8.1 Add 5 ml or equal larger amounts of each sample
(up to-5 samples are allowed) to a 25-mL glass syringe. Special
precautions must be made to maintain zero headspace in the
syringe.
7.4.1.8.2 The samples must be cooled at 4°C during this
step to minimize volatilization losses.
7.4.1.8.3 Mix well and draw out a 5 ml aliquot for
analysis.
7.4.-1.8.4 Follow sample introduction, purging, and
desorption steps described in the method.
7.4.1.8.5 If less than five samples are used for
compositing, a proportionately smaller syringe may be used
unless a 25 ml sample is to be purged.
7.4.1.9 Add 10.0 uL of surrogate spiking solution (Step 5.9)
and 10 uL of internal standard spiking solution (Step 5.10) through
the valve bore of the syringe; then close the valve. The surrogate
and internal standards may be mixed and added as a single spiking
solution. The addition of 10 uL of the surrogate spiking solution to
5 ml of sample is equivalent to a concentration of 50 ug/L of each
surrogate standard.
7.4.1.10 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.4.1.11 Close both valves and purge the sample for 11.0 ± 0.1
minutes at ambient temperature. Be sure the trap is cooler than 25°C.
7.4.1.12 Sample desorption - The mode of sample desorption is
determined by the type of capillary column employed for the analysis.
When using a wide bore capillary column, follow the desorption
conditions of Step 7.4.1.13. The conditions for using narrow bore
columns are described in Step 7.4.1.14.
7.4.1.13 Sample desorption for wide bore capillary column. Under
most conditions, this type of column must be interfaced to the MS
through an all glass jet separator.
7.4.1.13.1 After the 11 minute purge, attach the trap to
the chromatograph, adjust the purge and trap system to the
desorb mode (Figure 4) and initiate the temperature program
sequence of the gas chromatograph and start data acquisition.
Introduce the trapped materials to the GC column by rapidly
8260 - 16 Revision 1
December 1988
-------
heating the trap to 180'C while backflushing the trap with an
inert gas at 15 mL/min for 4 minutes. If the non-cryogenic
cooling technique is followed, the trap must be preheated to
150"C just prior to trap desorption at 180°C. While the purged
analytes are being introduced into the gas chromatograph, empty
the purging device using the sample syringe and wash the chamber
with two 5 or 25 ml portions of water depending on the size of
the purge device. After the purging device has been emptied,
leave the syringe valve open to allow the purge gas to vent
through the sample introduction needle.
7.4.1.13.2 Hold the column temperature at 10"C for
5 minutes, then program at 6"C/min to 160"C and hold until all
analytes elute.
7.4.1.13.3 After desorbing the sample for 4 minutes,
condition the trap by returning the purge-and-trap system to the
purge mode. Wait 15 seconds, then close the syringe valve on the
purging device to begin gas flow through the trap. Maintain the
trap temperature at 180°C. After approximately 7'minutes, turn
off the trap heater and open the syringe valve to stop the gas
flow through the trap. When the trap is cool, the next sample
can be analyzed.
7.4.1.14 Sample desorption for narrow bore capillary column.
Under normal operating conditions, most narrow bore capillary columns
can be interfaced directly to the MS without a jet separator.
7.4.1.14.1 After the 11 minute purge, attach the trap to
the cryogenically cooled interface at -150'C and adjust the
purge-and-trap system to the desorb mode (Figure 4). Introduce
the trapped materials to the interface by rapidly heating the
trap to 180'C while backflushing the trap with an inert gas at
4 mL/min for 5 minutes. While the extracted sample is being
introduced into the interface, empty the purging device using
the sample syringe and rinse the chamber with two 5 or 25 ml
portions of water depending on the size of the purging device.
After the purging device has been emptied, leave the syringe
valve open to allow the purge gas to vent through the sample
introduction needle. After desorbing for 5 minutes, flash heat
the interface to 250'C and quickly introduce the sample on the
chromatographic column. Start the temperature program sequence,
and initiate data acquisition.
7.4.1.14.2 Hold the column temperature at 10°C for
5 minutes, then program at 6"C/min to 70"C and then at 15°C/min
to 145"C. After desorbing the sample for 5 minutes, recondition
the trap by returning the purge-and-trap system to the purge
mode. Wait 15 seconds, then close the syringe valve on the
purging device to begin gas flow through the trap. Maintain the
trap temperature at 180°C. After approximately 15 minutes, turn
off the trap heater and open the syringe valve to stop the gas
8260 - 17 Revision 1
December 1988
-------
flow through the trap. When the trap is cool, the next sample
can be analyzed.
7.4.1.15 If the initial analysis of the sample or a dilution of
the sample has a concentration of analytes that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. Secondary ion quantitation is allowed only when there are
sample interferences with the primary ion. When a sample is analyzed
that has saturated ions from a compound, this analysis must be
followed by a blank water analysis. If the blank analysis is not free
of interferences, the system must be decontaminated. Sample analysis
may not resume until a blank can be analyzed that is free of
interferences.
7.4.1.16 For matrix spike analysis, add 10 uL of the matrix
spike solution (Step 5.13) to the 5 mL of sample purged. Disregarding
any dilutions, this is equivalent to a concentration of 50 ug/L of
each matrix spike standard.
7.4.1.17 All dilutions should keep the response of the major
constituents (previously saturated peaks) in the upper half of the
linear range of the curve. Proceed to Steps 7.5.1 and 7.5.2 for
qualitative and quantitative analysis.
7.4.2 Water-miscible liquids
7.4.2.1 Water-miscible liquids are analyzed as water samples
after first diluting them at least 50-fold with water.
7.4.2.2 Initial and serial dilutions can be prepared by
pipeting 2 mL of the sample to a 100-mL volumetric flask and diluting
to volume with water. Transfer immediately to a 5-mL gas-tight
syringe.
7.4.2.3 Alternatively, prepare dilutions directly in a 5-mL
syringe filled with water by adding at least 20 uL, but not more than
100-uL of liquid sample. The sample is ready for addition of internal
and surrogate standards.
7.4.3 Sediment/soil and waste samples - It is highly recommended
that all samples of this type be screened prior to the purge-and-trap
GC/MS analysis. The headspace method (Method 3810) or the hexadecane
extraction and screening method (Method 3820) may used for this purpose.
These samples may contain percent quantities of purgeable organics that
will contaminate the purge-and-trap system, and require extensive cleanup
and instrument downtime. Use the screening data to determine whether to
use the low-Jevel method (0.005-1 mg/kg) or the high-level method
(> 1 mg/kg).
7.4.3.1 Low-level method - This is designed for samples
containing individual purgeable compounds of < 1 mg/kg. It is limited
to sediment/soil samples and waste that is of a similar consistency
(granular and porous). The low-level method is based on purging a
8260 - 18 Revision 1
December 1988
-------
heated sediment/soil sample mixed with water containing the surrogate
and internal standards. Analyze all blanks and standards under the
same conditions as the samples. See Figure 9 for an illustration of a
low soils impinger.
7.4.3.1.1 Use a 5 g sample if the expected concentration
is < 0.1 mg/kg or a 1 g sample for expected concentrations
between 0.1 and 1 mg/kg.
7.4.3.1.2 The GC/MS system should be set up as in Steps
7.4.1.3-7.4.1.4. This should be done prior to the preparation of
the sample to avoid loss of volatiles from standards and
samples. A heated purge calibration curve must be prepared and
used for the quantitation of all samples analyzed with the low-
level methoxl. Follow the initial and daily calibration
instructions, except for the addition of a 40°C purge
temperature.
7.4.3.1.3 Remove the plunger from a 5-mL Luerlock type
syringe equipped with a syringe valve and fill until overflowing
with water. Replace the plunger and compress the water to vent
trapped air. Adjust the volume to 5.0 'ml. Add 10 uL each of
surrogate spiking solution (Step 5.9) and internal standard
solution (Step 5.10) to the syringe through the valve (surrogate
spiking solution and internal standard solution may be mixed
together). The addition of 10 uL of the surrogate spiking.
solution to 5 g of sediment/soil is equivalent to 50 ug/kg of
each surrogate standard.
7.4.3.1.4 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard any
supernatant liquids. Mix the contents of the sample container
with a narrow metal spatula. Weigh the amount determined in Step
7.4.3.1.1 into a tared purge device. Note and record the actual
weight to the nearest 0.1 g.
7.4.3.1.5 Determine the percent moisture of the
soil/sediment sample. This includes waste samples that are
amenable to moisture determination. Other wastes should be
reported on a wet-weight basis. Immediately after weighing the
sample, weigh (to 0.1 g) 5-10 g of additional sediment/soil into
a tared crucible. Dry the contents of the crucibles overnight at
105°C. Allow to cool in a desiccator and reweigh the dried
contents. Concentrations of individual analytes will be reported
relative to the dry weight of sediment.
grams of sample - grams of dry sample
% moisture = x 100
grams of sample
7.4.3.1.6 Add the spiked water to the purging device,
which contains the weighed amount of sample, and connect the
device to the purge-and-trap system.
8260 - 19 Revision 1
December 1988
-------
NOTE: Prior to the attachment of the purge device, the
procedures in Steps 7.4.3.1.4 and 7.4.3.1.6 must be
performed rapidly and without interruption to avoid loss
of volatile brganics. These steps must be performed in a
laboratory w°ee—&f solvent vapors. There must be no
solvents brought into the lab other than those used for
extracting samples for volatiles or dissolving volatile
standards (i.e. methanol , etc.). It is highly
recommended that GC and GC/MS analysis for pesticides and
semivolatiles be performed in a different room to avoid
high background levels of methylene chloride and hexane.
7.4.3.1.7 Heat the sample to 40°C ± 1°C and purge the
sample for 11.0 + 0.1 minutes. Be sure the trap is cooler than
25°C.
7.4.3.1.8 Proceed with the analysis as outlined in Steps
7.4.1.12-7.4.1.17. Use 5 ml of the same water as in the blank.
If saturated peaks occurred or would occur if a 1 g sample were
analyzed, the medium-level method must be followed.
7.4.3.1.9 For low-level sediment/soils, add 10 uL of the
matrix spike solution (Step 5.7) to the 5 ml of water (Step
7.4.3.1.3). The concentration for a 5 g sample would be
equivalent to 50 ug/kg of each matrix spike standard.
7.4.3.2 High-level method - The method is based on extracting
the sediment/soil with methanol. A waste sample is either extracted
or diluted, depending on its solubility in methanol. Wastes (i.e.
petroleum and coke wastes) that are insoluble in methanol are diluted
with tetraglyme or possibly polyethylene glycol (PEG). An aliquot of
the extract is added to water containing surrogate and internal
standards. This is purged at ambient temperature. All samples with an
expected concentration of > 1.0 mg/kg should be analyzed by this
method.
7.4.3.2.1 | The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard any
supernatant liquids. Mix the contents of the sample container
with a narrow metal spatula. For sediment/soil and solid wastes
that are insoluble in methanol weigh 4 g (wet weight) of sample
into a tared 20-mL vial. Use a top-loading balance. Note and
record the actual weight to 0.1 gram and determine the percent
moisture of the sample using the procedure in Step 7.4.3.1.5.
For waste that is soluble in methanol, tetraglyme, or PEG, weigh
1 g (wet weight) into a tared scintillation vial or culture tube
or a 10-mL volumetric flask. (If a vial or tube is used, it must
be calibrated prior to use. Pipet 10.0 ml of solvent into the
vial and mark the bottom of the meniscus. Discard this solvent.)
7.4.3.2.2 Quickly add 9.0 ml of appropriate solvent. Cap
and shake for 2 minutes.
8260 - 20 Revision 1
December 1988
-------
on
Vti
NOTE: Steps 7.4.3.2.1 and 7.4.3.2.2 must be performed rapidly
and without interruption to avoid loss of volatile
jrganics. These steps must be performed in a laboratory
from solvent vapors. There must be no solvents
brought into the lab other than those used for
extracting samples for volatiles or dissolving volatile
standards (i.e. methanol, etc.). It is highly
recommended that GC and GC/MS analysis for pesticides
and semivolatiles be performed in a different room to
avoid high background levels of methylene chloride and
hexane.
7.4.3.2.3 Pipet approximately 1 ml of the extract to a GC
vial for storage, using a disposable pipet. The remainder may be
disposed. Transfer approximately 1 ml of appropriate solvent to
a separate GC vial for use as the method blank for each set of
samples. These extracts may be stored at 4°C in the dark, prior
to analysis. The addition of a 100 uL aliquot of each of these
extracts in Step 7.4.3.2.6 will give a concentration equivalent
to 6,200 ug/kg of each surrogate standard.
7.4.3.2.4 The GC/MS system should be set up as in Steps
7.4.1.3-7.4.1.4. This should be done prior to the addition of
the solvent extract to water.
7.4.3.2.5 The following information can be used to
determine the volume of solvent extract to add to the 5 ml of
water for analysis. If a screening procedure was followed
(Method 3810 or 3820), use the estimated concentration to
determine the appropriate volume. Otherwise, estimate the
concentration range of the sample from the low-level analysis to
determine the appropriate volume. If the sample was submitted as
a medium-level sample, start with 100 uL. All dilutions must
keep the response of the major constituents (previously
saturated peaks) in the upper half of the linear range of the
curve.
QUANTITY OF EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-LEVEL SAMPLES
ApproximateVolume of
Concentration Range Extract3
500- 10,000 ug/kg 100 uL
1,000- 20,000 ug/kg 50 uL
5,000-100,000 ug/kg 10 uL
25,000-500,000 ug/kg 100 uL of 1/50 dilution^
Calculate appropriate dilution factor for concentrations exceeding this table.
8260 - 21 Revision 1
December 1988
-------
a The volume of solvent added to 5 mi of water being purged should be kept
constant. Therefore, add to the 5-mL syringe whatever volume of solvent is
necessary to maintain a volume of 100 uL added to the syringe.
b Dilute an aliquot of the solvent extract and then take 100 uL for analysis.
7.4.3.2.6 Remove the plunger from a 5.0-mL Luerlock type
syringe equipped with a syringe valve and fill until overflowing
with water. Replace the plunger and compress the water to vent
trapped air. Adjust the volume to 4.9 mL. Pull the plunger back
to 5.0 mL to allow volume for the addition of the sample extract
and of standards. Add 10 uL of internal standard solution; then
add 10 uL of the surrogate spiking solution. Also add the volume
of solvent extract determined in Step 7.4.3.2.5 and a volume of
extraction or dissolution solvent to total 100 uL (excluding
solvent in standards).
7.4.3.2.7 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valve and
inject the water/solvent sample into the purging chamber.
7.4.3.2.8 Proceed with the analysis as outlined in Steps
7.4.1.12-7.4.1.17. Analyze all blanks on the same instrument as
that used for the samples. The standards and blanks should also
contain 100 uL of the dilution solvent to simulate the sample
conditions.
7.4.3.2.9 For a matrix spike in the medium-level
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution (Step 5.9), and 1.0 ml of matrix spike
solution (Step 5.13) as in Step 7.4.3.2.2. This results in a
6,200 ug/kg concentration of each matrix spike standard when
added to a 4 g sample. Add a 100 uL aliquot of this extract to
5 ml of water for purging (as per Step 7.4.3-2.6).
7.5 Data interpretation
7.5.1 Qualitative analysis
7.5.1.1 The qualitative identification of compounds determined
by this method is based on retention time, and on comparison of the
sample mass spectrum after background correction with characteristic
ions in a reference mass spectrum. The reference mass spectrum must
be generated by the laboratory using the analytical conditions of
this method. The characteristic ions from the reference mass
spectrum are defined to be the three ions of greatest relative
intensity, or any ions over 30% relative intensity Jf less than three
such ions occur in the reference spectrum. Compounds should be
identified as present when the criteria below-are met.
7.5.1.1.1 The intensities of the characteristic ions of a
compound maximize in the same or within one scan of each other.
Selection of a peak by a data system target compound search
8260 - 22 Revision 1
December 1988
-------
routine where the search is based on the presence of a
chromatographic peak containing ions specific for the target
compound at a compound-specific retention time will be accepted
as meeting this criterion.
7.5.1.1.2 The RRT of the sample component is within 0.06
RRT units of the RRT of the standard component.
7.5.1.1.3 The relative intensities of the characteristic
ions agree within 30% of the relative intensities of these ions
in the reference spectrum. (Example: For an ion.with an
abundance of 50% in the reference spectrum, the corresponding
abundance in a sample spectrum can range between 20% and 80%.)
7.5.1.1.4 Structural isomers that produce. very similar
mass spectra should be identified as individual isomers if- they
have sufficiently different GC retention times. Sufficient GC
resolution is achieved if the height of the valley between.two
isomer peaks is less than 25% • of the sum of the two peak
heights. Otherwise, structural isomers are identified as
isomeric pairs.
7.5.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce mass
spectra containing ions contributed by more than one analyte.
When gas chromatographic peaks obviously represent more than one
sample component (i.e. a broadened peak with shoulder(s) or a
valley between two or more maxima), appropriate selection of
analyte spectra and background spectra is important.
Examination of extracted ion current profiles of appropriate
ions can aid in the selection of spectra, and in qualitative
identification of compounds. When analytes coelute (i.e. only
one chromatographic peak is apparent), the identification
criteria can be met, but each analyte spectrum will contain
extraneous ions contributed by the coeluting compound.
7.5.1.2 For samples containing components not associated with
the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should be
present in the sample spectrum.
8260 - 23 Revision 1
December 1988
-------
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.5.2 Quantitative analysis
7.5.2.1 When a compound has been identified, the quantification
of that compound will be based on the integrated abundance from the
EICP of the primary characteristic ion. Quantification will take
place using the internal standard technique. The internal standard
used shall be the one nearest the retention time of that of a given
analyte (e.g. see Table 6).
7.5.2.2 Calculate the concentration of each identified
analyte in the sample as follows:
Water and Water-Miscible Waste
(AX)(IS)
concentration (ug/L) = TT—T75pT7n-y
where:
Ax = Area of characteristic ion for compound being
measured.
Is = Amount of internal standard injected (ng).
ATS = Area of characteristic ion for the internal standard-
RF = Response factor for compound being measured (Step 7.2.6).
V0 = Volume of water purged (ml), taking into consideration
any dilutions made.
Sediment/Soil, Sludge, and Waste
8260 - 24 Revision 1
December 1988
-------
High-level:
(AJ(Is)(Vt)
concentration (ug/kg) = (AT'TTRFTIVTyiiTJ
Low-level:
(AX)(IS)
concentration (ug/kg) = (AT~y(RF)(W"T
where:
AX> Is> AiS, RF = Same as in water and water-miscble waste
above.
v"t = Volume of total extract (uL) (use 10,000 uL or a factor
of this when dilutions are made).
Vj = Volume of extract added (uL) for purging.
Ws = Weight of sample extracted or purged (g). The wet weight
or dry weight may be used, depending upon the specific
applications of the data.
7.5.2.3 Sediment/soil samples are generally reported on a dry
weight basis, while sludges and wastes are reported on a wet weight
basis. The % moisture of the sample (as calculated in Step 7.4.3.1.5)
should be reported along with the data in either instance.
7.5.2.4 Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made. The formulas
given above should be used with the following modifications: The
areas Ax and Ais should be from the total ion chromatograms, and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported indicating (1) that the value is an
estimate and (2) which internal standard was used to determine
concentration. Use the nearest internal standard free of
interferences.
7.5.2.5 Report results without correction for recovery data.
When duplicates and spiked samples are analyzed, report all data
obtained with the sample results.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an ongoing
analysis of spiked samples to evaluate and document quality data. The
laboratory must maintain records to document the quality of the data
generated. Ongoing data quality checks are compared with established
performance criteria to determine if the results of analyses meet the
8260 - 25 Revision 1
December 1988
-------
performance characteristics of the method. When results of sample spikes
indicate atypical method performance, a quality control check standard must be
analyzed to confirm that the measurements were performed in an in-control mode
of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a calibration blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a set
of samples is extracted or there is a change in reagents, a reagent blank
should be processed as a safeguard against chronic laboratory contamination.
The blanks should be carried through all stages of sample preparation and
measurement.
8.3 The experience of the analyst performing GC/MS analyses is invaluable
to the success of the methods. Each day that analysis is performed, the daily
calibration standard should be evaluated to determine if the chromatographic
system is operating properly. Questions that should be asked are: Do the
peaks look normal? Is the response obtained comparable to the response from
previous calibrations? Careful examination of the standard chromatogram can
indicate whether the column is still useable, the injector is leaking, the
injector septtum needs replacing, etc. If any changes are made to the system
(e.g. column changed), recalibration of the system must take place.
8.4 Required instrument QC
8.4.1 The GC/MS system must be tuned to meet the BFB specifications
in Step 7.2.1.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in Step 7.2.
8.4.3 The GC/MS system must meet the SPCC criteria specified in
Step 7.3.3 and the CCC criteria in Step 7.3.4, each 12 hours.
8.5 To establish the ability to generate acceptable accuracy and precision
on water samples, the analyst must perform the following operations.
8.5.1 A quality control (QC) reference sample concentrate is
required containing each analyte at a concentration of 10 ug/mL in
methanol. The QC reference sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If prepared by the
laboratory, the QC reference sample concentrate must be made using stock
standards prepared independently from those used for calibration.
8.5.2 Prepare a QC reference sample to contain 20 ug/L of each
analyte by adding 200 uL of QC reference sample concentrate to 100 ml of
water. For the low level 25 mL a sample, spike at 5 ug/L.
8.5.3 Four 5 ml aliquots (or 25 ml for low level) of the well-mixed
QC reference sample are analyzed according to the method beginning in Step
7.4.1.
8260 - 26 Revision 1
December 1988
-------
8.5.4 Calculate the average percent recovery (R) and the standard
deviation of the percent recovery (SR), for the results. Ground water
background corrections must be made before R and RR calculation.
8.5.5 Tables 7 and 8 provide single laboratory recovery and
precision data obtained for the method analytes from water. Similar
results from dosed water should be expected by any experienced laboratory.
Compare results obtained in Step 8.5.4 to the single laboratory recovery
and precision data. If the results are not comparable, review potential
problem areas and repeat the test. Results are comparable if the
calculated percent relative standard deviation (RSD) does not exceed 2.6
times the single laboratory RSD or 20%, whichever is greater and the mean
recovery lies within the interval R ± 3S or R ± 30%, which ever is
greater.
8.5.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Step
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and repeat
the test for all analytes beginning with Step 8.5.2.
8.5.6.2 Beginning with Step 8.5.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Step
8.5.2. -
8.6 The laboratory must, on an ongoing basis, analyze a blank and spiked
replicates for each analytical batch (up to a maximum of 20 samples/batch) to
assess accuracy. For soil and waste samples where detectable amounts of
organics are present, replicate samples may be appropriate in place of spiked
replicates. For laboratories analyzing one to ten samples per month, at least
one spiked sample per month is required.
8.6.1 The concentration of the spike in the sample should be
determined as follows:
8.6.1.1 If, as in compliance monitoring, the concentration of a
specific analyte in the sample is being checked against a regulatory
concentration limit, the spike should be at that limit or 1 to 5
times higher than the background concentration determined in Step
8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte in a water
sample is not being checked against a specific limit, the spike
should be at 20 ug/L (or 5 ug/L for low level) or 1 to 5 times higher
than the background concentration determined in Step 8.6.2, whichever
concentration would be larger. For other matrices, the recommended
spiking concentration is 10 times the PQL.
8260 - 27 Revision 1
December 1988
-------
8.6.2 Analyze one 5 ml sample aliquot (or 25 ml for low level) to
determine the background concentration (B) of each analyte. If necessary,
prepare a new QC check sample concentrate (Step 8.5.1) appropriate for the
background concentration in the sample. Spike a second 5 ml (or 25 ml for
low level) sample aliquot with 10 ui of the QC reference sample
concentrate and analyze it to determine the concentration after spiking
(A) of each analyte. Calculate each percent recovery (p) as 100(A-B)%/T,
where T is the known true value of the spike.
8.6.2.1 Compare the percent recovery (Ri) for each analyte with
QC acceptance criteria established from the analyses of laboratory
control standards (Step 8.5). Monitor all data from dosed samples.
Analyte recoveries must fall within the established control limits.
8.6.2.2 If recovery is not within limits, the following
procedures are required.
8.6.2.2.1 Check to be sure there are no errors in
calculations, matrix spike solutions, and internal standards.
Also,' check instrument performance.
8.6.2.2.2 Recalculate the data and/or reanalyze the
extract if any of the above checks reveal a problem.
8.6.2.2.3 If the checks in 8.6.2.2.1 reveal no errors, the
recovery problem encountered with the dosed sample is judged to
be matrix-related, non system-related. The result for that
analyte in the unspiked sample is labeled suspect/matrix to
inform the user that the results are suspect due to matrix
effects.
8.7 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After the
analysis, of five spiked samples (of the same matrix) as in Step 8.6, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (sp). Express the accuracy assessment as a percent recovery interval
from p - 2sp to p + 2sp. If p = 90% and Sp = 10%, for example, the accuracy
interval is expressed as 70-110%. Update the accuracy assessment for each
analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.8 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.8.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.8.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (p) and standard
deviation of the percent recovery (sp) for each of the surrogates.
8260 - 28 Revision 1
December 1988
-------
8.8.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = p + 3sp
Lower Control Limit (LCL) = p - 3sp
8.8.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Table 9. The limits given in Table 9 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Step 8.8.3 must
fall within those given in Table 9 for these matrices.
8.8.5 If recovery is not within limits, the following procedures are
required.
"•
Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.9.6 At a minimum, each laboratory should update surrogate recovery
limits on a matrix-by-matrix basis, annually.
8.10 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column or a different ionization mode using a mass
spectrometer must be used. Whenever possible, the laboratory should analyze
standard reference materials and participate in relevant performance
evaluation studies.
8.11 In recognition of the rapid advances occurring in chromatography, the
an'alyst is permitted to modify GC columns, GC conditions, or detectors to
improve the separations or lower the cost of measurements. Each time such
modifications to the method are made, the analyst is required to repeat the
procedure in Step 8.4.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined as the minimum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
8260 - 29 Revision 1
December 1988
'0
-------
9.2 This method has been tested in a single laboratory using spiked
water. Using a wide-bore capillary column, water was spiked at concentrations
between 0.5 and 10 ug/L. Single laboratory accuracy and precision data are
presented for the method analytes in Table 7. Calculated MDLs are presented in
Table 1.
9.3 The method was tested using water spiked at 0.1 to 0.5 ug/L and
analyzed on a cryofocussed narrow-bore column. The accuracy and precision data
for these compounds are presented in Table 8. MDL values were also calculated
from these data and are presented in Table 2.
10.0 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Methods for the Determination of Organic Compounds in Finished Drinking
Hater and Raw Source Water Method 524.2; U.S. Environmental Protection
Environmental Monitoring and
Agency.
Support
Office of
Laboratory:
Research Development.
Cincinnati, OH 1986.
U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
Bell'ar, T.A.; Lichtenberg, J.J.
739-744.
Amer. Water Works Assoc. 1974, 66(12).
Bellar, T.A.; Lichtenberg, J.J. "Semi -Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds"; in Van Hall, Ed.; Measurement of Organic Pollutants in Water
and Wastewater. ASTM STP 686, pp 108-129, 1979.
Budde, W.L.; Eichelberger, J.W. "Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass Spectrometry Equipment and
Laboratories"; U.S. Environmental Protection Agency. Environmental
Monitoring and Support Laboratory. Cincinnati, OH 45268, April 1980; EPA-
600/4-79-020.
Eichelberger, J.W.; Harris, L.E.; Budde, W.L. "Reference Compound to
Calibrate Ion Abundance Measurement in Gas Chromatography-Mass
Spectrometry Systems"; Analytical Chemistry 1975, 4_7, 995-1000.
Olynyk, P.; Budde, W.L.; Eichelberger, J.W. "Method Detection Limit for
Methods 624 and 625"; Unpublished report, October 1980.
Provost, L.P.; Elder R.S. "Interpretation of Percent Recovery Data";
American Laboratory 1983, 1_5, 58-63.
Non Cryogenic Temperatures Program and Chromatogram, Private
Communications; Myron Stephenson and Frank Allen, EPA Region IV
Laboratory, Athens, GA.
Test Methods for Evaluating Solid Waste. Physical/Chemical Methods. 3rd
ed.; U.S. Environmental Protection Agency. Office of Solid Waste and
Emergency Response. U.S. Government Printing Office: Washington, DC,
1987; SW-846; 955-001-00000-1.
8260 - 30
Revision 1
December 1988
-------
11. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
12. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
for Reagent Water"; ASTM: Philadelphia, PA, 1985;
D1193-77.
8260 - 31 Revision 1
December 1988
-------
TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON WIDE BORE CAPILLARY COLUMNS
ANALYTE
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethane
Methyl ene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis- 1,2-Di chl oroethene
Chloroform
Bromochl oromethane
1 , 1 , 1-Trichloroethane
Carbon tetrachloride
1,1-Dichloropropene
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
Toluene
1 , 1 , 2-Tri chloroethane
Tetrachl oroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
1-Chlorohexane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Styrene
Bromoform
Isopropyl benzene
1 , 1,2,2-Tetrachloroethane
Bromobenzene
Column ]
1.55
1.63
1.71
2.01
2.09
2.27
2.89
3.60
3.98
4.85
6.01
6.19
6.40
6.74
7.27
7.61
7.68
8.23
8.40
9.59
10.09
10.59
10.65
12.43
13.41
13.74
14.04
14.39
14.73
15.46
15.76
15.94
15.99
16.12
16.17
17.11
17.31
17.93
18.06
18.72
18.95
RETENTION TIME
(minutes)
1* Column 2°
0.70
0.73
0.79
0.96
1.02
1.19
1.57
2.06
2.36
2.93
3.80
3.90
4.80
4.38
4.84
5.26
5.29
5.67
5.83
7.27
7.66
8.49
7.93
10.00
11.05
11.15
11.31
11.85
11.83
13.29
13.01
13.33
13.39
13.69
13.68
14.52
14.60
14.88
15.46
16.35
15.86
Column 3
..
2.07
2.12
2.26
2.31
2.42
3.08
3.32
3.48
4.10
4.43
4.42
4.58
4.54
5.09
5.18
5.18
5.29
5.29
6.07
6.20
6.39
6.27
7.36
8.07
8.21
8.20
8.39
--
9.33
9.41
9.44
9.56
9.56
10.32
10.33
10.48
11.38
11.35
MDLd
(ug/L)
0.10
0.13
0.17
0.11
0.10
0.08
0.12
0.03
0.06
0.04
0.35
0.12
0.03
0.04
0.08
0.21
0.10
0.04
0.06
0.19
0.04
0.08
0.24
0.11
0.10
0.14
0.04
0.05
0.06
0.05
0.04
0.05
0.06
0.13
0.05 .
0.11
0.04
0.12
0.15
0.04
0.03
8260 - 32
Revision 1
December 1988
-------
TABLE 1.
(Continued)
ANALYTE
RETENTION TIME MDLd
(minutes) (ug/L)
Column la Column 2b Column 3C
1,2,3-Trichloropropane
n-Propyl benzene
2-Chlorotoluene
1 , 3 , 5-Tri methyl benzene
4-Chlorotoluene
tert-Butyl benzene
1, 2, 4-Tri methyl benzene
sec-Butyl benzene
p-Isopropyl toluene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Butyl benzene
1,2-Dichlorobenzene
1 , 2-Di bromo-3-chl oropropane
1,2, 4-Tri chlorobenzene
Hexachlorobutadiene
Naphthalene
1, 2, 3-Tri chlorobenzene
19.02
19.06
19.34
19.47
19.50
20.28
20.34
20.79
21.20
21.22
21.55
22.22
22.52
24.53
26.55
26.99
27.17
27.78
16.23
16.41
16.42
16.90
16.72
17.57
17.70
18.09
18.52
18.14
18.39
19.49
19.17
21.08
23.08
23.68
23.52
24.18
11.40
--
11.57
--
12.08
--
--
--
--
13.16
13.27
--
14.10
--
--
--
--
--
0.32
0.04
0.04
0.05
0.06
0.14
0.13-
0.13
0.12
0.12
0.03
0.11
0.03
0.26
0.04
0.11
0.04
0.03
INTERNAL STANDARDS/SURROGATES
4-Bromof1uorobenzene
18.63
15.71
11.22
aColumn 1 - 60 m x 0.75 mm i.d. VOCOL capillary. Hold at 10°C for
5 minutes, then program to 160°C at 6°/min.
^Column 2 - 30 m x 0.53 mm i.d. DB-624 wide-bore capillary using
cryogenic oven. Hold at 10°C for 5 minutes, then program to 160°C at
6°/min.
cColumn 3 - 30 m x 0.53 mm i.d. DB-624 wide-bore capillary, cooling GC
oven to ambient temperatures. Hold at 45°C for 2 minutes, then program to
200"C at 8°/min and hold for 6 minutes.
based on a 25 mL sample volume.
8260 - 33
Revision 1
December 1988
-------
TABLE 2.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
FOR VOLATILE ORGANIC COMPOUNDS ON NARROW-BORE CAPILLARY COLUMNS
ANALYTE
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl chloride .
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methylene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
cis -1,2-Di chl oroethene
2,2-Dichloropropane
Chloroform
Bromochloromethane
1 , 1, 1 -Tri chloroethane
1,2-Dichloroethane
1,1-Bichloropropene
Carbon tetrachloride
Benzene
1,2-Dichloropropane
Trichloroethene
Dibromomethane
Bromodi chloromethane
Toluene
1 , 1 , 2-Tri chl oroethane
1,3-Dichloropropane
Di bromochl oromethane
Tetrachl oroethene
1,2-Dibromoethane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
Bromoform
o-Xylene
Styrene
1,1,2, 2-Tetrachl oroethane
1,2,3-Trichloropropane
Isopropyl benzene
RETENTION TIME
(minutes)
Column 3a
0.88
0.97
1 ..04
1.29
1.45
. 1.77
2.33
2.66
3.54
4.03
5.07
5.31
5.55
5.63
6.76
7.00
7.16
7.41
7.41
8.94
9.02
9.09
9.34
11.51
11.99
12.48
12.80
13.20
13.60
14.33
14.73
14.73
15.30
15.30
15.70
15.78
15.78
15.78
16.26
16.42
MDLb
(ug/L)
0.11
0.05
0.04
0.06
0.02
0.07
0.05
0.09
0.03
0.03
0.06
0.08
0.04
0.09
0.04
0.02
0.12
0.02
0.03
0.02
0.02
0.01
0.03
0.08
0.08
0.08
0.07
0.05
0.10
0.03
0.07
0.03
0.06
0.03
0.20
0.06
0.27
0.20
0.09
0.10
8260 - 34
Revision 1
December 1988
-------
TABLE 2.
(Continued)
ANALYTE
RETENTION TIME
(minutes)
Column 3a
MDI_b
(ug/L)
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1 , 3, 5-Trimethyl benzene
tert-Butyl benzene
1,2,4-Trimethylbenzene .
sec-Butyl benzene
1,3-Dichlorobenzene
p-Isopropyltoluene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
n-Butyl benzene
l,2-Dibromo-3-chloropropane
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
1,2,3-Trichlorobenzene
16.42
16.74
16.82
16.82
16.99
17.31
17.31
17.47
17.47
17.63
17.63
17.79
17.95
18.03
18.84
19.07
19.24
19.24
0.11
0.08
0.10
0.06
0.06
0.33
0.09
0.12
0.05
0.26
0.04
0.05
0.10
0.50
0.20
0.10
0.10
0.14
aColumn 3 - 30 m x 0.32 mm i.d. DB-5 capillary with urn film thickness.
bMDL based on a 25 ml sample volume.
8260 - 35
Revision 1
December 1988
-------
TABLE 3.
PRACTICAL QUANTITATION LIMITS FOR VOLATILE ANALYTESa
Practical
Quantitation
Limits
Ground water Low Soil/Sedimentb
ug/L ug/kg
Volume of water purged 5 mL 25 mL
All analytes in Table 1 5 1
aPractical Quantitation Limit (PQL) - The lowest level that can be reliably
achieved within specified limits of precision and accuracy during routine
laboratory operating conditions. The PQL is generally 5 to 10 times the MDL.
However, it may be nominally chosen within these guidelines to simplify data
reporting. For many analytes the PQL analyte level is selected for the lowest
non-zero standard in the calibration curve. Sample PQLs are highly matrix-
dependent. The PQLs listed herein are provided for guidance and may not
always be achieveable. See the following information for further guidance on
matrix-dependent PQLs.
listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis; therefore, PQLs will be higher, based on the
% moisture in each sample.
Other Matrices: Factor0
Water miscible liquid waste 50
High-level soil and sludges 125
Non-water miscible waste 500
CPQL = [PQL for low soil sediment (Table 3)] X [Factor]. For non-aqueous
samples, the factor is on a wet-weight basis.
8260 - 36 Revision 1
December 1988
-------
TABLE 4.
BFB MASS - INTENSITY SPECIFICATIONS (4-BROMOFLUOROBENZENE)
Mass Intensity Required (relative abundance)
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
8260 - 37 Revision 1
December 1988
-------
TABLE 5.
CHARACTERISTIC MASSES (M/Z) FOR PURGEABLE ORGANIC COMPOUNDS
Analyte
Primary
Characteristic
Ion
Secondary
Characteristic
Ion(s)
Benzene
Bromobenzene
Bromochl oromethane
Bromod i chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chl oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1 ,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
78
156
128
83
173
94
91
105 •
119
117
112
64
83
50
126
91
75
129 '
107
93
146
146
146
85
63
62
96
96
96
63
76
77
75
91
225
105
119
84
128
120
104
131
8260 - 38
77,158
49,130
-85,127
175,254 >
96
92,134 -
134
91,134
119
77,114
66
85
52
126
126
155,157
127
109,188
95,174
111,148
111,148
111,148
87
65,83
98
61,63
61,98
61,98
112
78
97
110,77
106
223,227
120
134,91
86,49 .
-
120
78
133,119
Revision 1
December 1988
-------
TABLE 5.
(Continued)
• Primary Secondary
Characteristic Characteristic
Analyte Ion Ion(s)
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1 ,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Tri methyl benzene
1 ,3 , 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
83
166
92
180
180
. 97
83
95
101
75
105
105
62
106
106
106
131,85
168,129
91
182,145
182,145
99,61
97, "85
130,132
103
77
120
120
64
91
91
91
INTERNAL STANDARDS/SURROGATES
4-Bromofluorobenzene 95 174,176
Dibromofluoromethane 113
Toluene-da 98
Pentafluorobenzene 168
1,4-Difluorobenzene 114
Chlorobenzene-ds 117
l,4-Dichlorobenzene-d4 152
8260 - 39 Revision 1
December 1988
-------
TABLE 6.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
Pentafluorobenzene
Acetone
Acrolein
Acrylonitrile
Bromochloromethane
Bromomethane
2-Butanone
Carbon disulfide
Chloroethane
Chloroform
Chloromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
2,2-Dichloropropane
lodomethane
Methylene chloride
1,1,1-Trichloroethane
Tri chlorof1uoromethane
Vinyl acetate
Vinyl chloride
Chlorobenzene-ds
Bromoform
Chlorodi bromomethane
Chlorobenzene
1,3-Dichloropropane
Ethyl benzene
2-Hexanone
Styrene
1,1,1,2-Tetrachloroethane
Tetrachloroethene
Xylene
1,4-Difluorobenzene
Benzene
Bromodichloromethane
Bromofluorobenzene (surrogate)
Carbon tetrachloride
2-Chloroethyl vinyl ether
1,2-Dibromoethane
Dibromomethane
1,2-Dichloroethane
1,2-Dichloroethane-d4 (surrogate)
1,2-Di chloropropane
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
4-Methyl-2-pentanone
Toluene
Toluene-ds (surrogate)
1,1,2-Trichloroethane
Trichloroethene
1.4-Dichlorobenzene-d4
Bromobenzene
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
2-Chlorotoluene
4-Chlorotoluene
1,2-Dibromo-3-chloropropane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Naphthalene
n-Propylbenzene
1,1,2,2-Tetrachloroethane
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethyl benzene
8260 - 40
Revision 1
December 1988
-------
TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
ORGANIC COMPOUNDS IN WATER DETERMINED WITH A WIDE-
BORE .CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orod i f 1 uoromethane
1, 1-Dichlorobenzene
1,2-Dichlorobenzene
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans -1,2-Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Cone. Number
Range, of
ug/L Samples
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.1
0.1
0.5
0.1
0.5
0.5
0.1
0.5
0.2
0.5
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.5
0.5
0.1
0.5
0-.5
0.1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 20
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- JO
- 10
- 10
- 10
31
30
24
30
18
18
18
16
18
24
31
24
24
23
31
31
24
31
24
24
31
24
31
18
24
31
34
18
30
30
31
12
18
31
18
16
23
Recovery
%
97
100
90
95
101
95
100
100
102
84
98
89
90
93
90
99
83
92
102
100
93
99
103
90
96
95
94
101
93
97
96
86
98
99
100
101
99
Standard Percent
,a Deviation Rel . Std.
of Recovery0 Dev.
6.5
5.5
5.7
5.7
6.4
7.8
7.6
7.6
7.4
7.4
5.8
8.0
5.5
8.3
5.6
8.2
16.6
6.5
4.0
5.6
5.8
6.8
6.6
6.9
5.1
5.1
6.3
6.7
5.2
5.9
5.7
14.6
8.7
8.4
6.8
7.7
6.7
5.7
5.5
6.4
6.1
6.3
8.2
7.6
7.6
7.3
8.8
5.9
9.0
6.1
8.9
6.2
8.3
19.9
7.0
3.9
5.6
6.2
6.9
6.4
7.7
5.3
5.4
6.7
6.7
5.6
6.1
6.0
16.9
8.9
8.6
6.8
7.6
6.7
8260 - 41
Revision 1
December 1988
-------
TABLE 7.
(Continued)
Analyte
Cone.
Range,
ug/L
Number
of
Samples
Standard
Recovery,3 Deviation
% of Recovery*5
Percent
Rel. Std.
Dev.
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.1
0.1
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
- 10
-100
- 10
-100
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 31
- 10
- 10
30
31
31
39
24
30
24
18
18
18
18
18
24
24
16
18
23
18
18
31
18
95
104
100
102
90
91
89
102
109
108
98
104
90
89
108
99
92
98
103
97
104
5.0
8.6
5.8
7.3
6.1
5.7
6.0
8.1
9.4
9.0
.9
.6
6.5
7.2
15.6
8.0
6.8
6.5
7.4
6.3
8.0
7,
7.
5.3
8.2
5.8
7.2
6.8
6.3
6.8
8.0
8.6
8.3
8.1
7.
7.
8.
14.
8.1
7.4
6.7
7.2
6.5
7.7
.3
.3
,1
.4
Recoveries were calculated using internal standard method. Internal standard
was fluorobenzene.
^Standard deviation was calculated by pooling data form three levels.
8260 - 42
Revision 1
December 1988
-------
TABLE 8.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR
VOLATILE ORGANIC COMPOUNDS IN WATER DETERMINED
WITH A NARROW BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichlorome thane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Dibromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2, 2 -Di chl oropropane
1, 1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyl toluene
Cone.
ug/L
0.1
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery,3
%
99
97
97
100
101
99
94
110
110
108
91
100
105
101
99
96
92
99
97
93
97
' 101
! 106
, 99
• 98
i 100
! 95
1 100
: 98
96
99
99
102
99
100
102
113
Standard
Deviation
of Recovery*5
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6.8
5.8
5.8
3.2
4.7
4.6
7.0
10.0
5.6
5.6
5.6
3.5
6.0
6.5
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
6.7
6.4
13.0
Percent
Rel. Std,
Dev.
6.3
7.6
6.0
4.6
5.3
7.2
6.4
6.5
2.3
6.3
6.4
5.8
3.0
4.7
4.6
7.3
10.9
5.7
5.8
6.0
3.6
5.9
6.1
8.9
6.3
6.3
9.5
3.7
7.3
6.3
5.9
4.9
7.3
5.3
6.7
6.3
11.5
8260 - 43
Revision 1
December 1988
-------
TABLE 8.
(Continued)
Analyte
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Tri chl orofl uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1 , 3 , 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
Cone.
ug/L
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
0.5
0.5
0.1
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery,3
%
97
98
99
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery^
13.0
7.2
6.6
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6 "
6.1
Percent
Rel. Std
Dev.
13.4
7.3
6.7
19.8
4.7
1*2.0
5.2
5.9
8.7
17.6
4.0
4.8
1.9
4.7
6.8
6.8
4.2
0.2
7.1
4.3
6.3
Recoveries were calculated using internal standard method. Internal standard
was fluorobenzene.
8260 - 44
Revision 1
December 1988
-------
MINI-COLUMN TEST RESULTS
50
40
2 30
o
z
o
20
10
CARBORUNDUM GAC 830
TETRACHLOROETHVLEN6
TRICHLOROETHYLENE
/
I
1.1.1-TRICHLORO
ETHANE r—7
' ' /
IOOO 2000 3000
WATER TREATED (ml)
4000
Define:
Controlling VOC
Carbon Usaye based on:
Carbon usage (lbs/1,000 gal)
= W x 8461.5
V
wherr.- W = weight of carbon (0.1 gin)
V = volume treated (ml)
Preliminary Process Design
-12-
-------
TABLE 9.
SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/Medium Low/Medium
Surrogate Compound Water Soil/Sediment
4-Bromofluorobenzenea 86-115 74-121
Dibromofluoromethane3 86-118 80-120
Toluene-da* 88-110 81-117
aSingle laboratory data for. guidance only.
8260 - 45 Revision 1
December 1988
-------
METHOD 8270
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORGANICS;
CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 8270 1s used to determine the concentration of semi volatile
organic compounds 1n extracts prepared from all types of solid waste
matrices, soils, and ground water. Direct injection of a sample may be used
in limited applications.
1.2 Method 8270 can be used to quantify most neutral, acidic, and basic
organic compounds that are soluble 1n methylene chloride and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic
fused-silica capillary column coated with a slightly polar silicone. Such
compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons
and pesticides, phthalate esters, organophosphate esters, nitrosamlnes,
haloethers, aldehydes, ethers, ketones, anilines, pyridines, quinolines,
aromatic nitro compounds, and phenols, Including nltrophenols. See Table 1
for a list of compounds and their characteristic Ions that have been
evaluated on the specified GC/MS system.
1.3 The following compounds may require special treatment when being
determined by this method. Benzldine can be subject to oxldative losses
during solvent concentration. Also, chromatography is poor. Under the
alkaline conditions of the extraction step, a-BHC, 7 -BHC, endosulfan I and
II, and endrin are subject to decomposition. Neutral extraction should be
performed if these compounds are expected. Hexachlorocyclopentadiene is
subject to thermal decomposition in the inlet of the gas chromatograph,
chemical reaction 1n acetone solution, and photochemical decomposition.
N-nitrosod1methyl amine is difficult to separate from the solvent under the
chromatographic conditions described. N-nitrosod1phenylam1ne decomposes in
the gas chromatographic Inlet and cannot be separated from diphenylamlne.
Pentachlorophenol, 2,4-dinitrophenol, 4-n1trophenol, 4,6-din1tro-2-
methylphenol, 4-chloro-3-methylphenol, benzole acid, 2-n1troan1line, 3-
nltroaniUne, 4-chloroan1line, and benzyl alcohol are subject to erratic
chromatographic behavior, especially 1f the GC system 1s contaminated with
high boiling material.
1.4 The practical quantltatlon limit (PQL) of Method 8270 for
determining an individual compound 1s approximately rmg/kg (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes (dependent on matrix and method
of preparation), and 10 ug/L for ground water samples (see Table 2). PQLs
will be proportionately higher for sample extracts that require dilution to
avoid saturation of the detector.
1.5 This method 1s restricted to use by or under the supervision of
analysts experienced 1n the use of gas chromatograph/mass spectrometers and
skilled 1n the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method.
8270 - 1
Revision 0
Date September 1986
-------
TABLE 1. CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Retention
Compound Time (m1n)
Acenaphthene
Acenaphthene-dio (I.S.)
Acenaphthylene
Acetophenone
Aldrin
Aniline
Anthracene
4-Aminobiphenyl
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Benzidine
Benzole acid
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k)fl uoranthene
Benzo (g,h,i)peryl ene
Benzo(a)pyrene
Benzyl alcohol
a-BHC
/J-BHC
5-BHC
7-BHC (Lindane)
Bi s (2-chl oroethoxy) methane
Bi s (2-chl oroethy 1 ) ether
Bi s (2-chl oroi sopropyl ) ether
Bi s (2-ethyl hexyl ) phthal ate
4-Bromophenyl phenyl ether
Butyl benzyl phthal ate
Chlordane
4-Chloroaniline
1-Chl oronaphthal ene
2-Chl oronaphthal ene
4-Chloro-r3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-di2 (I.S.)
4,4'-DDD
4,4'-DDE
15.13
15.05
14.57
7.96a
—
5.68
19.77
19.18a
—
—
--
—
—
—
—
23.87
9.38
27.83 .
31.45
31.55
41.43
32.80
6.78
—
— . ;
—
;
9.23
5.82
7.22
28.47
18.27
26.43
—
10.08
13.65a
13.30
11.68
5.97
16.78
27.97
27.88
—
!
Primary Ion
154
164
152
105
66
93
178
169
222
190
190
222
292
292
360
184
122
228
252
252
276
252
108
183
181
183
183
93
93
45
149
248
149
373
127
162
162
107
128
204
228
240
235
246
Secondary Ion(s)
153, 152
162, 160
151, 153
77, 51
263, 220
66, 65
176, 179
168, 170
260, 292
224, 260
224, 260
256, 292
362, 326
362, 326
362, 394
92, 185
105, 77
229, 226
253, 125
253, 125
138, 277
253, 125
79, 77
181, 109
183, 109
181, 109
181, 109
95, 123
63, 95
77, 121
167, 279
250, 141
91, 206
375, 377
129
127, 164
127, 164
144, 142
64, 130
206, 141
226, 229
120, 236
237, 165
248, 176
8270 - 2
Revision 0
Date September 1986
-------
TABLE 1. CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS (Continued)
Retention
Compound Time (m1n)
4,4'-DDT
D1benz(a,j)acr1d1ne
D1 benz (a , h) anthracene
Dlbenzofuran
D1 -n-butyl phthal ate
1,3-Dichlorobenzene
1 , 4-D1 chl orobenzene
l,4-D1chlorobenzene-d4 (I.S.)
1,2-01 chl orobenzene
3,3'-D1chlorobenz1d1ne
2,4-D1chlorophenol
2,6-D1chlorophenol
D1eldr1n
D1 ethyl phthal ate
p-D1 methyl ami noazobenzene
7 , 12-D1methy 1 benz (a) anthracene
a- , a-D1 methyl phenethy 1 ami ne
2, 4-D1methyl phenol
Dimethyl phthal ate
4 , 6-D1 n1 tro-2-methy 1 phenol
2,4-D1m'trophenol
2,4-D1n1trotoluene
2,6-D1n1trotoluene
Dlphenylamlne
1 , 2-D1 pheny 1 hydrazl ne
D1 -n-octyl phthal ate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Endrln ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorob1phenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxlde
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl orocycl opentadl ene
Hexachl oroethane
Indeno(l,2,3-cd)pyrene
— —
32.55a
39.82
15.63
21.78
6.27
6.40
6.35
6.85
27.88
9.48
10.05a
—
16.70
24.48a
29.54a
9.51a
9.03
14.48
17.05
15.35
15.80
14.62
17.54a
—
30.48
—
—
—
—
—
—
5.33a
23.33
16.70
—
—
—
—
18.65
10.43
12.60
7.65
39.52
Primary Ion
235
279
278
168
149
146
146
152
146
252
162
162
79
149
120
256
58
122
163
198
184
165
165
169
77
149
195
337
272
263
67
317
79
202
166
172
112
100
353
284
225
237
117
276
Secondarylon(s)
237, 165
280, 277
139, 279
139
150, 104
148, 111
148, 111
150, 115
148, 111
254, 126
164, 98
164, 98
263, 279
177, 150
225, 77
241, 257
91, 42
107, 121
194, 164
51, 105
63, 154
63, 89
63, 89
168, 167
105, 182
167, 43
339, 341
339, 341
387, 422
82, 81
345, 250
67, 319
109, 97
101, 203
165, 167
171
64
272, 274
355, 351
142, 249
223, 227
235, 272
201, 199
138, 227
8270 - 3
Revision 0
Date September 1986
-------
TABLE 1. CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS (Continued)
Retention
Compound Time (m1n)
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphthal ene
2-Methy 1 phenol (o-cresol )
4-Methyl phenol (p-cresol)
Naphthalene
Naphthal ene-dg (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-N1troan1line
4-Nitroan1l1ne
Nitrobenzene
Nitrobenzene-ds (surr.)
2-N1trophenol
4-N1trophenol
N-N1 troso-di -n-butyl ami ne
N-N1trosod1 methyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni trosodi propy 1 ami ne
N-N1 trosopi peri di ne
Pentachl orobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-dj2 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-dio (I.S.)
Phenol
Phenol-ds (surr.)
2-P1coline
Pronamide
Pyrene
Terphenyl-dj4 (surr.)
1,2, 4, 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
2,4,6-Tribromophenol (surr.)
1, 2, 4-Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Toxaphene
8.53
—
31.14a
4.32a ;
11.87
7.22
7.60
9.82
9.75
15.80a
16.00a
13.75
15.02
16.90
7.87
__ i
8.75
15.80
10.99a
—
17.17
7.55
—
15.64a
19.47a
19.25
33.05
18.59a
19.62
19.55
5.77
—
3.75a
19.61a
24.02
—
13.62a
16.09a
—
9.67
13.00
12.85
--
Primary Ion
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
330
180
196
196
159
Secondarylon(s)
95, 138
228
253, 267
79, 65
141
107, 79
107, 79
129, 127
68
115, 116
115, 116
92, 138
108, 92
108, 92
123, 65
128, 54
109, 65
109, 65
57, 41
74, 44
168, 167
42, 101, 130
114, 55
252, 248
237, 142
264, 268
260, 265
109, 179
179, 176
94, 80
65, 66
42, 71
66, 92
175, 145
200, 203
122, 212
214, 218
230, 131
332, 141
182, 145
198, 200
198, 200
231, 233
I.S. = internal standard
surr. = surrogate
Estimated retention times.
8270 - 4
Revision 0
Date September 1986
-------
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
Practical Quantisation
Limits*
Ground Water
Semlvolatlles
Phenol
b1s(2-Chloroethyl) ether
2-Chlorophenol
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Benzyl Alcohol
1 , 2-D1 chl orobenzene
2-Methylphenol
b1 s (2-Chl oroi sopropyl )
ether
4-Methyl phenol
N-Ni troso-DI -N-propy 1 ami ne
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2, 4-Di methyl phenol
Benzole Add
bis(2-Chloroethoxy)
methane
2,4-Dichlorophenol
1,2, 4-Tri chl orobenzene
Naphthalene
4-Chloroaniline
Hexachl orobutadi ene
4-Chl oro-3-methy 1 phenol
2-Methyl naphthal ene
Hexach 1 orocycl opentadi ene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
CAS Number
108-95-2
111-44-4
95-57-8
541-73-1
106-46-7
100-51-6
95-50-1
95-48-7
39638-32-9
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
ug/L
10
10
10
10
10
20
10
10
10
10
10
10
10
10
10
10
50
10
10
10
10
20
10
20
10
10
10
10
Low Soil /Sediment1
ug/Kg
660
660
660
660
660
1300
660
660
660
660
660
660
660
660
660
660
3300
660
660
660
660
1300
660
1300
660
660
660
660
8270 - 5
Revision 0
Date September 1986
-------
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
(Continued)
Practical Quantisation
Limits*
Ground Water
SemlvolatHes
2-Chloronaphthalene
2-Nitroan1Hne
Dimethyl phthalate
Acenaphthylene
3-N1troanil1ne
Acenaphthene
2,4-D1n1trophenol
4-N1trophenol
Dlbenzofuran
2,4-D1nitrotoluene
2,6-D1n1trotoluene
D1 ethyl phthalate
4-Chlorophenyl phenyl
ether
Fluorene
4-N1troan1l1ne
4 , 6-D1 n1 tro-2-methyl phenol
N-N1 trosodl phenyl ami ne
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
D1 -n-buty 1 phthal ate
Fluoranthene
Pyrene
Butyl benzyl phthalate
3,3'-D1chlorobenz1d1ne
Benzo (a) anthracene
b1 s (2-ethyl hexy 1 ) phthal ate
CAS Number
91-58-7
88-74-4
131-11-3
208-96-8
99-09-2
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
ug/L
10
50
10
10
50
10
50
50
10
10
10
10
10
10
50
50
10
10
10
50
10
10
10
10
10
10
20
10
10
Low Soil /Sediment1
ug/Kg
660
3300
660
660
3300
660
3300
3300
660
660
660
660
660
660
3300
3300
660
660
660
3300
660
660
660
660
660
660
1300
660
660
8270 - 6
Revision 0
Date September 1986
-------
TABLE 2. PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
(Continued)
Practical Quantisation
Limits*
Semi-Volatiles
Ground Water Low Soil/Sediment1
CAS Number
ug/L
ug/Kg
Chrysene
Di-n-octyl phthalate
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Di benz (a , h) anthracene
Benzo (g , h , i ) peryl ene
218-01-9
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
10
10
10
10
10
10
10
10
660
660
660
660
660
660
660
660 r
*PQLs listed for soil/sediment are based on wet weight. Normally data is
reported on a dry weight basis, therefore, PQLs will be higher based on the
% moisture in each sample. This is based on a 30-g sample and gel permeation
chromatography cleanup.
**Sample PQLs are highly matrix-dependent. The PQLs
provided for guidance and may not always be achleveable.
listed herein are
Other Matrices
Medium-level soil and sludges by sonicator
Non-water-miscible waste
Factor1
7.5
75
= [PQL for Ground Water (Table 2)] X [Factor].
8270 - 7
Revision 0
Date September 1986
-------
2.0 SUMMARY OF METHOD
2.1 Prior to using this method, the samples should be prepared for
chromatography using the appropriate sample preparation and cleanup methods.
This method describes chromatographic conditions that will allow for the
separation of the compounds in the extract.
3.0 INTERFERENCES
3.1 Raw GC/MS data from all blanks, samples, and spikes must be
evaluated for interferences. Determine if the source of interference is in
the preparation and/or cleanup of the samples and take corrective action to
eliminate the problem.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe must be rinsed out between samples with solvent. Whenever an
unusually concentrated sample 1s encountered, it should be followed by the
analysis of solvent to check for cross contamination.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph/mass spectrometer system;
4.1.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection and all required accessories, including syringes, analytical
columns, and gases. The capillary column should be directly coupled to
the source.
4.1.2 Column: 30-m x 0.25-mm I.D. (or 0.32-mm I.D.) 1-um film
thickness silicon-coated fused-silica capillary column (J&W Scientific
DB-5 or equivalent).
4.1.3 Mass spectrometer: Capable of scanning from 35 to 500 amu
every 1 sec or less, using 70 volts (nominal) electron energy in the
electron impact ionization mode. The mass spectrometer must be capable
of producing a mass spectrum for decafluorotriphenylphosphlne (DFTPP)
which meets all of the criteria 1n Table 3 when 1 uL of the GC/MS tuning
standard is injected through the GC (50 ng of DFTPP).
4.1.4 GC/MS Interface: Any GC-to-MS interface that gives
acceptable calibration points at 50 ng per injection for each compound of
interest and achieves acceptable tuning performance criteria may be used.
4.1.5 Data system: A computer system must be Interfaced to the
mass spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained throughout
the duration of the chromatographic program. The computer must have
8270 - 8
Revision 0
Date September 1986
-------
TABLE 3. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA3
Mass Ion Abundance Criteria
51 30-60% of mass 198
68 <2% of mass 69
70 <2% of mass 69
127 40-60% of mass 198
197 <1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 >1% of mass 198
441 Present but less than mass 443
442 >40% of mass 198
443 17-23% of mass 442
3J.W. Eichelberger, I.E. Harris, and W.L. Budde. "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry",
Analytical Chemistry, 47, 995 (1975).
8270 - 9
Revision
Date September 1986
-------
software that can search any GC/MS data file for ions of a specific mass
and that can plot such ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current Profile (EICP).
Software must also be available that allows integrating the abundances in
any EICP between specified time or scan-number limits. The most recent
version of the EPA/NIH Mass Spectral Library should also be available.
4.2 Syringe; 10-uL.
5.0 REAGENTS
5.1 Stock standard solutions (1.00 ug/uL): Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.
5.1.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure material. Dissolve the material in pesticide quality
acetone or other suitable solvent and dilute to volume in a 10-mL
volumetric flask. Larger volumes can be used at the convenience of the
'analyst. When compound purity is assayed to be 96% or greater, the
weight may be used without correction to calculate the concentration of
the stock standard. Commercially prepared stock standards may be used at
any concentration if they are certified by the manufacturer or by an
independent source.
5.1.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
5.1.3 Stock standard solutions must be replaced after 1 yr or
sooner if comparison with quality control check samples Indicates a
problem.
5.2 Internal standard solutions; The internal standards recommended are
l,4-dichlorobenzene-d4,naphthalene-ds, acenaphthene-djo, phenanthrene-dio,
chrysene-di2, and perylene-di2. Other compounds may be used as internal
standards as long as the requirements given in Paragraph 7.3.2 are met.
Dissolve 200 mg of each compound with a small volume of carbon disulfide.
Transfer to a 50-mL volumetric flask and dilute to volume with methylene
chloride so that the final solvent is approximately 20% carbon disulfide.
Most of the compounds are also soluble 1n small volumes of methanol, acetone,
or toluene, except for perylene-di2. The resulting solution will contain each
standard at a concentration of 4,000 ng/uL. Each 1-mL sample extract
undergoing analysis should be spiked with 10 uL of the internal standard
solution, resulting in a concentration of 40 ng/uL of each internal standard.
Store at 4*C or less when not being used.
5.3 GC/MS tuning standard; A methylene chloride solution containing
50 ng/uL of decaf1uorotriphenylphosphlne (DFTPP) should be prepared. The
8270 - 10
Revision 0
Date September 1986
-------
standard should also contain 50 ng/uL each of 4,4'-DDT, pentachlorophenol, and
benzldlne to verify Injection port Inertness and GC column performance. Store
at 4*C or less when not being used.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels should be prepared. One of the calibration standards
should be at a concentration near, but above, the method detection limit; the
others should correspond to the range of concentrations found in real samples
but should not exceed the working range of the GC/MS system. Each standard
should contain each analyte for detection by this method (e.g., some or all of
the compounds listed in Table 1 may be included). Each 1-mL aliquot of
calibration standard should be spiked with 10 uL of the internal standard
solution prior to analysis. All standards should be stored at -10'C to -20°C
and should be freshly prepared once a year, or sooner if check standards
Indicate a problem. The dally calibration standard should be prepared weekly
and stored at 4°C.
5.5 Surrogate standards; The recommended surrogate standards are
phenol-ds,2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-ds, 2-fluoro-
biphenyl, and p-terphenyl-di4. See Method 3500 for the Instructions on
preparing the surrogate standards. Determine what concentration should be in
the blank extracts after all T extraction, cleanup, and concentration steps.
Inject this concentration into the GC/MS to determine recovery of surrogate
standards in all blanks, spikes, and sample extracts. Take into account all
dilutions of sample extracts.
5.6 Matrix spike standards; See Method 3500 for Instructions on
preparing the matrix spike standard. Determine what concentration should be
1n the blank extracts after all extraction, cleanup, and concentration steps.
Inject this concentration Into the GC/MS to determine recovery of surrogate
standards 1n all blanks, spikes, and sample extracts. Take Into account all
dilutions of sample extracts.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE .
7.1 Sample preparation; Samples must be prepared by one of the
following methods prior to GC/MS analysis.
Matrix Methods
Water ; 3510, 3520
Soil/sediment 3540, 3550
Waste 3540, 3550, 3580
8270 - 11
Revision 0
Date September 1986
-------
7.1.1 Direct Injection: In very limited applications direct
Injection of the sample Into the GC/MS system with a 10 uL syringe may be
appropriate. The detection limit 1s very high (approximately 10,000
ug/L); therefore, 1t 1s only permitted where concentrations 1n excess of
10,000 ug/L are expected. The system must be calibrated by direct
Injection.
7.2 Extract cleanup; Extracts may be cleaned up by any of the following
methods prior to GC/MS analysis.
Compounds Methods
Phenols 3630, 3640, 8040a
Phthalate esters 3610, 3620, 3640
Nitrosamines 3610, 3620, 3640
Organochlorlne pesticides & PCBs 3620, 3640, 3660
Nltroaromatlcs and cyclic ketones 3620, 3640
Polynuclear aromatic hydrocarbons 3611, 3630, 3640
Haloethers 3620, 3640
Chlorinated hydrocarbons 3620, 3640
Organophosphorous pesticides 3620, 3640
Petroleum waste 3611, 3650
All priority pollutant base,
neutral, and adds 3640
aMethod 8040 Includes a der1vat1zat1on technique followed by GC/ECD
analysis, 1f Interferences are encountered on GC/FID.
7.3 Initial calibration; The recommended GC/MS operating conditions:
Mass range: 35-500 amu ;
Scan time: 1 sec/scan !
Initial column temperature and hold time: 40*C for 4 m1n
Column temperature program: 40-270*C at !0*C/m1n
Final column temperature hold: 270*C (until benzo[g,h,1]perylene
has eluted)
Injector temperature: 250-300*C
Transfer line temperature: 250-300*C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
Sample volume: 1-2 uL
Carrier gas: Hydrogen at 50 cm/sec or helium at 30 cm/sec.
7.3.1 Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50-ng injection of DFTPP. Analyses should not begin
until all these criteria are met. Background subtraction should be
straightforward and designed only to eliminate column bleed or instrument
background ions. The GC/MS tuning standard should also be used to assess
GC column performance and injection port inertness. Degradation of DDT
to DDE and DDD should not exceed 20%. Benzidine and pentachlorophenol
should be present at their normal responses, and no peak tailing should
be visible. If degradation is excessive and/or poor chromatography is
noted, the injection port may require cleaning. It may also be necessary
to break off the first 6-12 in. of the capillary column.
8270 - 12
Revision 0
Date September 1986
-------
7.3.2 The Internal standards selected 1n Paragraph 5.1 should
permit most of the components of Interest in a chromatogram to have
retention times of 0.80-1.20 relative to one of the Internal standards.
Use the base peak ion from the specific Internal standard as the primary
ion for quantitation (see Table 1). If interferences are noted, use the
next most intense ion as the quantitation ion, I.e., for 1,4-
dichlorobenzene-d4 use m/z 152 for quantitation.
7.3.3 Analyze 1 uL of each calibration standard (containing
internal standards) and tabulate the area of the primary characteristic
ion against concentration for each compound (as indicated in Table 1).
Figure 1 shows a chromatogram of a calibration standard containing
base/neutral and acid analytes. Calculate response factors (RFs) for
each compound as follows:
RF = (AxCis)/(AisCx)
where:
Ax = Area of the characteristic ion for the compound being
measured.
AIS = Area of the characteristic 1on for the specific internal
standard.
Cx = Concentration of the compound being measured (ng/uL).
C^s = Concentration of the specific internal standard (ng/uL).
7.3.4 The average RF should be calculated for each compound. The
percent relative standard deviation (%RSD = 100[SD/RF]) should also be
calculated for each compound. The %RSD should be less than 30% for each
compound. However, the %RSD for each individual Calibration Check
Compound (CCC) (see Table 4) must be less than 30%. The relative
retention times of each compound in each calibration run should agree
within 0.06 relative retention time units. Late-eluting compounds
usually have much better agreement.
7.3.5 A system performance check must be performed to ensure that
minimum average RFs are met before the calibration curve is used. For
semivolatiles, the System Performance Check Compounds (SPCCs) are:
N-nitroso-di-n-propylamine; hexachlorocyclopentadiene; 2,4-dinitrophenol;
and 4-nitrophenol. The minimum acceptable average RF for these compounds
SPCCs is 0.050. These SPCCs typically have very low RFs (0.1-0.2) and
tend to decrease in response as the chromatographic system begins to
deteriorate or the standard material begins to deteriorate. They are
usually the first to show poor performance. Therefore, they must meet
the minimum requirement when the system is calibrated.
8270 - 13
Revision 0
Date September 1986
-------
00
ro
O 73
O» O>
rt <
ft) — '•
C/> O
O) =5
cr
(T)
VO
OD
01
R1C DATA: 51BHS680736 fcl SCANS 2*8 TO 2700
38/07/86 6:26:38 CHLI: 51BHS680786 13
SHMPLE: BASE ACID STD,2U-/20rtG--Ul.
COMDS.:
RuNCE: G 1,2788 LABEL: N 8, 4.0 OUnN: A U, 1.8 J 8 BASE: U 28, 3
RIC
598
8:28
16:48
33:28
13S523.
2598
41:48
TI1Z
Figure 1. Gas chromatogram of base/neutral and add calibration standard.
-------
TABLE 4. CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction Add Fraction
Acenaphthene 4-Chloro-3-methy1 phenol
1,4-01chlorobenzene 2,4-Dichlorophenol
Hexachlorobutadiene 2-N1trophenol
N-Ni troso-di-n-pheny1 ami ne Phenol
01-n-octy1phthalate Pentachlorophenol
Fluoranthene 2,4,6-Trichlorophenol
Benzo(a)pyrene
8270 - 15
Revision
Date September 1986
-------
7.4 Dally GC/MS calibration;
7.4.1 Prior to analysis of samples, the GC/MS tuning standard must
be analyzed. A 50-ng injection of DFTPP must result in a mass spectrum
for DFTPP which meets the criteria given in Table 3. These criteria must
be demonstrated during each 12-hr shift.
7.4.2 A calibration standard(s) at mid-level concentration
containing all semi volatile analytes, including all required surrogates,
must be performed every 12-hr during analysis. Compare the response
factor data from the standards every 12-hr with the average response
factor from the initial calibration for a specific instrument as per the
SPCC (Paragraph 7.4.3) and CCC (Paragraph 7.4.4) criteria.
7.4.3 System Performance Check Compounds (SPCCs): A system
performance check must be made during every 12 hr shift. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the Initial
calibration. If the minimum response factors are not met, the system
must be evaluated, and corrective action must be taken before sample
analysis begins. The minimum RF for semivolatile SPCCs is 0.050. Some
possible problems are standard mixture degradation, Injection port inlet
contamination, contamination at the front end of the analytical column,
and active sites in the column or chromatographic system. This check
must be met before analysis begins.
7.4.4 Calibration Check Compounds (CCCs): After the system
performance check is met, CCCs listed in Table 4 are used to check the
validity of the initial calibration. Calculate the percent difference
using:
RF - RF
=
RF
r
% Difference = — - - X 100
i
where:
RFj = average response factor from initial calibration.
RFC = response factor from current verification check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. If the percent
difference for each CCC is less than 30%, the initial calibration is
assumed to be valid. If the criterion is not met (>30% difference) for
any one CCC, corrective action MUST be taken. Problems similar to those
listed under SPCCs could affect this criterion. If no source of the
problem can be determined after corrective action has been taken, a new
five-point calibration MUST be generated. This criterion MUST be met
before sample analysis begins.
8270 - 16
Revision
Date September 1986
-------
7.4.5 The Internal standard responses and retention times 1n the
calibration check standard must be evaluated Immediately after or during
data acquisition. If the retention time for any Internal standard
changes by more than 30 sec from the last check calibration (12 hr), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. If the EICP area for any of the Internal
standards changes by a factor of two (-50% to +100%) from the last dally
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate.
7.5 GC/MS analysis;
7.5.1 It is highly recommended that the extract be screened on a
GC/FID or GC/PID using the same type of capillary column. This will
minimize contamination of the GC/MS system from unexpectedly high
concentrations of organic compounds.
7.5.2 Spike the 1-mL extract obtained from sample preparation with
10 uL of the internal standard solution just prior to analysis.
7.5.3 Analyze the 1-mL extract by GC/MS using a 30-m x 0.25-mm (or
0.32-mm) si 11 cone-coated fused-sH1ca capillary column. The volume to be
Injected should ideally contain 100 ng of base/neutral and 200 ng of add
surrogates (for a 1 uL Injection). The recommended GC/MS operating
conditions to be used are specified in Paragraph 7.3.
7.5.4 If the response for any quantitation ion exceeds the initial
calibration curve range of the GC/MS system, extract dilution must take
place. Additional internal standard must be added to the diluted extract
to maintain the required 40 ng/uL of each internal standard in the
extracted volume. The diluted extract must be reanalyzed.
7.5.5 Perform all qualitative and quantitative measurements as
described in Paragraph 7.6. Store the extracts at 4*C, protected from
light 1n screw-cap vials equipped with unpierced Teflon-lined septa.
7.6 Data Interpretation;
7.6.1 Qualitative analysis:
7.6.1.1 An analyte (e.g., those listed in Table 1) is
identified by comparison of the sample mass spectrum with the mass
spectrum of a standard of the suspected compound (standard reference
spectrum). Mass spectra for standard reference should be obtained
on the user's GC/MS within the same 12 hours as the sample analysis.
These standard reference spectra may be obtained through analysis of
the calibration standards. Two criteria must be satisfied to verify
identification: (1) elution of sample component at the same GC
relative retention time (RRT) as the standard component; and (2)
correspondence of the sample component and the standard component
mass spectrum.
8270 - 17
Revision 0
Date September 1986
-------
7.6.1.1.1 The sample component RRT must compare within
+0.06 RRT units of the RRT of the standard component. For
reference, the standard must be run within the same 12 hrs as
the sample. If coelutlon of Interfering components prohibits
accurate assignment of the sample component RRT from the total
ion chromatogram, the RRT should be assigned by using extracted
ion current profiles for ions unique to the component of
interest.
7.6.1.1.2 All ions present in the standard mass spectra
at a relative intensity greater than 10% (most abundant ion in
the spectrum equals 100% must be present in the sample
spectrum.
7.6.1.1.3 The relative intensities of ions specified in
Paragraph 7.6.1.1.2 must agree within plus or minus 20% between
the standard and sample spectra. (Example: For an ion with an
abundance of 50% in the standard spectra, the corresponding
sample abundance must be between 30 and 70 percent.
7.6.1.2 For samples containing components not associated with
the calibration standards, a library search may be made for the
purpose of tentative Identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Computer generated library search routines should
not use normalization routines that would misrepresent the library
or unknown spectra when compared to each other. Only after visual
comparison of sample spectra with the nearest library searches will
the mass spectral interpretation specialist assign a tentative
identification. Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference spectrum
(ions >10% of the most abundant ion) should be present in the sample
spectrum.
(2) The relative intensities of the major ions should agree within
+20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should be
present in sample the spectrum.
(4) Ions present in the sample spectrum but not 1n the reference
spectrum should be reviewed for possible background contamination or
presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coeluting peaks.
Data system library reduction programs can sometimes create these
discrepancies.
8270 - 18
Revision 0
Date September 1986
-------
7.6.2 Quantitative analysis:
7.6.2.1 When a compound has been Identified, the quantltatlon
of that compound will be based on the Integrated abundance from the
EICP of the primary characteristic 1on. Quantltatlon will take
place using the Internal standard technique. The Internal standard
used shall be the one nearest the retention time of that of a given
analyte (e.g., see Table 5).
7.6.2.2 Calculate the concentration of each Identified analyte
1n the sample as follows:
Water:
(Ax)(Is)(Vt)
concentration (ug/L) = (A
where:
Ax = Area of characteristic 1on for compound being
measured.
Is = Amount of Internal standard Injected (ng).
Vt = Volume of total extract, taking Into account dilutions
(I.e., a l-to-10 dilution of a 1-mL extract will mean
Vt = 10,000 uL. If half the base/neutral extract and
half the add extract are combined, Vt = 2,000.
A^s = Area of characteristic 1on for the Internal standard.
RF = Response factor for compound being measured (Paragraph
7.3.3).
V0 = Volume of water extracted (ml).
\l\ = Volume of extract Injected (uL).
Sed1ment/Spn Sludge (on a dry-weight basis) and Waste (normally on
a wet-weight basis;
(AJ(IS)(V )
concentration (ug/kg) = (A.S)(RF)(V.)(W$)(D)
where:
AXI Is» Vti Ais* RF' vi = same as ^or water-
Ws = weight of sample extracted or diluted in grams.
D = (100 - % moisture In sample)/100, or 1 for a wet-weight
basis.
8270 - 19
Revision 0
Date September 1986
-------
TABLE 5. SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
1,4-D1chlorobenzene-d4
Naphthalene-ds
Acenaphthene-djo
Aniline
Benzyl alcohol
Bi s(2-chloroethyl)ether
Bi s(2-chloroi sopropyl)ether
2-Chlorophenol
1,3-Di chlorobenzene
1,4-Dichlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-N1trosodlmethyl amine
N-N1 troso-d1-n-propylamine
Phenol
Phenol-ds (surr.)
2-P1col1ne
Acetophenone
Benzole acid
B1s(2-chloroethoxy)methane
4-Chloroanil1ne
4-Chloro-3-methy1 phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl -
phenethylamine
2,4-Dimethyl phenol
Hexachlorobutadi ene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-ds (surr.)
2-N1trophenol
N-N1 troso-'d1 -n-butyl ami ne
N-N1trosop1per1d1ne
1,2,4-Tri chlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthal ene
2-Chloronaphthalene
4-Chlorophenyl
phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorob1phenyl
(surr.)
Hexachlorocyclo-
pentadlene
l-Naphthylam1ne
2-Naphthylam1ne
2-Nitroan1l1ne
3-Nitroan1line
4-N1troan1line
4-N1trophenol
Pentachlorobenzene
1,2,4,5-Tetra-
chlorobenzene
2,3,4,6-Tetra-
chlorophenol
2,4,6-Tribromo-
phenol (surr.)
2,4,6-Trichloro-
phenol
2,4,5-Trichloro-
phenol
(surr.) = surrogate
8270 - 20
Revision 0
Date September 1986
-------
TABLE 5. SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION (Continued)
Phenanthrene-dio
Chrysene-di2
Perylene-dj2
4-Amlnoblphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Di ni tro-2-methy1 phenol
Diphenylamine
1,2-Di phenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Ni trosodi phenylami ne
Pentachlorophenol
Pentachloroni trobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bi s(2-ethylhexyl)phthalate
Butyl benzylphthalate
Chrysene
3,3'-Di chlorobenzidi ne
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-di4 (surr.)
Benzo(b)fluor-
anthene
Benzo(k)fluor-
anthene
Benzo(g,h,i)
perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
D1benz(a,h)
anthracene
7,12-Dimethylbenz-
(a)anthracene
D1-n-octy1phthalate
Indeno(l,2,3-cd)
pyrene
3-Methylchol-
anthrene
(surr.) = surrogate
8270 - 21
Revision 0
Date September 1986
-------
7.6.2.3 Where applicable, an estimate of concentration for
noncallbrated components 1n the sample should be made. The formulas
given above should be used with the following modifications: The
areas Ax and AIS should be from the total. ion chromatograms and the
RF for the compound should be assumed to be 1. The concentration
obtained should be reported Indicating (1) that the value Is an
estimate and (2) which Internal standard was used to determine
concentration. Use the nearest Internal standard free of
Interferences.
7.6.2.4 Report results without correction for recovery data.
When duplicates and spiked samples are analyzed, report all data
obtained with the sample results.
7.6.2.5 Quantisation of multicomponent compounds (e.g.,
Aroclors) 1s beyond the scope of Method 8270. Normally,
quantltation is performed using a GC/ECD by Method 8080.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods 1s required to operate a
formal quality control program. The minimum requirements of this program
consist of an Initial demonstration of laboratory capability and an ongoing
analysis of spiked samples to evaluate and document quality data. The labor-
atory must maintain records to document the quality of the data generated.
Ongoing data quality checks are compared with established performance criteria
to determine 1f the results of analyses meet the performance characteristics
of the method. When results of sample spikes indicate atypical method
performance, a quality control check standard must be analyzed to confirm that
the measurements were performed in an 1n-control mode of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent water blank, that Interferences from the
analytical system, glassware, and reagents are under control. Each time a set
.of samples 1s extracted or there is a change in reagents, a reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 The experience of the analyst performing GC/MS analyses is
Invaluable to the success of the methods. Each day that analysis is
performed, the daily calibration standard should be evaluated to determine if
the chromatographic system is operating properly. Questions that should be
asked are: Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g, columnichanged), recalibration of the system must take place.
8270 - 22
Revision 0
Date September 1986
-------
8.4 Required Instrument QC Is found 1n the following sections:
8.4.1 The GC/MS system must be tuned to meet the DFTPP
specifications in Section 7.3.1 and 7.4.1.
8.4.2 There must be an initial calibration of the GC/MS system as
specified in 7.3.
8.4.3 The GC/MS system must meet the SPCC criteria specified 1n
7.4.3 and the CCC criteria in 7.4.4, each 12 hr.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality (QC) check sample concentrate is required
containing each analyte at a concentration of 100 ug/mL 1n acetone. The
QC check sample concentrate may be prepared from pure standard materials
or purchased as certified solutions. If prepared by the laboratory, the
QC check sample concentrate must be made using stock standards prepared
independently from those used for calibration.
8.5.2 Using a pipet, prepare QC check samples at a concentration of
100 ug/L by adding 1.00 ml of QC check sample concentrate to each of four
1-L aliquots of reagent water.
8.5.3 Analyze the well-mixed QC check samples according to the
method beginning in Section 7.1 with extraction of the samples.
8.5.4 Calculate the average recovery (X) in ug/L, and the standard
deviation of the recovery (s) in ug/L, for each analyte of interest using
the four results.
8.5.5 For each analyte compare s and 7. with the corresponding
acceptance criteria for precision and accuracy, respectively, found 1n
Table 6. If s and 7 for all analytes meet the acceptance criteria, the
system performance 1s acceptable and analysis of actual samples can
begin. If any individual s exceeds the precision limit or any individual
7 falls outside the range for accuracy, then the system performance 1s
unacceptable for that analyte.
NOTE: The large number of analytes in Table 6 present a substantial
probability that one or more will fail at least one of the
acceptance criteria when all analytes of a given method are
analyzed.
8.5.6 When one or more of the analytes tested fall at least one of
the acceptance criteria, the analyst must proceed according to Section
8.5.6.1 or 8.5.6.2.
8.5.6.1 Locate and correct the source of the problem and
repeat the test for all analytes of interest beginning with Section
8.5.2.
8270 - 23
Revision 0
Date September 1986
-------
TABLE 6. QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Benzo (ghl)perylene
Benzyl butyl phthalate
/J-BHC
5-BHC
B1 s (2-chl oroethyl ) ether
B1 s (2-chl oroethoxy)methane
B1 s (2-chl orol sopropyl ) ether
Bi s (2-ethy 1 hexy 1 ) phthal ate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4, 4 '-DDE
4,4'-DDT
Dibenzo (a, h) anthracene
D1-n-butyl phthalate
l,2-D1chl orobenzene
1 , 3-D1 chl orobenzene
l,4-D1chl orobenzene
3,3'-D1chlorobenz1d1ne
D1eldr1n
Dlethyl phthalate
Dimethyl phthalate
2,4-D1n1trotoluene
2,6-D1m'trotoluene
D1-n-octyl phthal ate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl oroethane
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
24.5
Range
for 7
(ug/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
55.2-100.0
Range
P. Ps
(%)
47-145
33-145
D-166
27.133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
40-113
8270 - 24
Revision 0
Date September 1986
-------
TABLE 6. QC ACCEPTANCE CRITERIA3 - Continued
Parameter
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-N1 trosodl -n-propy 1 ami ne
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-01 methyl phenol
2,4-D1m'trophenol
2-Methyl -4 , 6-dl n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
Range
for 7
(ug/L)
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
Range
P, Ps
(X)
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
p, ps = Percent recovery measured.
D = Detected; result must be greater than zero.
3Cr1ter1a from 40 CFR Part 136 for Method 625. These criteria are based
directly on the method performance data 1n Table 7. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 7.
8270 - 25
Revision
Date September 1986
-------
8.5.6.2 Beginning with Section 8.5.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of Interest beginning with Section
8.5.2.
8.6 The laboratory must, on an ongoing basis, analyze a reagent blank, a
matrix spike, and a matrix spike duplicate/duplicate for each analytical batch
(up to a maximum of 20 samples/batch) to assess accuracy. For laboratories
analyzing one to ten samples per month, at least one spiked sample per month
1s required.
8.6.1 The concentration of the spike 1n the sample should be
determined as follows:
8.6.1.1 If, as 1n compliance monitoring, the concentration of
a specific analyte 1n the sample 1s being checked against a
regulatory concentration limit, the spike should be at that limit or
1 to 5 times higher than the background concentration determined 1n
Section 8.6.2, whichever concentration would be larger.
8.6.1.2 If the concentration of a specific analyte 1n the
sample 1s not being checked against a limit specific to that
analyte, the spike should be at 100 ug/L or 1 to 5 times higher than
the background concentration determined 1n Section 8.6.2, whichever
concentration would be larger.
8.6.1.3 If 1t Is Impractical to determine background levels
before spiking (e.g., maximum holding times will be exceeded), the
spike concentration should be at (1) the regulatory concentration
limit, 1f any; or, 1f none (2) the larger of either 5 times higher
than the expected background concentration or 100 ug/L.
8.6.2 Analyze one sample aliquot to determine the background
concentration (B) of each analyte. If necessary, prepare a new QC check
sample concentrate (Section 8.5.1) appropriate for the background
concentration 1n the sample. Spike a second sample aliquot with 1.00 ml
of the QC check sample concentrate and analyze 1t to determine the
concentration after spiking (A) of each analyte. Calculate each percent
recovery (p) as 100(A-B)%/T, where T Is the known true value of the
spike. .
8.6.3 Compare the percent recovery (p) for each analyte with the
corresponding QC acceptance criteria found 1n Table 6. These acceptance
criteria were calculated to Include an allowance for error 1n measurement
of both the background and spike concentrations, assuming a spike to
background ratio of 5:1. This error will be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1. If spiking
was performed at a concentration lower than 100 ug/L, the analyst must
use either the QC acceptance criteria presented 1n Table 6, or optional
QC acceptance criteria calculated for the specific spike concentration.
To calculate optional acceptance criteria for the recovery of an analyte:
8270 4- 26
Revision 0
Date September 1986
-------
(1) Calculate accuracy (x1) using the equation found 1n Table 7,
substituting the spike concentration (T) for C; (2) calculate overall
precision (S1) using the equation 1n Table 7, substituting x1 for X; (3)
calculate the range for recovery at the spike concentration as (lOOx'/T)
+ 2.44(100S'/T)%.
8.6.4 If any Individual p falls outside the designated range for
recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be
analyzed as described 1n Section 8.7.
8.7 If any analyte fails the acceptance criteria for recovery in Section
8.6, a QC check standard containing each analyte that failed must be prepared
and analyzed.
NOTE: The frequency for the required analysis of a QC check standard
will depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the laboratory.
If the entire list of analytes in Table 6 must be measured in the sample
1n Section 8.6, the probability that the analysis of a QC check standard
will be required is high. In this case the QC check standard should be
routinely analyzed with the spiked sample.
8.7.1 Prepare the QC check standard by adding 1.0 ml of the QC
check sample concentrate (Section 8.5.1 or 8.6.2) to 1 L of reagent
water. The QC check standard needs only to contain the analytes that
failed criteria in the test in Section 8.6.
8.7.2 Analyzed the QC check standard to determine the concentration
measured (A) of each analyte. Calculate each percent recovery (ps) as
100 (A/T)%, where T is the true value of the standard concentration.
8.7.3 Compare the percent recovery (ps) for each analyte with the
corresponding QC acceptance criteria found in Table 6. Only analytes
that failed the test 1n Section 8.6 need to be compared with these
criteria. If the recovery of any such analyte falls outside the
designated range, the laboratory performance for that analyte is judged
to be out of control, and the problem must be Immediately Identified and
corrected. The analytical result for that analyte 1n the unspiked sample
1s suspect and may not be reported for regulatory compliance purposes.
8.8 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After
the analysis of five spiked samples (of the same matrix) as in Section 8.6,
calculate the average percent recovery (JJ) and the standard deviation of the
percent recovery (sp). Express the accuracy assessment as a percent recovery
interval from p - 2sp to p + 2sp. If p = 90% and sp = 10%, for example, the
accuracy interval is expressed as 70-110%. Update the accuracy assessment for
each analyte on a regular basis (e.g. after each five to ten new accuracy
measurements). > .
8.9 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8270 - 27
Revision 0
Date September 1986
-------
TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Aldrln
Anthracene
Benzo (a) anthracene
Chloroethane
Benzo (b) fl uoranthene
Benzo (k)fl uoranthene
Benzo(a)pyrene
Benzo (ghi)perylene
Benzyl butyl phthalate
/7-BHC
5-BHC
Bis(2-chloroethyl) ether
B1 s (2-chl oroethoxy) methane
Bi s (2-chl orol sopropyl ) ether
B1 s (2-ethy 1 hexy 1 ) phthal ate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE.
4,4'-DDT
Dibenzo (a, h) anthracene
Dl-n-butyl phthalate
1,2-Dichl orobenzene
1 , 3-Di chl orobenzene
l,4-D1chlorobenzene
3,3'-D1chlorobenzid1ne
Dleldrin
D1 ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di -n-octyl phthal ate
Endosulfan sulfate
Endrln aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl oroethane
Accuracy, as
recovery, x'
(ug/L)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
Single analyst
precision, sr'
(ug/L)
0.157-0.12
0.247-1.06
0.277-1.28
0.217-0.32
0.157+0.93
0.147-0.13
0.227+0.43
0.197+1.03
0.227+0.48
0.297+2.40
0.187+0.94
0.207-0.58
0.347+0.86
0.357-0.99
0.167+1.34
0.247+0.28
0.267+0.73
0.137+0.66
0.077+0.52
0.207-0.94
0.287+0.13
0.297-0.32
0.267-1.17
0.427+0.19
0.307+8.51
0.137+1.16
0.207+0.47
0.257+0.68
0.247+0.23
0.287+7.33
0.207-0.16
0.287+1.44
0.547+0.19
0.127+1.06
0.147+1.26
0.217+1.19
0.127+2.47
0.187+3.91
0.227-0.73
0.127+0.26
0.247-0.56
0.337-0.46
0.187-0.10
0.197+0.92
0.177+0.67
Overall
precision,
S1 (ug/L)
0.217-0.67
0.267-0.54
0.437+1.13
0.277-0.64
0.267-0.21
0.177-0.28
0.297+0.96
0.357+0.40
0.327+1.35
0.517-0.44
0.537+0.92
0.307+1.94
0.937-0.17
0.357+0.10
0.267+2.01
0.257+1.04
0.367+0.67
0.167+0.66
0.137+0.34
0.307-0.46
0.337-0.09
0.667-0.96
0.397-1.04
0.657-0.58
0.597+0.25
0.397+0.60
0.247+0.39
0.417+0.11
0.297+0.36
0.477+3.45
0.267-0.07
0.527+0.22
1.057-0.92
0.217+1.50
0.197+0.35
0.377+1.19
0.637-1.03
0.737-0.62
0.287-0.60
0.137+0.61
0.507-0.23
0.287+0.64
0.437-0.52
0.267+0.49
0.177+0.80
8270 - 28
Revision 0
Date September 1986
-------
TABLE 7. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3 -
Continued
Parameter
Indeno(l , 2, 3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Ni trosodi -n-propyl ami ne
PCB-1260
Phenanthrene
Pyrene
1,2, 4-TH chl orobenzene
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-D1nitrophenol
2-Methyl -4 , 6-di ni trophenol
2-Nitrophenol
4-Ni trophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x1
(ug/L)
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, sr'
(ug/L)
0.297+1.46
0.277+0.77
0.217-0.41
0.197+0.92
0.277+0.68
0.357+3.61
0.127+0.57
0.167+0.06
0.157+0.85
0.237+0.75
0.187+1.46
0.157+1.25
0.167+1.21
0.387+2.36
0.107+42.29
0.167+1.94
0.387+2.57
0.247+3.03
0.267+0.73
0.167+2.22
Overall
precision,
S1 (ug/L)
0.507-0.44
0.337+0.26
0.307-0.68
0.277+0.21
0.447+0.47
0.437+1.82
0.157+0.25
0.157+0.31
0.217+0.39
0.297+1.31
0.287+0.97
0.217+1.28
0.227+1.31
0.427+26.29
0.267+23.10
0.277+2.60
0.447+3.24
0.307+4.33
0.357+0.58
0.227+1.81
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, in ug/L.
S1 = Expected interlaboratory standard deviation of measurements at an
average concentration found of 7, in ug/L.
C = True value for the concentration, in ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
8270 - 29
Revision 0
Date September 1986
-------
8.9.1 For each sample analyzed, calculate the percent recovery of
each surrogate 1n the sample.
8.9.2 Once a minimum of thirty samples of the same matrix have been
analyzed, calculate the average percent recovery (P) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.9.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
8.9.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed 1n Table 8. The limits given 1n Table 8 are multi-
laboratory performance based limits for soil and aqueous samples, and
therefore, the single-laboratory limits established in Paragraph 8.9.3
must fall within those given in Table 8 for these matrices.
8.9.5 If recovery is not within limits, the following procedures
are required.
• Check to be sure there are no errors in calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
• Reextract and reanalyze the sample 1f none of the above are
a problem or flag the data as "estimated concentration."
8.9.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrix-by-matrix basis, annually.
8.10 It 1s recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the Identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column, specific element detector, or mass spectrometer must
be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
8270 - 30
Revision
Date September 1986
-------
TABLE 8. SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Low/Medium Low/Medium
Surrogate Compound Water Soil/Sediment
Nitrobenzene-ds 35-114 23-120
2-Fluorobiphenyl 43-116 30-115
p-Terphenyl-di4 33-141 18-137
Phenol-d6 10-94 24-113
2-Fluorophenol 21-100 25-121
2,4,6-Tribromophenol 10-123 19-122
8270 - 31
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 Method 8250 was tested by 15 laboratories using reagent water,
drinking water, surface water, and Industrial wastewaters spiked at six
concentrations over the range 5-1,300 ug/L. Single operator accuracy and
precision, and method accuracy were found to be directly related to the
concentration of the analyte and essentially Independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act, Method 625," October 26,
1984.
2. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 1J5, 58-63, 1983.
4. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.
5. "Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.
6. "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Adds, and
Pesticides," Final Report for EPA Contract 68-03-3102 (1n preparation).
7. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
8270 - 32
Revision
Date September 1986
-------
METHOD 8270
GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOUATILE ORGANICS:
CAPILLARY COLUMN TECHNIQUE
7. 1
Prepare cample
using Method
3540 or 3550
7. 1
Prepare cample
using Method
3510 or 3520
Prepare
cample using
Method 3540.
3550 or 3560
7.2
Cleanup extract
7.3
Set GC/MS
operating
conditions and
perform initial
calibration
7.4
Perform dally GC/MS
calibration with
SPCCc and CCCc prior
to analyclc of
camples
o
8270 - 33
Revision 0
Date September 1986
-------
METHOD 8270
GAS CHRONATOGRAPHY/MASS SPECTHOMETRY FOR SEMIVOLATILE ORGANICS:
CAPILLARY COLUMN TECHNIQUE
(Continued)
7.5. 1
o
Screen
extract
on GC/FIO or
GC/PIO to elim-
inate too-high
concentration
7.5
7.6.1
Identify
> enalyte
by comparing
the cample and
standard mase
spectra
Analyze extract by
GC/HS using
silIcone-coated
fueed-sillea
capillary column
7.6.2
Calculate
concentration
of each
Identified
analyte'
Does response
exceed Initial
7.6.2.4
Report results
f Stop J
8270 - 34
Revision o
Date September 1986
-------
METHOD 8280
THE ANALYSIS OF POLYCHLORINATED DIBENZO-P-DIOXINS
AND POLYCHLORINATED DIBENZOFURANS
1.0 SCOPE AND APPLICATION
1.1 This method is appropriate for the determination of tetra-, penta-,
hexa-, hepta-, and octachlorinated dibenzo-p-dioxins (PCDD's) and dibenzo-
furans (PCDF's) in chemical wastes including still bottoms, fuel oils,
sludges, fly ash, reactor residues, soil and water.
1.2 The sensitivity of this method is dependent upon the level of
interferents within a given matrix. Proposed quantification levels for target
analytes were 2 ppb in soil samples, up to 10 ppb in other solid wastes and
10 ppt in water. Actual values have been shown to vary by homologous series
and, to a lesser degree, by individual isomer. The total detection limit for
each CDD/CDF homologous series is determined by multiplying the detection
limit of a given isomer within that series by the number of peaks which can be
resolved under the gas chromatographic conditions.
1.3 Certain 2,3,7,8-substituted congeners are used to provide
calibration and method recovery information. Proper column selection and
access to reference isomer standards, may in certain cases, provide isomer
specific data. Special instructions are included which measure 2,3,7,8-
substituted congeners.
1.4 This method is recommended for use only by analysts experienced with
residue analysis and skilled in mass spectral analytical techniques.
1.5 Because of the extreme toxicity of these compounds, the analyst must
take necessary precautions to prevent exposure to himself, or to others, of
materials known or believed to contain PCDD's or PCDF's. Typical infectious
waste incinerators are probably not satisfactory devices for disposal of
materials highly contaminated with PCDD's or PCDF's. A laboratory planning to
use these compounds should prepare a disposal plan to be reviewed and approved
by EPA's Dioxin Task Force (Contact Conrad Kleveno, WH-548A, U.S. EPA, 401 M
Street S.W., Washington, D.C. 20450). Additional safety instructions are
outlined in Appendix B.
2.0 SUMMARY OF THE METHOD
2.1 This procedure uses a matrix-specific extraction, analyte-specific
cleanup, and high-resolution capillary column gas chromatography/low
resolution mass spectrometry (HRGC/LRMS) techniques.
2.2 If interferents are encountered, the method provides selected
cleanup procedures to aid the analyst in their elimination. The analysis flow
chart is shown in Figure 1.
8280 - 1
Revision 0
Date September 1986
-------
Complex
Waste
Sample
(1) Add Internal Standards: 13C12-PCDD's
and I3C12-PCDF's.
(2) Perform matrix-specific extraction.
Sample
Extract
(1) Wash with 20% KOH
(2) Wash with 5% Nad
(3) Wash with cone. H2S04
(4) Wash with 5% NaCl
(5) Dry extract
(6) Solvent exchange
(7) Alumina column
60% CH2Cl2/hexane
Fraction
(1) Concentrate eluate
(2) Perform carbon column cleanup
(3) Add recovery standard(s)-13C12-l,2,3,4-TCDD
Analyze by GC/MS
Figure 1. Method 8280 flow chart for sample extraction and cleanup as
used for the analysis of PCDD's and PCDF's 1n complex waste samples.
8280 - 2
Revision p
Date September 1986
-------
3.0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines which may cause
misinterpretation of chromatographic data. All of these materials must be
demonstrated to be free from interferents under the conditions of analysis by
running laboratory method blanks.
3.2 The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all glass
systems may be required.
3.3 Interferents co-extracted from the sample will vary considerably
from source to source, depending upon the industrial process being sampled.
PCDD's and PCDF's are often associated with other interfering chlorinated
compounds such as PCB's and polychlorinated diphenyl ethers which may be found
at concentrations several orders of magnitude higher than that of the analytes
of interest. Retention times of target analytes must be verified using
reference standards. These values must correspond to the retention time
windows established in Section 6-3. While certain cleanup techniques are
provided as part of this method, unique samples may require additional cleanup
techniques to achieve the method detection limit (Section 11.6) stated in
Table 8.
3.4 High resolution capillary columns are used to resolve as many PCDD
and PCDF isomers as possible; however, no single column is known to resolve
all of the isomers.
3.5 Aqueous samples cannot be aliquoted from sample containers. The
entire sample must be used and the sample container washed/rinsed out with the
extracting solvent.
4.0 APPARATUS AND MATERIALS
4.1 Sampling equipment for discrete or composite sampling;
4.1.1 Grab sample bottle—amber glass, 1-liter or 1-quart volume.
French or Boston Round design is recommended. The container must be acid
washed and solvent rinsed before use to minimize interferences.
4.1.2 Bottle caps—threaded to screw onto the sample bottles. Caps
must be lined with Teflon. Solvent washed foil, used with the shiny side
toward the sample, may be substituted for Teflon if the sample is not
corrosive. Apply tape around cap to completely seal cap to bottom.
4.1.3 Compositing equipment—automatic or manual compositing
system. No tygon or rubber tubing may be used, and the system must
incorporate glass sample containers for the collection of a minimum of
250 ml_. Sample containers must be kept refrigerated after sampling.
4.2 Water bath—heated, with concentric ring cover, capable of
temperature control (+2°C). The bath should be used in a hood.
8280 - 3
Revision 0
Date September 1986
-------
4.3 Gas chromatograph/mass spectrometer data system;
4.3.1 Gas chromatograph: An analytical system with a temperature-
programmable gas chromatograph and all required accessories Including
syringes, analytical columns, and gases.
4.3.2 Fused silica capillary columns are required. As shown 1n
Table 1, three columns were evaluated using a column performance check
mixture containing 1,2,3,4-TCDD, 2,3,7,8-TCDD, 1,2,3,4,7 PeCDD,
1,2,3,4,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, and 2,3,7,8-TCDF.
The columns include the following: (a) 50-m CP-Sil-88 programmed 60°-
190' at 20*/minute, then 190*-240* ,at 5°/minute; (b) DB-5 (30-m x 0.25-mm
I.D.; 0.25-um film thickness) programmed 170° for 10 minutes, then 170*-
320* at SVminute, hold at 320°C for 20 minutes; (c) 30-m SP-2250
programmed 70°-320° at lO'/minute. Column/conditions (a) provide good
separation of 2,3,7,8-TCDD from the other TCDD's at the expense of longer
retention times for higher homologs. Column/conditions (b) and (c) can
also provide acceptable separation of 2,3,7,8-TCDD. Resolution of
2,3,7,8-TCDD from the other TCDD's is better on column (c), but column
(b) is more rugged, and may provide better separation from certain
classes of interferents. Data presented in Figure 2 and Tables 1 to 8 of
this Method were obtained using a DB-5 column with temperature
programming described in (b) above. However, any capillary column which
provides separation of 2,3,7,8-TCDD from all other TCDD isomers
equivalent to that specified in Section 6.3 may be used; this separation
must be demonstrated and documented using the performance test mixture
described 1n Paragraph 6.3.
4.3.3 Mass spectrometer: A,low resolution instrument is specified,
utilizing 70 volts (nominal) electron energy in the electron impact
lonization mode. The system must be capable of selected ion monitoring
(SIM) for at least 11 ions simultaneously, with a cycle time of 1 sec or
less. Minimum integration time for SIM is 50 ms per m/z. The use of
systems not capable of monitoring 11 ions simultaneously will require the
analyst to make multiple injections.
4.3.4 GC/MS .Interface: Any GC-to-MS interface that gives an
acceptable calibration response for each analyte of interest at the
concentration required and achieves the required tuning performance
criteria (see Paragraphs 6.1.-6.3) may be used. GC-to-MS interfaces
constructed of all glass or glass-lined materials are required. Glass
can be deactivated by silanizing with dichlorodimethylsilane. Inserting
a fused silica column directly into the MS source is recommended; care
must be taken not to expose the end of the column to the electron beam.
4.3.5 Data system: A computer system must be Interfaced to the
mass spectrometer. The system must allow for the continuous acquisition
and storage on machine-readable media of all data obtained throughout the
duration of the chromatographic program. The computer must have software
that can search any GC/MS data file for ions of a specific mass and can
plot such ion abundances versus time or scan number. This type of plot
8280 - 4
Revision
Date September 1986
-------
1s defined as an Selected Ion Current Profile (SICP). Software must also
be able to integrate the abundance, 1n any SICP, between specified time
or scan number limits.
4.4 Pipets-Disposable, Pasteur, 150-mm long x 5-mrn I.D. (Fisher
Scientific Company, No. 13-678-6A, or equivalent).
4.4.1 Pipet, disposable, serological 10-mL (American Scientific
Products No. P4644-10, or equivalent) for preparation of the carbon
column specified in Paragraph 4.19.
4.5 Amber glass bottle (500-mL, Teflon-lined screw-cap).
4.6 Reacti-vial 2-mL, amber glass (Pierce Chemical Company). These
should be silanized prior to use.
4.7 500-mL Erlenmeyer flask (American Scientific Products Cat. No. f4295
500fO) fitted with Teflon stoppers (ASP No. S9058-8, or equivalent).
4.8 Wrist Action Shaker (VWR No. 57040-049, or equivalent).
4.9 125-mL and 2-L Separatory Funnels (Fisher Scientific Company,
No. 10-437-5b, or equivalent).
4.10 500-mL Kuderna-Danish fitted with a 10-mL concentrator tube and
3-ball Snyder column (Ace Glass No. 6707-02, 6707-12, 6575-02, or equivalent).
4.11 Teflon boiling chips (Berghof/American Inc., Main St., Raymond, New
Hampshire 03077, No. 15021-450, or equivalent). Wash with hexane prior to
use.
4.12 300-mm x 10.5-mm glass chromatographlc column fitted with Teflon
stopcock.
4.13 15-mL conical concentrator tubes (Kontes No. K-288250, or
equivalent).
4.14 Adaptors for concentrator tubes (14/20 to 19/22) (Ace Glass No.
9092-20, or equivalent).
4.15 Nitrogen blowdown apparatus (N-Evap (reg. trademark) Analytical
Evaporator Model 111, Organomation Associates Inc., Northborough,
Massachusetts or equivalent). Teflon tubing connection to trap and gas
regulator is required.
4.16 Microflex conical vials 2.0-mL (Kontes K-749000, or equivalent).
4.17 Filter paper (Whatman No. 54, or equivalent). Glass fiber filters
or glass wool plugs are also recommended.
4.18 Solvent reservoir (125-mL) Kontes; (special order item) 12.5-cm
diameter, compatible with gravity carbon column.
8280 - 5
Revision 0
Date September 1986
-------
4.19 Carbon column (gravity flow); Prepare carbon/silica gel packing
material bymlx1ng5percent (byweight) active carbon AX-21 (Anderson
Development Co., Adraln, Michigan), pre-washed with methanol and dried Iji
vacuo at 110'C and 95 percent (by weight) Silica gel (Type 60, EM reagent 70
to 230 mesh, CMS No. 393-066) followed by activation of the mixture at 130*
for 6 hr. Prepare a 10-mL disposable serologlcal plpet by cutting off each
end to achieve a 4-1n. column. F1re polish both ends; flare 1f desired.
Insert a glass-wool plug at one end and pack with 1 g of the carbon/siHca gel
mixture. Cap the packing with a glass-wool plug. (Attach reservoir to column
for addition of solvents).
Option: Carbon column (HPLC): A sllanlzed glass HPLC column (10 mm x 7
cm), or equivalent, which contains 1 g of a packing prepared by mixing 5
percent (by weight) active carbon AX-21, (Anderson Development Co., Adrian,
Michigan), washed with methanol and dried in vacuo at 110*C, and 95 percent
(by weight) 10 urn silica (Spherisorb S10W from Phase Separations, Inc.,
Norwalk, Connecticut). The mixture must then be stirred and sieved through a
38-um screen (U.S. Sieve Designation 400-mesh, American Scientific Products,
No. S1212-400, or equivalent) to remove any clumps.1
4.20 HPLC pump with loop valve (1.0 ml) Injector to be used 1n the
optional carbon column cleanup procedure.
4.21 Dean-Stark trap, 5- or 10-mL with T joints, (Fisher Scientific
Company, No. 09-146-5, or equivalent) condenser and 125-mL flask.
4.22 Continuous liquid-liquid extractor (Hershberg-Wolfe type, Lab Glass
No. LG-6915; or equivalent.).
4.23 Roto-evaporator, R-110. Buchi/Brinkman - American Scientific No.
E5045-10; or equivalent. ;
5.0 REAGENTS
5.1 Potassium hydroxide (ASC): 20 percent (w/v) in distilled water.
5.2 Sulfuric acid (ACS), concentrated.
5.3 Methylene chloride, hexane, benzene, petroleum ether, methanol,
trldecane, Isooctane, toluene, cyclohexane. Distilled 1n glass or highest
available purity.
5.4 Prepare stock standards in a glovebox from concentrates or neat
materials. The stock solutions (50 ppm) are stored in the dark at 4*C, and
checked frequently for signs of degradation or evaporation, especially Just
prior to the preparation of working standards.
1 The carbon column preparation and use is adapted from W. A. Korfmacher,
L. G. Rushing, D. M. Nestorick, H. C. Thompson, Jr., R. K. Mltchum, and J. R.
Kominsky, Journal of High Resolution Chromatography and Chromatography
Communications, 8, 12-19 (1985).
8280 - 6
Revision 0
Date September 1986
-------
5.5 Alumina, neutral, Super 1, Woelm, 80/200 mesh. Store in a sealed
container at room temperature in a desiccator over self-indicating silicafgel.
5.6 Prepurified nitrogen gas.
5.7 Anhydrous sodium sulfate (reagent grade): Extracted by manual
shaking with several portions of hexane and dried at 100*C.
5.8 Sodium chloride - (analytical reagent), 5 percent (w/v) in distilled
water.
6.0 CALIBRATION
6.1 Two types of calibration procedures are required. One type, initial
calibration, is required before any samples are analyzed and is required
intermittently throughout sample analyses as dictated by results of routine
calibration procedures described below. The other type, routine calibration,
consists of analyzing the column performance check solution and a
concentration calibration solution of 500 ng/mL (Paragraph 6.2). No samples
are to be analyzed until acceptable calibration as described in Paragraphs 6.3
and 6.6 is demonstrated and documented.
6.2 Initial calibration;
6.2.1 Prepare multi-level calibration standards2 keeping one of
the recovery standards and the internal standard at fixed concentrations (500
ng/mL). Additional internal standards (13Ci2-OCDD 1,000 ng/mL) are
recommended when quantification of the hepta- and octa-isomers is required.
The use of separate internal standards for the PCDF's is also recommended.
Each calibration standard should contain the following compounds:
2,3,7,8-TCDD,
1,2,3,7,8-PeCDD or any available 2,3,7,8,X-PeCDD isomer,
1,2,3,4,7,8-HxCDD or any available 2,3,7,8,X,Y-HxCDD isomer,
1,2,3,4,6,7,8-HpCDD or any available 2,3,7,8,X,Y,Z-HpCDD isomer,
2,3,7,8-TCDF
l,2,3,7,8,PeCDF or any available 2,3,7,8,X-PeCDF isomer,
1,2,3,4,7,8-HxCDF or any available 2,3,7,8,X,Y,HxCDF isomer,
1,2,3,4,6,7,8-HpCDF or any available 2,3,7,8,X,Y,Z-HpCDF isomer,
OCDD, OCDF, 13C12-2,3,7,8-TCDD, i3Ci2-l,2,3,4-TCDD and 13C12-OCDD.
2 *3Ci2-labeled analytes are available from Cambridge Isotope Laboratory,
Woburn, Massachusetts. Proper quantification requires the use of a specific
labeled isomer for each congener to be determined. When labeled PCDD's and
PCDF's of each homolog are available, their use will be required consistent
with the technique of isotopic dilution.
8280 - 7
Revision
Date September 1986
-------
Recommended concentration levels for standard analytes are 200, 500, 1,000,
2,000', and 5,000 ng/mL. These values may be adjusted in order to insure that
the analyte concentration falls within the calibration range. Two uL
injections of calibration standards should be made. However, some GC/MS
instruments may require the use of a 1-uL injection volume; if this injection
volume is used then all injections of standards, sample extracts and blank
extracts must also be made at this injection volume. Calculation of relative
response factors is described in Paragraph 11.1.2. Standards must be analyzed
using the same solvent as used in the final sample extract. A wider
calibration range is useful for higher level samples provided it can be
described within the linear range of the method, and the identification
criteria defined in Paragraph 10.4 are met. All standards must be stored in
an isolated refrigerator at 4°C and protected from light. Calibration
standard solutions must be replaced routinely after six months.
6.3 Establish operating parameters for the GC/MS system; the instrument
should be tuned to meet the isotopic ratio criteria listed in Table 3 for
PCDD's and PCDF's. Once tuning and mass calibration procedures have been
completed, a column performance check mixture^ containing the isomers listed
below should be injected into the GC/MS system:
TCDD 1,3,6,8; 1,2,8,9; 2,3,7,8; 1,2,3,4; 1,2,3,7; 1,2,3,9
PeCDD 1,2,4,6,8; 1,2,3,8,9
HxCDD 1,2,3,4,6,9; 1,2,3,4,6,7
HpCDD 1,2,3,4,6,7,8; 1,2,3,4,6,7,9
OCDD 1,2,3,4,6,7,8,9
TCDF 1,3,6,8; 1,2,8,9 ;
PeCDF 1,3,4,6,8; 1,2,3,8,9
HxCDF 1,2,3,4,6,8; 1,2,3,4,8,9
HpCDF 1,2,3,4,6,7,8; 1,2,3,4,7,8,9
OCDF 1,2,3,4,6,7,8,9
Because of the known overlap between the late-eluting tetra-isomers and
the early-eluting penta-isomers under certain column conditions, it may be
necessary to perform two injections to define the TCDD/TCDF and PeCDD/PeCDF
elution windows, respectively. Use of this performance check mixture will
enable the following parameters to be checked: (a) the retention windows for
each of the homologues, (b) the GC resolution of 2,3,7,8-TCDD and 1,2,3,4-
TCDD, and (c) the relative ion abundance criteria listed for PCDD's and PCDF's
in Table 3. GC column performance should be checked daily for resolution and
peak shape using this check mixture.
The chromatographic peak separation between 2,3,7,8-TCDD and 1,2,3,4-TCDD
must be resolved with a valley of £25 percent, where
Valley Percent = (x/y) (100)
x = measured as in Figure 2
y = the peak height of 2,3,7,8-TCDD
3 Performance check mixtures are available from Brehm Laboratory, Wright
State University, Dayton, Ohio.
8280 - 8
Revision 0
Date September 1986
-------
It is the responsibility of the laboratory to verify the conditions
suitable for maximum resolution of 2,3,7,8-TCDD from all other TCDD Isomers.
The peak representing 2,3,7,8-TCDD should be labeled and Identified as such on
all chromatograms.
6.4 Acceptable SIM sensitivity 1s verified by achieving a minimum
s1gnal-to-no1se ratio of 50:1 for the m/z 320 1on of 2,3,7,8-TCDD obtained
from Injection of the 200 ng/mL calibration standard.
6.5 From Injections of the 5 calibration standards, calculate the
relative response factors (RRF's) of analytes vs. the appropriate Internal
standards, as described in Paragraph 11.1.2. Relative response factors for
the hepta- and octa-chlorinated CDD's and CDF's are to be calculated using the
corresponding 13Ci2-octachlorinated standards.
6.6 For each analyte calculate the mean relative response factor (RRF),
the standard deviation, and the percent relative standard deviation from
triplicate determinations of relative response factors for each calibration
standard solution.
6.7 The percent relative standard deviations (based on triplicate
analysis) of the relative response factors for each calibration standard
solution should not exceed 15 percent. If this condition is not satisfied,
remedial action should be taken.
6.8 The Laboratory must not proceed with analysis of samples before
determining and documenting acceptable calibration with the criteria specified
in Paragraphs 6.3 and 6.7.
6.9 Routine calibration;
6.9.1 Inject a 2-uL aliquot of the column performance check
mixture. Acquire at least five data points for each GC peak and use the
same data acquisition time for each of the ions being monitored.
NOTE: The same data acquisition parameters previously used to
analyze concentration calibration solutions during initial
calibration must be used for the performance check solution.
The column performance check solution must be run at the
beginning and end of a 12 hr period. If the contractor
laboratory operates during consecutive 12-hr periods
(shifts), analysis of the performance check solution at the
beginning of each 12-hr period and at the end of the final
12-hr period is sufficient.
Determine and document acceptable column performance as described in
Paragraph 6.3.
6.9.2 Inject a 2-uL aliquot of the calibration standard solution at
500 ng/mL at the beginning of a 2-hr period. Determine and document
acceptable calibration as specified in Paragraph 6.3, I.e., SIM
sensitivity and relative 1on abundance criteria. The measured RRF's of
8280 - 9
Revision 0
Date September 1986
-------
.all analytes must be within +30 percent of the mean values established by
Initial analyses of the callBratlon standard solutions.
7.0 QUALITY CONTROL
7.1 Before processing any samples, the analyst must demonstrate through
the analysis of a method blank that all glassware and reagents are
interferent-free at the method detection limit of the matrix of Interest.
Each time a set of samples is extracted, or there is a change in reagents, a
method blank must be processed as a safeguard against laboratory
contamination.
7.2 A laboratory "method blank" must be run along with each analytical
batch (20 or fewer samples). A method blank is performed by executing all of
the specified extraction and cleanup steps, except for the introduction of a
sample. The method blank is also dosed with the Internal standards. For
water samples, one liter of deionized and/or distilled water should be used as
the method blank. Mineral oil may be used as the method blank for other
matrices.
7.3 The laboratory will be expected to analyze performance evaluation
samples as provided by the EPA on a periodic basis throughout the course of a
given project. Additional sample analyses will not be permitted if the
performance criteria are not achieved. Corrective action must be taken and
acceptable performance must be demonstrated before sample analyses can resume.
7.4 Samples may be split with other participating labs on a periodic
basis to ensure interlaboratory consistency. At least one sample per set of
24 must be run in duplicate to determine Intralaboratory precision.
7.5 Field duplicates (Individual samples taken from the same location at
the same time) should be analyzed periodically to determine the total
precision (field and lab).
7.6 Where appropriate, "field blanks" will be provided to monitor for
possible cross-contamination of samples in the field. The typical "field
blank" will consist of uncontaminated soil (background soil taken off-site).
7.7 GC column performance must be demonstrated Initially and verified
prior to analyzing any sample 1n a 12-hr period. The GC column performance
check solution must be analyzed under the same chromatographic and mass
spectrometric conditions used for other samples and standards.
7.8 Before using any cleanup procedure, the analyst must process a
series of calibration standards (Paragraph 6.2) through the procedure to
validate elution patterns and the absence of interferents from reagents. Both
alumina column and carbon column performance must be checked. Routinely check
the 8 percent CH2Cl2/hexane eluate of environmental extracts from the alumina
column for presence of target analytes.
NOTE: This fraction is intended to contain a high level of Interferents
and analysis near the method detection limit may not be possible.
8280 - 10
Revision 0
Date September 1986
-------
8.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
8.1 Grab and composite samples must be collected In glass containers.
Conventional sampling practices must be followed. The bottle must not be
prewashed with sample before collection. Composite samples should be
collected 1n glass containers. Sampling equipment must be free of tygon,
rubber tubing, other potential sources of contamination which may absorb the
target analytes.
8.2 All samples must be stored at 4*C, extracted within 30 days and
completely analyzed within 45 days of collection.
9.0 EXTRACTION AND CLEANUP PROCEDURES
9.1 Internal standard addition. Use a sample aliquot of 1 g to 1,000 mL
(typical sample size requirements for each type of matrix are provided 1n
Paragraph 9.2) of the chemical waste or soil to be analyzed. Transfer the
sample to a tared flask and determine the weight of the sample. Add an
appropriate quantity of 13Ci2-2,3,7,8-TCDD, and any other material which is to
be used as an internal standard, (Paragraph 6.2). All samples should be
spiked with at least one internal standard, for example, 13Ci2-2,3,7,8-TCDD,
to give a concentration of 500 ng/mL 1n the final concentrated extract. As an
example, a 10 g sample concentrated to a final volume of 100 uL requires the
addition of 50 ng of 13Ci2-2,3,7,8-TCDD, assuming 100% recovery. Adoption of
different calibration solution sets (as needed to achieve different
quantification limits for different congeners) will require a change 1n the
fortification level. Individual concentration levels for each homologous
series must be specified.
9.2 Extraction
9.2.1 Sludge/fuel oil. Extract aqueous sludge samples by refluxlng
a sample (e.g. 2 g) with 50 mL of toluene (benzene) in a 125-mL flask
fitted with a Dean-Stark water separator. Continue refluxlng the sample
until all the water has been removed. Cool the sample, filter the
toluene extract through a fiber filter, or equivalent, into a 100-mL
round bottom flask. Rinse the filter with 10 mL of toluene, combine the
extract and rinsate. Concentrate the combined solution to near dryness
using a rotary evaporator at 50'C. Use of an inert gas to concentrate
the extract is also permitted. Proceed with Step 9.2.4.
9.2.2 Still bottom. Extract still bottom samples by mixing a
sample (e.g., 1.0 g) with 10 mL of toluene (benzene) 1n a small beaker
and filtering the solution through a glass fiber filter (or equivalent)
into a 50-mL round bottom flask. Rinse the beaker and filter with 10 mL
of toluene. Concentrate the combined toluene solution to near dryness
using a rotary evaporator at 50*C while connected to a water aspirator.
Proceed with Step 9.2.4.
8280 - 11
Revision 0
Date September 1986
-------
9.2.3> Fly ash. Extract fly ash samples by placing a sample (e.g.
10 g) and an equivalent amount of anhydrous sodium sulfate 1n a Soxhlet
extraction apparatus charged with 100 ml of toluene (benzene) and extract
for 16 hr using a three cycle/hour schedule. Cool and filter the toluene
extract through a glass fiber filter paper Into a 500-mL round bottom
flask. Rinse the filter with 5 ml of toluene. Concentrate the combined
toluene solution to near dryness using a rotary evaporator at 50*C.
Proceed with Step 9.2.4.
9.2.4 Transfer the residue to a 125-mL separatory funnel using
15 ml of hexane. Rinse the flask with two 5-mL allquots of hexane and
add the rinses to the funnel. Shake 2 min with 50 ml of 5% NaCl
solution, discard the aqueous layer and proceed with Step 9.3.
9.2.5 Soil. Extract soil samples by placing the sample (e.g. 10 g)
and an equivalent amount of anhydrous sodium sulfate in a 500-mL
Erlenmeyer flask fitted with a teflon stopper. Add 20 ml of methanol and
80 ml of petroleum Aether, in that order, to the flask. Shake on a wrist-
action shaker for two hr. The solid portion of sample should mix freely.
If a smaller soil aliquot 1s used, scale down the amount of methanol
proportionally.
9.2.5.1 Filter the extract from Paragraph 9.2.5 through a
glass funnel fitted with a glass fiber filter and filled with
anhydrous sodium sulfate Into a 500-mL Kuderna-Danish (KD)
concentrator fitted with a 10-mL concentrator tube. Add 50 mL of
petroleum ether to the Erlenmeyer flask, restopper the flask and
swirl the sample gently, remove the stopper carefully and decant the
solvent through the funnel as above. Repeat this procedure with two
additional 50-mL aliquots of petroleum ether. Wash the sodium
sulfate 1n the funnel with two additional 5-mL portions of petroleum
ether.
9.2.5.2 Add a Teflon or PFTE boiling chip and a three-ball
Snyder column to the KD flask. Concentrate in a 70*C water bath to
an apparent volume of 10 mL. Remove the apparatus from the water
bath and allow it to cool for 5 min.
9.2.5.3 Add 50 mL of hexane and a new boiling chip to the KD
flask. Concentrate in a water bath to an apparent volume of 10 mL.
Remove the apparatus from the water bath and allow to cool for 5
min.
9.2.5.4 Remove and Invert the Snyder column and rinse 1t down
Into the KD with two 1-mL portions of hexane. Decant the contents
of the KD and concentrator tube into a 125-mL separatory funnel.
Rinse the KD with two additional 5-mL portions of hexane, combine.
Proceed with Step 9.3.
9.2.6 Aqueous samples: Mark the water meniscus on the side of the
1-L sample bottle for later determination of the exact sample volume.
8280 - 12
Revision 0
Date September 1986
-------
Pour the entire sample (approximately 1-L) Into a 2-L separatory funnel.
Proceed with Step 9.2.6.1.
NOTE: A continuous liquid-liquid extractor may be used 1n place of
a separatory funnel when experience with a sample from a
given source indicates that a serious emulsion problem will
result or an emulsion 1s encountered using a separatory
funnel. Add 60 ml of methylene chloride to the sample
bottle, seal, and shake for 30 sec to rinse the Inner
surface. Transfer the solvent to the extractor. Repeat the
sample bottle rinse with an additional 50- to 100-mL portion
of methylene chloride and add the rinse to the extractor.
Add 200 to 500 ml of methylene chloride to the distilling
flask; add sufficient reagent water to ensure proper
operation, and extract for 24 hr. Allow to cool, then detach
the distilling flask. Dry and concentrate the extract as
described 1n Paragraphs 9.2.6.1 and 9.2.6.2. Proceed with
Paragraph 9.2.6.3.
9.2.6.1 Add 60 ml methylene chloride to the sample bottle,
seal and shake 30 sec to rinse the Inner surface. Transfer the
solvent to the separatory funnel and extract the sample by shaking
the funnel for 2 min with periodic venting. Allow the organic layer
to separate from the water phase for a minimum of 10 m1n. If the
emulsion Interface between layers 1s more than one-third the volume
of the solvent layer, the analyst must employ mechanical techniques
to complete the phase separation. Collect the methylene chloride
(3 x 60 ml) directly into a 500-mL Kuderna-Danish concentrator
(mounted with a 10-mL concentrator tube) by passing the sample
extracts through a filter funnel packed with a glass wool plug and
5 g of anhydrous sodium sulfate. After the third extraction, rinse
the sodium sulfate with an additional 30 ml of methylene chloride to
ensure quantitative transfer.
9.2.6.2 Attach a Snyder column and concentrate the extract on
a water bath until the apparent volume of the liquid reaches 5 ml.
Remove the K-D apparatus and allow it to drain and cool for at least
10 min. Remove the Snyder column, add 50 ml hexane, re-attach the
Snyder column and concentrate to approximately 5 ml. Add a new
boiling chip to the K-D apparatus before proceeding with the second
concentration step.
Rinse the flask and the lower joint with 2 x 5 ml hexane and combine
rinses with extract to give a final volume of about 15 ml.
9.2.6.3 Determine the original sample volume by refilling the
sample bottle to the mark and transferring the liquid to a 1,000-mL
graduated cylinder. Record the sample volume to the nearest 5 ml.
Proceed with Paragraph 9.3.
9.3 In a 250-mL Separatory funnel, partition the solvent (15 ml hexane)
against 40 ml of 20 percent (w/v) potassium hydroxide. Shake for 2 m1n.
8280 - 13
Revision 0
Date September 1986
-------
Remove and discard the aqueous layer (bottom). Repeat the base washing until
no color 1s visible 1n the bottom layer (perform base washings a maximum of
four times). Strong base (KOH) 1s known to degrade certain PCDD/PCDF's,
contact time must be minimized.
9.4 Partition the solvent (15 ml hexane) against 40 ml of 5 percent
(w/v) sodium chloride. Shake for 2 m1n. Remove and discard aqueous layer
(bottom).
NOTE: Care should be taken due to the heat of neutralization and
hydratlon.
9.5 Partition the solvent (15 ml hexane) against 40 ml of concentrated
sulfuric acid. Shake for 2 min. Remove and discard the aqueous layer
(bottom). Repeat the acid washings until no color is visible in the add
layer. (Perform acid washings a maximum of four times.)
9.6 Partition the extract against 40 ml of 5 percent (w/v) sodium
chloride. Shake for 2 min. Remove and discard the aqueous layer (bottom).
Dry the organic layer by pouring through a funnel containing anhydrous sodium
sulfate into a 50-mL round bottom flask, wash the separatory funnel with two
15-mL portions of hexane, pour through the funnel, and combine the hexane
extracts. Concentrate the hexane solution to near dryness with a rotary
evaporator (35°C water bath), making sure all traces of toluene are removed.
(Use of blowdown with an inert gas to concentrate the extract 1s also
permitted).
9.7 Pack a gravity column (glass 300-mm x 10.5-mm), fitted with a Teflon
stopcock, in the following manner:
Insert a glass-wool plug into the bottom of the column. Add a 4-g layer
of sodium sulfate. Add a 4-g layer of Woelm super 1 neutral alumina. Tap the
top of the column gently. Woelm super 1 neutral alumina need not be activated
or cleaned prior to use but should be stored 1n a sealed desiccator. Add a 4-
g layer of sodium sulfate to cover the alumina. Elute with 10 ml of hexane
and close the stopcock just prior to the exposure of the sodium sulfate layer
to air. Discard the eluant. Check the column for channeling. If channeling
1s present discard the column. Do not tap a wetted column.
9.8 Dissolve the residue from Step 9.6 in 2 ml of hexane and apply the
hexane solution to the top of the column. Elute with enough hexane (3-4 mL)
to complete the transfer of the sample cleanly to the surface of the alumina.
Discard the eluant.
9.8.1 Elute with 10 ml of 8 percent (v/v) methylene chloride in
hexane. Check by GC/MS analysis that no PCDD's or PCDF's are eluted in
this fraction. See Paragraph 9.9.1.
9.8.2 Elute the PCDD's and PCDF's from the column with 15 ml of 60
percent (v/v) methylene chloride in hexane and collect this fraction in a
conical shaped (15-mL) concentrator tube.
8280 - 14
Revision 0
Date September 1986
-------
9.9 Carbon column cleanup:
Prepare a carbon column as described in Paragraph 4.18.
9.9.1 Using a carefully regulated stream of nitrogen (Paragraph
4.15), concentrate the 8 percent fraction from the alumina column
(Paragraph 9.8.1) to about 1 ml. Wash the sides of the tube with a small
volume of hexane (1 to 2 ml) and reconcentrate to about 1 ml. Save this
8 percent concentrate for GC/MS analysis to check for breakthrough of
PCDD's and PCDF's. Concentrate the 60 percent fraction (Paragraph 9.8.2)
to about 2 to 3 ml. Rinse the carbon with 5 ml cyclohexane/methylene
chloride (50:50 v/v) 1n the forward direction of flow and then 1n the
reverse direction of flow. While still 1n the reverse direction of flow,
transfer the sample concentrate to the column and elute with 10 ml of
cyclohexane/methylene chloride (50:50 v/v) and 5 ml of methylene
chloride/methanol/benzene (75:20:5, v/v). Save all above eluates and
combine (this fraction may be used as a check on column efficiency). Now
turn the column over and 1n the direction of forward flow elute the
PCDD/PCDF fraction with 20 ml toluene.
NOTE: Be sure no carbon fines are present 1n the eluant.
9.9.2 Alternate carbon column cleanup. Proceed as in Section 9.9.1
to obtain the 60 percent fraction re-concentrated to 400 uL which is
transferred to an HPLC Injector loop (1 ml). The injector loop 1s
connected to the optional column described in Paragraph 4.18. Rinse the
centrifuge tube with 500 uL of hexane and add this rinsate to the
injector loop. Load the combined concentrate and rlnsate onto the
column. Elute the column at 2 mL/m1n, ambient temperature, with 30 ml of
cyclohexane/methylene chloride 1:1 (v/v). Discard the eluant. Backflush
the column with 40 ml toluene to elute and collect PCDD's and PCDF's
(entire fraction). The column 1s then discarded and 30 ml of
cyclohexane/methylene chloride 1:1 (v/v) is pumped through a new column
to prepare it for the next sample.
9.9.3 Evaporate the toluene fraction to about 1 ml on a rotary
evaporator using a water bath at 50*C. Transfer to a 2.0-mL Reacti-vial
using a toluene rinse and concentrate to the desired volume using a
stream of N2- The final volume should be 100 uL for soil samples and
500 uL for sludge, still bottom, and fly ash samples; this is provided
for guidance, the correct volume will depend on the relative concentra-
tion of target analytes. Extracts which are determined to be outside the
calibration range for individual analytes must be diluted or a smaller
portion of the sample must be re-extracted. Gently swirl the solvent on
the lower portion of the vessel to ensure complete dissolution of the
PCDD's and PCDF's.
9.10 Approximately 1 hr before HRGC/LRMS analysis, transfer an aliquot
of the extract to a micro-vial (Paragraph 4.16). Add to this sufficient
recovery standard (13Cj2l,2,3,4-TCDD) to give a concentration of 500 ng/mL.
(Example: 36 uL aliquot of extract and 4 uL of recovery standard solution.
Remember to adjust the final result to correct for this dilution. Inject an
appropriate aliquot (1 or 2 uL) of the sample into the GC/MS instrument.
8280 - 15
Revision 0
Date September 1986
-------
10.0 GC/MS ANALYSIS
10.1 When toluene Is employed as the final solvent use of a bonded phase
column from Paragraph 4.3.2 is recommended. Solvent exchange Into trldecane
1s required for other liquid phases or nonbonded columns (CP-S11-88).
NOTE: Chromatographlc conditions must be adjusted to account for solvent
boiling points.
10.2 Calculate response factors for standards relative to the Internal
standards, 13Ci2-2,3.7,8-TCDD and 13Ci2-OCDD (see Section 11). Add the
recovery standard (l3Ci2-l,2,3,4-TCDD) to the samples prior to Injection. The
concentration of the recovery standard in the sample extract must be the same
as that in the calibration standards used to measure the response factors.
10.3 Analyze samples with selected 1on monitoring, using all of the ions
listed 1n Table 2. It is recommended that the GC/MS run be divided into five
selected 1on monitoring sections, namely: (1) 243, 257,, 304, 306, 320, 322,
332, 334, 340, 356, 376 (TCDD's, TCDF's, 13Ci2-labeled Internal and recovery
standards, PeCDD's, PeCDF's, HxCDE); (2) 277, 293, 306, 332, 338, 340, 342,
354, 356, 358, 410 (peCDD's, PeCDF's, HpCDE); (3) 311, 327, 340, 356, 372,
374, 376, 388, 390, 392, 446, (HxCDD's, HxCDF's, OCDE); (4) 345, 361, 374,
390, 406, 408, 410, 422, 424, 426, 480 (HpCDD's, HpCDF's, NCDE) and (5) 379,
395, 408, 424, 442, 444, 458, 460, 470, 472, 514 (OCDD, OCDF, 13Ci2-OCDD,
DCDE). Cycle time not to exceed 1 sec/descriptor. It Is recommended that
selected ion monitoring section 1 should be applied during the GC run to
encompass the retention window (determined in Paragraph 6.3) of the first- and
last-elutlng tetra-chlorinated isomers. If a response 1s observed at m/z 340
or 356, then the GC/MS analysis must be repeated; selected ion monitoring
section 2 should then be applied to encompass the retention window of the
first- and last-eluting penta-chlorinated Isomers. HxCDE, HpCDE, OCDE, NCDE,
DCDE, are abbreviations for hexa-, hepta-, octa-, nona-, and decachlorinated
dlphenyl ether, respectively.
10.4 Identification criteria for PCDD's and PCDF's;
10.4.1 All of the characteristic ions, i.e. quantltation ion,
confirmation ions, listed in Table 2 for each class of PCDD and PCDF,
must be present in the reconstructed ion chromatogram. It is desirable
that the M - COC1 ion be monitored as an additional requirement.
Detection limits will be based on quantltation ions within the molecules
1n cluster.
10.4.2 The maximum intensity of each of the specified charac-
teristic ions must coincide within 2 scans or 2 sec.
10.4.3 The relative intensity of the selected, isotopic ions within
the molecular ion cluster of a homologous series of PCDD's of PCDF's must
lie within the range specified in Table 3.
10.4.4 The GC peaks assigned to a given homologous series must have
retention times within the window established for that series by the
column performance solution.
8280 - 16
Revision 0
Date September 1986
-------
10.5 Quantltate the PCDD and PCDF peaks from the response relative to
the appropriate Internal standard. Recovery of each Internal standard) vs.
the recovery standard must be greater than 40 percent. It Is recommended that
samples with recoveries of less than 40 percent or greater than 120 percent be
re-extracted and re-analyzed.
NOTE: These criteria are used to assess method performance; when
properly applied, Isotope dilution techniques are Independent of
Internal standard recovery.
In those circumstances where these procedures do not yield a definitive
conclusion, the use of high resolution mass spectrometry or HRGC/MS/MS 1s
suggested.
11.0 CALCULATIONS
NOTE: The relative response factors of a given congener within any
homologous series are known to be different. However, for
purposes of these calculations, 1t will be assumed that every
congener within a given series has the same relative response
factor. In order to minimize the effect of this assumption on
risk assessment, a 2,3,7,8-substltuted Isomer that 1s
commercially available was chosen as representative of each
series. All relative response factor calculations for a given
homologous series are based on that compound.
11.1 Determine the concentration of Individual Isomers of tetra-, penta,
and hexa-CDD/CDF according to the equation:
Concentration, ng/g =
where:
QJS = ng of Internal standard 13Ci2-2,3,7,8-TCDD, added to the sample
before extraction.
G = g of sample extracted.
As = area of quantltatlon 1on of the compound of Interest.
Ajs = area of quantltatlon 1on (m/z 334) of the Internal standard,
13Ci2-2,3,7,8-TCDD.
RRF = response factor of the quantltatlon 1on of the compound of
Interest relative to m/z 334 of 13Ci2-2,3,7,8-TCDD.
NOTE: Any dilution factor Introduced by following the procedure 1n
Paragraph 9.10 should be applied to this calculation.
8280 - 17
Revision 0
Date September 1986
-------
.1.1.1.1 Determine the concentration of Individual isomers of hepta-
CDD/CDF and the concentration of OCDD and OCDF according to the equation:
Q1s x As
Concentration, ng/g - G x x RRF
where:
Qls = n9 °f Internal standard 13Ci2-OCDD, added to the, sample before
extraction.
G = g of sample extracted.
As = area of quantitatlon 1on of the compound of Interest.
A^s = area of quantitatlon Ion (m/z 472) of the Internal standard,
13C12-OCDD.
RRF = response factor of the quantitatlon ion of the compound of
Interest relative to m/z 472 of 13Ci2-OCDD.
NOTE: Any dilution factor introduced by following the procedure 1n
Paragraph 9.10 should be applied to this calculation.
11.1.2 Relative response factors are calculated using data obtained
from the analysis of multi -level calibration standards according to the
equation: f
RRF = * * 'J
A1s x Ls
where:
AS = area of quantitatlon ion of the, compound of Interest.
Ajs = area of quantisation ion of the appropriate internal standard
(m/z 334 for 13C12-2,3,7,8-TCDD; m/z 472 for 13C12-OCDD).
Cis = concentration of the appropriate internal standard,
13C12-2,3,7,8-TCDD or 13C12-OCDD)
Cs = concentration of the compound of interest.
11.1.3 The concentrations of unknown isomers of TCDD shall be
calculated using the mean RRF determined for 2,3,7,8-TCDD.
The concentrations of unknown Isomers of PeCDD shall be calculated
using the mean RRF determined for 1,2,3,7,8-PeCDD or any available
2,3,7,8,X-PeCDD isomer.
8280 - 18
Revision
Date September 1986
-------
The concentrations of unknown Isomers of HxCDD shall be calculated
using the mean RRF determined for 1,2,3,4,7,8-HxCDD or any available
2,3,7,8,-X,Y-HXCDD Isomer.
The concentrations of unknown Isomers of HpCDD shall be calculated
using the mean RRF determined for 1,2,3,4,6,7,8-HpCDD or any available
2,3,7,8,X,Y,Z-HpCDD Isomer.
The concentrations of unknown Isomers of TCDF shall be calculated
using the mean RRF determined for 2,3,7,8-TCDF.
The concentrations of unknown isomers of PeCDF shall be calculated
using the mean RRF determined for 1,2,3,7,8-PeCDF or any available
2,3,7,8,X-PeCDF isomer.
The concentrations of unknown Isomers of HxCDF shall be calculated
using the mean RRF determined for 1,2,4,7,8-HxCDF or any available
2,3,7,8-X,Y-HxCDF isomer.
The concentrations of unknown Isomers of HpCDF shall be calculated
using the mean RRF determined for 1,2,3,4,6,7,8-HpCDF or any available
2,3,7,8,X,Y,Z-HpCDF Isomer.
The concentration of the octa-CDD and octa-CDF shall be calculated
using the mean RRF determined for each.
Mean relative response factors for selected PCDD's and PCDF's are
given 1n Table 4.
11.1.4 Calculate the percent recovery, Ris, for each Internal
standard 1n the sample extract, using the equation:
"1s Ars X RFr X Q,s
where:
Ars = Area of quantitation ion (m/z 334) of the recovery standard,
13Ci2-l,2,3,4-TCDD.
Qrs = n9 °f recovery standard, 13Ci2-l,2,3,4-TCDD, added to
extract.
The response factor for determination of recovery is calculated using
data obtained from the analysis of the multi-level calibration standards
according to the equation:
DF A1s x Crs
r ~ A x C
r Ars x Lis
8280 - 19
Revision
Date September 1986
-------
where:
Crs = Concentration of the recovery standard, 13Ci2-1.2,3,4-TCDD.
11.1.5 Calculation of total concentration of all Isomers within
each homologous series of PCDD's and PCDF's.
Total concentration = Sum of the concentrations of the Individual
of PCDD's or PCDF's PCDD or PCDF Isomers
11.4 Report results In nanograms per gram; when duplicate and spiked
samples are reanalyzed, all data obtained should be reported.
11.5 Accuracy and Precision. Table 5 gives the precision data for
revised Method 8280 for selected analytes 1n the matrices shown. Table 6
lists recovery data for the same analyses. Table 2 shows the linear range and
variation of response factors for selected analyte standards. Table 8
provides the method detection limits as measured 1n specific sample matrices.
11.6 Method Detection Limit. The Method Detection Limit (MDL) is
defined as the minimum concentration of a substance that can be measured and
reported with 99 percent confidence that the value Is above zero. The
procedure used to determine the MDL values reported in Table 8 was obtained
from Appendix A of EPA Test Methods manual, EPA-600/4-82-057 July 1982,
"Methods for Organic Chemical Analysis of Municipal and Industrial
Wastewater."
11.7 Maximum Holding Time (MHT). Is that time at which a 10 percent
change 1n the analyte concentration (Ctio) occurs and the precision of the
method of measurement allows the 10 percent change to be statistically
different from the 0 percent change (Cto) at the 90 percent confidence level.
When the precision of the method 1s not sufficient to statistically
discriminate a 10 percent change 1n the concentration from 0 percent change,
then the maximum holding time 1s that time where the percent change in the
analyte concentration (Ctn) is statistically different than the concentration
at 0 percent change (Cto) ancl greater than 10 percent change at the 90 percent
confidence level.
8280 -; 20
Revision 0
Date September 1986
-------
TABLE 1. REPRESENTATIVE GAS CHROMATOGRAPH RETENTION TIMES* OF ANALYTES
Analyte
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,4-TCDD
1, 2,3,4, 7-PeCDD
1, 2,3,4,7, 8-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
50-m
CP-Sil-88
25.2
23.6
24.1
30.0
39.5
57.0
NM
30-m
DB-5
17.8
17.4
17.3
20.1
22.1
24.1
25.6
3—m
SP-2250
26.7
26.7
26.5
28.1
30.6
33.7
NM
*Retent1on time in min, using temperature programs shown below.
NM = not measured.
Temperature Programs;
CP-Sil-88 60°C-190'C at 20'/m1n; 190'-240° at 5Vm1n.
DB-5 170*, 10 min; then at 8°/min to 320'C, hold
30 m x 0.25 mm at 320*C 20 min (until OCDD elutes).
Thin film (0.25 urn)
SP-2250 70'-320» at lOVminute.
Column Manufacturers
CP-S11-88 Chrompack, Incorporated, Bridgewater, New Jersey
DB-5, J and W Scientific, Incorporated, Rancho Cordova,
California
SP-2250 Supelco, Incorporated, Bellefonte, Pennsylvania
8280 - 21
Revision
Date September 1986
-------
TABLE 2. IONS SPECIFIED3 FOR SELECTED ION MONITORING
FOR PCDD'S AND PCDF'S
Quantitation
ion
Confirmation
ions
M-COC1
PCDD'S
13Cj2-Tetra
Tetra
Penta
Hexa
Hepta
Octa
13Ci2-Octa
PCDF's
Tetra
Penta
Hexa
Hepta
Octa
334
322
356
390
424
460
472
306
340
374
408
444
332
320
354;358
388; 392
422; 426
458
470
304
338; 342
372; 376
406; 410
442
__ _
257
293
327
361
395
243
277
311
345
379
alons at m/z 376 (HxCDE), 410 (HpCDE), 446 (OCDE), 480 (NCDE) and 514 (DCDE)
are also included in the scan monitoring sections (1) to (5), respectively.
See Paragraph 10.3.
TABLE 3. CRITERIA FOR ISOTOPIC RATIO MEASUREMENTS FOR PCDD'S AND PCDF'S
Selected ions (m/z)
Relative intensity
PCDD's
Tetra
Penta
Hexa
Hepta
Octa
PCDF's
320/322
358/356
392/390
426/424
458/460
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
Tetra
Penta
Hexa
Hepta
Octa
304/306
342/340
376/374
410/408
442/444
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
8280 - 22
Revision 0
Date September 1986
-------
TABLE 4. MEAN RELATIVE RESPONSE FACTORS OF CALIBRATION STANDARDS
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
l,2,3,4,6,7,8-HpCDDb
OCDDb
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-HxCDF
l,2,3,4,6,7,8-HpCDFb
OCDFb
13Ci2-2t3,7,8-TCDD
13Ci2-l,2,3,4-TCDD
13C12-OCDD
RRFa
1.13
0.70
0.51
1.08
1.30
1.70
1.25
0.84
1.19
1.57
1.00
0.75
1.00
RSD%
(n = 5)
3.9
10.1 ^
6.6
6.6
7.2
8.0
8.7
9.4
3.8
8.6
-
4.6
-
Quantltatlon 1on
(•/z)
322
356
390
424
460
306
340
374
444
408
334
334
472
aThe RRF value is the mean of the five determinations made. Nominal weights
injected were 0.2, 0.5, 1.0, 2.0 and 5.0 ng.
bRRF values for these analytes were determined relative to 13Ci2-OCDD. All
other RRF's were determined relative to 13Ci2-2,3,7,8-TCDD.
Instrument Conditions/Tune - GC/MS system was tuned as specified in
Paragraph 6.3. RRF data was acquired under
SIM control, as specified in Paragraph 10.3.
GC Program - The GC column temperature was programmed as specified in
Paragraph 4.3.2(b).
8280 - 23
Revision
Date September 1986
-------
TABLE 5. PRECISION DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD
1,2,3,4-TCDD
1,3,6,8-TCDD
•
1,3,7,9-TCDD
1,3,7,8-TCDD
1,2,7,8-TCDD
1,2,8,9-TCDD
Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
NDb
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
422
ND
ND
: ND
2.6
ND
ND
ND
ND
ND
ND
Native
+ spike
5.0
378
125
46
487
5.0
25.0
125
38.5
2500
2.5
25.0
125
19.1
2727
2.5
25.0
125.0
58.4
2500
5.0
25.0
125
16.0
2920
5.0
25.0
125
2.6
2500
5.0
25.0
125
46
2500
N
4
4
4
2
4
3
4
4
4
4
4
4
4
2
2
4
4
4
2
2
4
4
4
4
2
4
4
4
3
2
4
4
4
2
2
Percent
RSD
4.4
2.8
4.8
-
24
1.7
1.1
9.0
7.9
-
7.0
5.1
3.1
-
-
19
2.3
6.5
_
-
7.3
1.3
5.8
3.5
-
7.7
9.0
7.7
23
-
10
0.6
1.9
-
_
8280 - 24
Revision 0
Date September 1986
-------
TABLE 5 (Continued)
Compound
1,2,3,4, 7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-HxCDF
Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge0
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
NO
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8760
ND
ND
ND
ND
ND
7.4
ND
ND
ND
ND
ND
25600
ND
ND
13.6
24.2
ND
Native
+ spike
5.0
25.0
125
25.8
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
8780
-
-
5.0
25.0
125
7.4
2500
5.0
25.0
125
46
28100
5.0
25.0
139
24.2
2500
N
4
4
4
2
2
4
4
4
2
2
4
4
4
2
2
4
4
4
-
-
4
4
4
3
2
4
4
4
2
2
4
4
4
4
2
Percent
RSD
10
2.8
4.6
6.9
-
25
20
4.7
-
-
38
8.8
3.4
-
-
_
-
-
-
-
3.9
1.0
7.2
7.6
-
6.1
5.0
4.8
.
-
26
6.8
5.6
13.5
-
8280 - 25
Revision 0
Date September 1986
-------
TABLE 5. (Continued)
Compound
OCDF
Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native Percent
Native + spike N RSD
ND ...
ND -
192 317 4 3.3
ND -
ND -
amatr1x types:
clay: pottery clay.
soil: Times Beach, Missouri, soil blended to form a homogeneous sample.
This sample was analyzed as a performance evaluation sample for the Contract
Laboratory Program (CLP) in April 1983. The results from EMSL-LV and 8
contract laboratories using the CLP protocol were 305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.
fly ash: ash from a municipal incinerator; resource recovery ash No. 1.
still bottom: distillation bottoms (tar) from 2,4-dichlorophenol production.
sludge: sludge from cooling tower which received both creosote and
pentachl orophenol i c wastewaters .
Cleanup of clay, soil and fly ash samples was through alumina column only.
(Carbon column not used.)
- not detected at concentration injected (final volume 0.1 mL or greater).
GEst1mated concentration out of calibration range of standards.
8280 - 26
Revision
Date September 1986
-------
TABLE 6. RECOVERY DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD
1,2,3,4-TCDD
1,3,6,8-TCDD
1,3,7,9-TCDD
1,3,7,8-TCDD
1,2,7, 8-TCDD
1,2,8,9-TCDD
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
615
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
Sp1kedc
level
(ng/g)
5.0
-
125
46
-
5.0
25.0
125
46
2500
2.5
25.0
125
46
2500
2.5
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
61.7
-
90.0
90.0
-
67.0
60.3
73.1
105.6
93.8
39.4
64.0
64.5
127.5
80.2
68.5
61.3
78.4
85.0
91.7
68.0
79.3
78.9
80.2
90.5
68.0
75.3
80.4
90.4
88.4
59.7
60.3
72.8
114.3
81.2
8280 - 27
Revision 0
Date September 1986
-------
TABLE 6. (Continued)
Compound
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3, 4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
2,3,7,8-TCDD
(C-13)
1,2,7,8-TCDF
1,2,3,7,8-PeCDF
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
•— • * — j
soil
sludge^
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nativeb
(ng/g)
< ND
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8780
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.4
ND
ND
ND
! ND
ND
25600
Spikedc
level
(ng/g)
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
•i
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
58.4
62.2
79.2
102.4
81.8
61.7
68.4
81.5
104.9
84.0
46.8
65.0
81.9
125.4
89.1
ND
ND
-
-
64.9
78.8
78.6
88.6
69.7
65.4
71.1
' 80.4
90.4
104.5
57.4
64.4
84.8
105.8
_
8280 - 28
Revision 0
Date September 1986
-------
TABLE 6. (Continued)
Compound
1,2,3,4,7,8-HxCDF
OCDF
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
ND
13.6
24.2
ND
ND
ND
192
ND
ND
Spikedc
level
(ng/g)
5.0
25.0
125
46
2500
_
-
125
-
-
Mean
percent
recovery
54.2
68.5
82.2
91.0
92.9
_
-
86.8
-
-
amatn'x types:
clay: pottery clay.
soil: Times Beach, Missouri soil blended to form a homogeneous sample. This
sample was analyzed as a performance evaluation sample for the Contract
Laboratory Program (CLP) In April 1983. The results from EMSL-LV and 8
contract laboratories using the CLP protocol were 305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.
fly ash: ash from a municipal incinerator: resource recovery ash No. 1.
still bottom: distillation bottoms (tar) from 2,4-dichlorophenol production.
sludge: sludge from cooling tower which received both creosote and
pentachlorophenol wastewaters.
The clay, soil and fly ash samples were subjected to alumina column cleanup,
no carbon column was used.
bFinal volume of concentrate 0.1 mL or greater, ND means below quantification
limit, 2 or more samples analyzed.
cAmount of analyte added to sample, 2 or more samples analyzed.
^Estimated concentration out of calibration range of standards.
8280 - 29
Revision 0
Date September 1986
-------
TABLE 7. LINEAR RANGE AND VARIATIOIN OF RESPONSE FACTORS
Analyte Linear range tested (pg) n&
l,2,7,8-TCDFa
2,3,7,8-TCDDa
2,3,7,8-TCDF
50-6000
50-7000
300-4000
8
7
5
Mean RF
1.634
0.721
2.208
%RSD
12.0
11.9
7.9
aResponse factors for these analytes were calculated using 2,3,7,8-TCDF as the
Internal standard. The response factors for 2,3,7,8-TCDF were calculated vs.
13Ci2-l,2,3,4-TCDD.
DEach value of n represents a different concentration level.
8280 - 30
Revision
Date September 1986
-------
TABLE 8. METHOD DETECTION LIMITS OF C12 - LABELED PCDD'S and PCDF'S
IN REAGENT WATER (PPT) AND ENVIRONMENTAL SAMPLES (PPB)
1 ^-Labeled
Analyte
2,3,7,8-TCDD
i,2,3,7,8-PeCDD
1,2,3,6,7,8-HxQDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-ttcCDF
Reagent
Water3
0.44
1.27
2.21
2.77
3.93
0.63
1.64
2.53
Missouri
Soi?
0.17
0.70
1.25
1.87
2.35
0.11
0.33
0.83
rs»
Ash
0.07
0.25
0.55
1.41
2.27
0.06
0.16
0.30
Industrial
Sludge0
0.82
1.34
2.30
4.65
6.44
0.46
0.92
2.17
Still-d
Bottom
1.81
2.46
6.21
4.59
10.1
0.26
1.61
2.27
Fuel
Oil*
0.75
2.09
5.02
8.14
23.2
0.48
0.80
2.09
Fuel Oil/
Sawdust
0.13
0.18
0.36
0.51
1.48
0.40
0.43
2.22
.Sample size 1 ,000 mL.
Sample size 10 g.
.Sample size 2 g.
Sample size 1 g.
Note: The final sample-extract volume was 100 uL for all samples.
Matrix types used in MDL Study:
- Reagent water: distilled, deionized laboratory water.
- Missouri soil: soil blended to form a homogeneous sample.
- Fly-ash: alkaline ash recovered from the electrostatic precipitator of
a coal-burning power plant.
- Industrial sludge: sludge from cooling tower which received creosotic
and pentachlorophenolic wastewaters. Sample was ca. 70 percent water,
mixed with oil and sludge.
- Still-bottom: distillation bottoms (tar) from 2,4-dichlorophenol
production.
- Fuel oil: wood-preservative solution from the modified Thermal Process
tanks. Sample was an oily liquid (>90 percent oil) containing no
water.
- Fuel oil/Sawdust: sawdust was obtained as a very fine powder from the
local lumber yard. Fuel oil (described above) was mixed at the 4
percent (w/w) level.
Procedure used for the Determination of Method Detection Limits was obtained
from "Methods for Organic Chemical Analysis of Municipal and Industrial
Wastewater" Appendix A, EPA-600/4-82-057, July 1982. Using this procedure,
the method detection limit is defined as the minimum concentration of a
substance that can be measured and reported with 99 percent confidence that
the value is above zero.
8280 - 31
Revision 0
Date September 1986
-------
lOO.On
00
ro
oo
o
to
po
O 73
cu n>
00 O
fD 3
O
IT
ft)
vo
00
15:00
18:00 21:00
Retention Time
24:00
27:00
Figure 2. Mass Chromatogram of Selected PCDD and PCDF Congeners.
-------
METHOD easo
POLYCHLORINATEO OIBENZO-P-DIOXIINS AND POLYCHLOHINATED OIBENZONFUHANS
( Start )
Q
6. 1
Perform Initial
calibration on
GC/MS system
6.9
10.2
Calculate
response
factors for
standards
Do routine
calibration
10.3
Analyze
samples with
selected ion
monitoring
S.Z
1 Extract
•ample using
appropriate
method for the
waste matrix
9.9 |
Prepare
carbon column:
do carbon
column cleanup
10. S
Quantitate PCOO
and PCOF peaks
Yes
o
11.01
Determine
concentrations
•nd report
results
f Stop J
8280 - 33
Revision 0
Date September 1986
-------
APPENDIX A
SIGNAL-TO-NOISE DETERMINATION METHODS
MANUAL DETERMINATION
This method corresponds to a manual determination of the S/N from a GC/MS
signal, based on the measurement of Its peak height relative to the baseline
noise. The procedure is composed of four steps as outlined below. (Refer to
Figure 1 for the following discussion).
1. Estimate the peak-to-peak noise (N) by tracing the two lines (EI and
£2) defining the noise envelope. The lines should pass through the
estimated statistical mean of the positive and the negative peak
excursions as shown in Figure 1. In addition, the signal offset (0)
should be set high enough such that negative-going noise (except for
spurious negative spikes) is recorded.
2. Draw the line (C) corresponding to the mean noise between the
segments defining the noise envelope.
3. Measure the height of the GC/MS signal (S) at the apex of the peak
relative to the mean noise C. For noisy GC/MS signals, the average
peak height should be measured from the estimated mean apex signal D
between £3 and,£4.
4. Compute-the S/N.
This method of S/N measurement 1s a conventional, accepted method of
noise measurement in analytical chemistry.
s
INTERACTIVE COMPUTER GRAPHICAL METHOD
This method calls for the measurement of the GC/MS peak area using the
computer data system and Eq. 1:
A/t
S/N = Aj/2t + A /2t
where t is the elution time window (time interval, t2~t2, at the base of the
peak used to measure the peak area A). (Refer to Figure 2, for the following
discussion).
AI and Ar correspond to the areas of the noise level 1n a region to the
left (AI) and to the right (Ar) of the GC peak of Interest.
8280 - A - 1
Rev'i s 1 on 0
Date September 1986
-------
The procedure to determine the S/N 1s as follows:
1. Estimate the average negative peak excursions of the noise (I.e.,
the low segment-E2-of the noise envelope). Line £3 should pass
through the estimated statistical mean of the negative-going noise
excursions. As stated earlier, 1t 1s Important to have the signal
offset (0) set high enough such that negative-going noise 1s
; recorded.
2. Using the cross-hairs of the video display terminal, measure the
peak area (A) above a baseline corresponding to the mean negative
noise value (£3) and between the time t\ and t£ where the GC/MS peak
Intersects the baseline, £3. Make note of the time width t=t2-tj.
3. Following a similar procedure as described above, measure the area
of the noise 1n a region to the left (AI) and to the right (Ar) of
the GC/MS signal using a time window twice the size of t, that 1s,
2 x t.
The analyst must sound judgement 1n regard to the proper selection of
Interference-free regions 1n the measurement of Aj and Ar. It 1s not
recommended to perform these noise measurements (Aj and Ar) 1n remote regions
exceeding ten time widths (lot).
4. Compute the S/N using Eq. 1.
NOTE: If the noise does not occupy at least 10 percent of the vertical
axis (I.e., the noise envelope cannot be defined accurately), then
1t 1s necessary to amplify the vertical axis so that the noise
occupies 20 percent of the terminal display (see Figure 3).
8280 - A - 2
Revision
Date September 1986
-------
FIGURE CAPTIONS
Figure 1. Manual determination of S/N.
The peak height (S) Is measured between the mean noise (lines C and
D). These mean signal values are obtained by tracing the line
between the baseline average noise extremes, Ej and £?, and between
the apex average noise extremes, £3 and £4, at the apex of the
signal. Note, 1t Is Imperative that the Instrument's Interface
amplifier electronlc's zero offset be set high enough such that
negative-going baseline noise 1s recorded.
Figure 2. Interactive determination of S/N.
The peak area (A) 1s measured above the baseline average negative
noise £2 and between times ti and t2. The noise 1s obtained from
the areas AI and Ar measured to the left and to the right of the
peak of Interest using time windows Tj and Tr (Ti=Tr=2t).
Figure 3. Interactive determination of S/N.
A) Area measurements without amplification of the vertical axis.
Note that the noise cannot be determined accurately by visual
means. B) Area measurements after amplification (10X) of the
vertical axis so that the noise level occupies approximately 20
percent of the display, thus enabling a better visual estimation of
the baseline noise, Ej, £2, and C.
8280 - A - 3
Revision 0
Date September 1986
-------
00
ro
oo
o
O 73
01 n
r+ <
(0 -*
(ft
OO O
0> 3
a
CT
a>
(O
00
100-,
90-
80-
70-
60-
50-
40-
30-
20-
10-
E3
I
E4
117
N
= 19.5
20:00
22:00
26:00
28:00
30:00
Figure 1. Manual Determination of S/N.
-------
100
90-
80-
70-
60-
50-
40-
30-
20-
10-
0
= 558.10
iv
14.7
=75.88
Ar = 88.55
25:30 26:00 26:30
27:00 27:30 28:00
17 sec.
Figure 2. Interactive Determination of S/N.
8280 - A - 5
Revision p
Date September 1986
-------
100-
90-
80-
70-
60-
60-
40-
30-
20-
10-
0-
A = 686.41
= 17.18
Ar= 13.32
26:30 26:00 36:30 27:00 27:30 28:00
A = 706.59
Ar = 41.88
26:30 26:00 26:30 27:00 27:30 28:00
Figure 3. Interactive Determination of S/N.
8280 - A - 6
Revision 0
Date September 1986
-------
APPENDIX B
RECOMMENDED SAFETY AND HANDLING PROCEDURES FOR PCDD'S/PCDF'S
1. The human toxicology of PCDD/PCDF 1s not well defined at present,
although the 2,3,7,8-TCDD Isomer has been found to be acnegenlc, carcinogenic,
and teratogenlc in the course of laboratory animal studies. The 2,3,7,8-TCDD
1s a solid at room temperature, and has a relatively low vapor pressure. The
solubility of this compound 1n water 1s only about 200 parts-per-tr1H1on, but
the solubility 1n various organic solvents ranges from about 0.001 perent to
0.14 percent. The physical properties of the 135 other tetra- through octa-
chlorinated PCDD/PCDF have not been well established, although 1t 1s presumed
that the physical properties of these congeners are generally similar to those
of the 2,3,7,8-TCDD Isomer. On the basis of the available toxlcologlcal and
physical property data for TCDD, this compound, as well as the other PCDD and
PCDF, should be handled only by highly trained personnel who are thoroughly
versed 1n the appropriate procedures, and who understand the associated risks.
2. PCDD/PCDF and samples containing these are handled using essentially
the same techniques as those employed 1n handling radioactive or Infectious
materials. Well-ventilated, controlled-access laboratories are required, and
laboratory personel entering these laboratories should wear appropriate safety
clothing, Including disposable coveralls, shoe covers, gloves, and face and
head masks. During analytical operations which may give rise to aerosols or
dusts, personnel should wear respirators equipped with activated carbon
filters. Eye protection equipment (preferably full face shields) must be worn
at all times while working 1n the analytical laboratory with PCDD/PCDF.
Various types of gloves can be used by personnel, depending upon the
analytical operation being accomplished. Latex gloves are generally utilized,
and when handling samples thought to be particularly hazardous, an additional
set of gloves are also worn beneath the latex gloves (for example, Playtex
gloves supplied by American Scientific Products, Cat. No. 67216). Bench-tops
and other work surfaces 1n the laboratory should be covered with plastic-
backed absorbent paper during all analytical processing. When finely divided
samples (dusts, soils, dry chemicals) are processed, removal of these from
sample contaners, as well as other operations, Including weighing,
transferring, and mixing with solvents, should all be accomplished within a
glove box. Glove boxes, hoods and the effluents from mechanical vacuum pumps
and gas chromatographs on the mass spectrometers should be vented to the
atmosphere preferably only after passing through HEPA particulate filters and
vapor-sorblng charcoal.
3. All laboratory ware, safety clothing, and other Items potentially
contaminated with PCDD/PCDF 1n the course of analyses must be carefully
secured and subjected to proper disposal. When feasible, liquid wastes are
concentrated, and the residues are placed 1n approved steel hazardous waste
drums fitted with heavy gauge polyethylene liners. Glass and combustible
Items are compacted using a dedicated trash compactor used only for hazardous
waste materials and then placed 1n the same type of disposal drum. Disposal
of accumulated wastes 1s periodically accomplished by high temperature
Incineration at EPA-aproved facilities.
8280 - B - 1
Revision 0
Date September 1986
-------
4. Surfaces of laboratory benches, apparatus and other appropriate areas
should be periodically subjected to surface wipe tests using solvent-wetted
filter paper which 1s then analyzed to check for PCDD/PCDF contamination 1n
the laboratory. Typically, 1f the detectable level of TCDD or TCDF from such
a test is greater than 50 ng/m2, this indicates the need for decontamination
of the laboratory. A typical action limit 1n terms of surface contamination
of the other PCDD/PCDF (summed) is 500 ng/m2. In the event of a spill within
the laboratory, absorbent paper is used to wipe up the spilled material and
this is then placed into a hazardous waste drum. The contaminated surface is
subsequently cleaned thoroughly by washing with appropriate solvents
(methylene chloride followed by methanol) and laboratory detergents. This 1s
repeated until wipe tests Indicate that the levels of surface contamination
are below the limits cited.
5. In the unlikely event that analytical personnel experience skin
contact with PCDD/PCDF or samples containing these, the contaminated skin
area should Immediately be thoroughly scurbbed using mild soap and water.
Personnel involved 1n any such accident should subsequently be taken to the
nearest medical facility, preferably a facility whose staff is knowledgeable
in the toxicology of chlorinated hydrocarbons. Again, disposal of
contaminated clothing is accomplished by placing 1t in hazardous waste drums.
6. It 1s desirable that personnel working 1n laboratories where
PCDD/PCDF are handled be given periodic physical examinations (at least
yearly). Such examinations should Include specialized tests, such as those
for urinary porphyrins and for certain blood parameters which, based upon
published clinical observations, are appropriate for persons who may be
exposed to PCDD/PCDF. Periodic facial photographs to document the onset of
dermatologlc problems are also advisable.
8280 - B - 2
Revision 0
Date September 1986
-------
Page 1 of 2
DIOXIN SAMPLE DATA SUMMARY FORM 8280-1
LAB NAME
CONTRACT No.
CASE No.
QUANTITY FOUND (ng/g)
SAMPLE NO. FILE NAME TCDD PeCDD HxCDD HpCDD OCDD
DATA RELEASE AUTHORIZED BY
8280 - B - 3
Revision 0
Date September 1986
-------
Page 2 of 2
DIOXIN SAMPLE DATA SUMMARY FORM 8280-1
LAB NAME CONTRACT No.
CASE No. __^
QUANTITY FOUND (ng/g)
SAMPLE NO. FILE NAME TCDF PeCDF' HxCDF HpCDF OCDF
8280 - B - 4
Revision
Date September 1986
-------
Page 1 of 2
DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W
LAB NAME
CONTRACT No.
CASE No.
QUANTITY FOUND (ug/L)
SAMPLE NO. FILE NAME TCDD PeCDD HxCDD HpCDD OCDD
DATA RELEASE AUTHORIZED BY
8280 - B - 5
Revision 0
Date September 1986
-------
Page 2 of 2
DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W
LAB NAME CONTRACT No.
CASE No.
QUANTITY FOUND (ug/L)
SAMPLE NO. FILE NAME TCDF PeCDF HxCDF HpCDF OCDF
8280 - B - 6
Revision
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-2
LAB NAME ANALYST(s) CASE No.
SAMPLE No. TYPE OF SAMPLE CONTRACT No.
SAMPLE SIZE % MOISTURE FINAL EXTRACT VOLUME
EXTRACTION METHOD ALIQUOT USED FOR ANALYSIS
CLEAN UP OPTION
CONCENTRATION FACTOR DILUTION FACTOR
DATE EXTRACTED DATA ANALYZED
VOLUME 13Ci2-l,2,3,4-TCDD ADDED TO SAMPLE VOLUME
VOLUME INJECTED Wt 13c12-l,2,3,4-TCDD ADDED
Wt 13C12-2,3,7,8-TCDD ADDED 13C12-2,3,7,8-TCDD % RECOVERY
Wt 13C12-2,3,7,8-OCDD ADDED 13C12-OCDD % RECOVERY
13Ci2-2,3,7,8-TCDD RRF 13C12-OCDD RRF
13Ci2-2,3,7,8-TCDD
AREA 332 AREA 334 RATIO 332/334 _
13Ci2-OCDD AREA 470 AREA 472 RATIO 470/472
RT 2,3,7,8-TCDD (Standard) RT 2,3,7,8-TCDD (Sample)
13C12-2,3,7,8-TCDD - 13Ci2-l,2,3,4-TCDD Percent Valley
8280 - B - 7
Revision
Date September 1986
-------
DIOXIN INITIAL CALIBRATION STANDARD DATA SUMMARY
FORM 8280-3
CASE No.
Lab Name
Date of Initial Calibration
Contract No.
Analyst(s)
Relative to 13Ci2-2,3,7,8-TCDD_
or 13Ci2-l,2,3,4-TCDD_
CALIBRATION
STANDARD
RRF
1
RRF
2
RRF RRF
3 4
RRF
5
MEAN %RSD
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
8280 - B - 8
Revision 0
Date September 1986
-------
FORM 8280-3 (Continued)
CONCENTRATIONS IN PG/UL
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
8280 - B - 9
Revision 0
Date September 1986
-------
DIOXIN CONTINUING CALIBRATION SUMMARY
FORM 8280-4
CASE No.
Lab Name
Date of Initial Calibration
Relative to 13Ci2-2,3,7,8-TCDD_
Contract No.
Analyst(s)
or 13Ci2-l,2,3,4-TCDD
COMPOUND
RRF
RRF
%D
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
8280 - B - 10
Revision 0
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-5-A
LAB NAME ANALYST(s) CASE No.
CONTRACT No. SAMPLE No.
TCDD REQUIRED 320/322 RATIO WINDOW IS 0.65 - 0.89
QUANTITATED FROM 2,3,7,8-TCDD 1,2,3,4-TCDD RRF
SCAN # RRT AREA AREA AREA 320/ CONFIRM
322 320 257 322 AS TCDD
• Y/N CONC.
TOTAL TCDD
TCDF REQUIRED 304/306 RATIO WINDOW IS 0.65 - 0.89
QUANTITATED FROM 2,3,7,8-TCDD 1,2,3,4-TCDD RRF
SCAN # RRT AREA AREA AREA 304/ CONFIRM
306 304 243 306 AS TCDD
: Y/N CONC.
TOTAL TCDD
8280 - B - 11
Revision
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-5-B
LAB NAME
ANALYST(s)
CASE No.
CONTRACT No.
SAMPLE No.
PeCDD REQUIRED 320/322 RATIO WINDOW IS 0.55 - 0.75
QUANTITATED FROM 2,3,7,8-TCDD
SCAN # RRT AREA AREA
356 358
AREA
354
1,2,3,4-TCDD
AREA
293
358/
356
RRF
CONFIRM
AS PeCDD
Y/N
CONC.
TOTAL PeCDD
PeCDF REQUIRED 342/340 RATIO WINDOW IS 0.55 - 0.75
QUANTITATED FROM 2,3,7,8-TCDD 1,2,3,4-TCDD
SCAN # RRT AREA AREA AREA AREA 342/
340 342 338 277 340
RRF
CONFIRM
AS PeCDF
Y/N
CONC.
TOTAL PeCDF
8280 - B - 12
Revision 0
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-5-C
LAB NAME
ANALYST(s)
CASE No.
CONTRACT No.
SAMPLE No.
HxCDD REQUIRED 392/390 RATIO WINDOW IS 0.69 - 0.93
QUANTITATED FROM 2,3,7,8-TCDD
SCAN # RRT AREA AREA
390 392
1,2,3,4-TCDD
AREA
388
AREA
327
3927
390
RRF
CONFIRM
AS HxCDD
Y/N
CONC.
TOTAL HxCDD
HxCDF REQUIRED 376/374
QUANTITATED FROM 2,3,7
SCAN # RRT AREA
376
RATIO WINDOW IS
,8-TCDD
AREA
374
AREA
372
0.69 - 0.93
1,2,3,4-TCDD
AREA
311
376/
374
RRF
CONFIRM
AS HxCDF
Y/N CONC.
TOTAL HxCDF
8280 - B - 13
Revision 0
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-5-D
LAB NAME
ANALYST(s)
CASE No.
CONTRACT No.
SAMPLE No.
HpCDD REQUIRED 426/444 RATIO WINDOW IS 0.83 - 1.12
QUANTITATED FROM 2,3,7,8-TCDD
SCAN # RRT AREA AREA
424 426
AREA
422
1,2,3,4-TCDD
AREA
361
4267
424
RRF
CONFIRM
AS HpCDD
Y/N
CONC.
TOTAL HpCDD
HpCDF REQUIRED 410/408
QUANTITATED FROM 2,3,7,
SCAN # RRT AREA
408
RATIO WINDOW IS
8-TCDD
AREA
410
AREA
406
0.83 - 1.
1,2,3
AREA
345
12
,4-TCDD
410/
408
RRF
CONFIRM
AS HpCDF
Y/N CONC.
TOTAL HpCDF
8280 - B - 14
Revision 0
Date September 1986
-------
DIOXIN RAW SAMPLE DATA FORM 8280-5-E
LAB NAME ANALYST(s) CASE No..
CONTRACT No. SAMPLE No.
OCDD REQUIRED 458/460 RATIO WINDOW IS 0.75 - 1.01
QUANTITATED FROM 2,3,7,8-TCDD 1,2,3,4-TCDD RRF
SCAN # RRT AREA * AREA AREA 458/ CONFIRM
460 458 395 460 AS OCDD
Y/N CONC.
TOTAL OCDD
OCDF REQUIRED 442/444 RATIO WINDOW IS 0.75 - 1.01
QUANTITATED FROM 2,3,7,8-TCDD 1,2,3,4-TCDD RRF
SCAN # RRT AREA AREA AREA 442/ CONFIRM
444 442 379 444 AS OCDF
Y/N CONC.
TOTAL OCDF
8280 - B - 15
Revision
Date September 1986
-------
DIOXIN SYSTEM PERFORMANCE CHECK ANALYSIS FORM 8280-6
LAB NAME
CASE No.
BEGINNING DATE
ENDING DATE
TIME
TIME
CONTRACT No._
ANALYST(s)
PC SOLUTION IDENTIFIER
PCDD's
ISOTOPIC RATIO CRITERIA MEASUREMENT
IONS
RATIOED
RATIO AT
BEGINNING OF
12 HOUR PERIOD
RATIO AT
END OF 12 ACCEPTABLE
HOUR PERIOD WINDOW
Tetra
320/322
0.65-0.89
Penta
358/356
0.55-0.75
Hexa
392/390
0.69-0.93
Hepta
426/424
0.83-1.12
Octa
458/460
0.75-1.01
PCDF's
Tetra
304/306
0.65-0.89
Penta
342-340
0.55-0.75
Hexa
376-374
0.69-0.93
Hepta
410/408
0.83-1.12
Octa
442/444
0.75-1.01
Ratios out of criteria
PCDD
PCDF
Beginning
_ out of
out of
End
out of
out of
NOTE: One form 1s required for each 12 hour period samples are analyzed.
8280 - B - 16
Revision 0
Date September 1986
-------
4.3 DETERMINATION OF ORGANIC ANALYTES
4.3.3 HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC METHODS
FOUR - 11
Revision
Date September 1986
-------
METHOD 8310
POLYNUCLEAR AROMATIC HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 Method 8310 1s used to determine the concentration of certain poly-
nuclear aromatic hydrocarbons (PAH) 1n ground water and wastes. Specifically,
Method 8310 is used to detect the following substances:
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)f 1uoranthene
Benzo(ghi)perylene
Benzo(k)f1uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
1.2 Use of Method 8310 presupposes a high expectation of finding the
specific compounds of Interest. If the user is attempting to screen samples
for any or all of the compounds listed above, he must develop independent
protocols for the verification of Identity.
1.3 The method detection limits for each compound 1n reagent water are
listed 1n Table 1. Table 2 lists the practical quantisation limit (PQL) for
other matrices. The sensitivity of this method usually depends on the level
of Interferences rather than instrumental limitations. The limits of
detection listed in Table 1 for the liquid chromatographic approach represent
sensitivities that can be achieved in the absence of Interferences. When
Interferences are present, the level of sensitivity will be lower.
1.4 This method 1s recommended for use only by experienced residue
analysts or under the close supervision of such qualified persons.
2.0 SUMMARY OF METHOD
2.1 Method 8310 provides high performance liquid chromatographic (HPLC)
conditions for the detection of ppb levels of certain polynuclear aromatic
hydrocarbons. Prior to use of this method, appropriate sample extraction
techniques must be used. A 5- to 25-uL aliquot of the extract is injected
Into an HPLC, and compounds in the effluent are detected by ultraviolet (UV)
and fluorescence detectors.
2.2 If interferences prevent proper detection of the analytes of
interest, the method may also be performed on extracts that have undergone
cleanup using silica gel column cleanup (Method 3630).
8310 - 1
Revision 0
Date September 1986
-------
TABLE 1. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF PAHsa
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
D1 benzo (a , h) anthracene
Benzo (ghl)perylene
Indeno(l,2,3-cd)pyrene
Retention
time (m1n)
16.6
18.5
20.5
21.2
22.1
23.4
24.5
25.4
28.5
29.3
31.6
32.9
33.9
35.7
36.3
37.4
Col umn
capacity
factor (k1)
12.2
13.7
15.2
15.8
16.6
17.6
18.5
19.1
21.6
22.2
24.0
25.1
25.9
27.4
27.8
28.7
Method Detection
limit (ug/L)
UV Fluorescence
1.8
2.3
1.8
0.21
0.64
0.66
0.21
0.27
0.013
0.15
0.018 .
0.017
0.023
0.030
0.076
0.043
a HPLC conditions: Reverse phase HC-ODS S11-X, 5 micron particle size,
1n a 250-mrn x 2.6-mm I.D. stainless steel column. Isocratlc elutlon for 5 mln
using aceton1tr1le/water (4:6)(v/v), then linear gradient elutlon to 100%
acetonltrlle over 25 m1n at 0.5 mL/m1n flow rate. If columns having other
Internal diameters are used, the flow rate should be adjusted to maintain a
linear velocity of 2 mm/sec.
TABLE 2. DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
MATRICES3
Matrix
Factorb
Ground water
Low-level soil by sonlcation with GPC cleanup
High-level soil and sludges by sonlcatlon
Non-water mlsclble waste
10
670
10,000
100,000
aSample PQLs are highly matrix-dependent. The PQLs listed herein are
provided for guidance and may not always be achievable.
bPQL = [Method Detection Limit (Table 1) X [Factor (Table 2)].
aqueous samples, the factor 1s on a wet-weight basis.
For non-
8310 - 2
Revision 0
Date September 1986
-------
3.0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines, causing misinterpreta-
tion of the chromatograms. All of these materials must be demonstrated to be
free from Interferences, under the conditions of the analysis, by running
method blanks. Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source. Although a general cleanup technique 1s provided as
part of this method, individual samples may require additional cleanup
approaches to achieve the sensitivities stated 1n Table 1.
3.3 The chromatographlc conditions described allow for a unique
resolution of the specific PAH compounds covered by this method. Other PAH
compounds, in addition to matrix artifacts, may interfere.
4.0 APPARATUS AND MATERIALS
4.1 Kuderna-Danish (K-D) apparatus:
4.1.1 Concentrator tube: 10-mL, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper 1s used to prevent evaporation of
extracts.
4.1.2 Evaporation flask: 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.1.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.1.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.2 Boiling chips; Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.3 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5'C). The bath should be used 1n a hood.
4.4 Syringe; 5-mL.
4.5 High pressure syringes.
4.6 HPLC apparatus;
4.6.1 Gradient pumping system: Constant flow.
4.6.2 Reverse phase column: HC-ODS Sil-X, 5-micron particle size
diameter, in a 250-mm x 2.6-mm I.D. stainless steel column (Perkin Elmer
No. 089-0716 or equivalent).
8310 - 3
Revision 0
Date September 1986
-------
4.6.3 Detectors: Fluorescence and/or UV detectors may be used.
4.6.3.1 Fluorescence detector: .For excitation at 280-nm and
emission greater than 389-nm cutoff - (Corning 3-75.or equivalent).
Fluorometers should have dispersive optics for excitation and can
utilize either filter or.dispersive optics at the emission detector.
4.6.3.2 UV detector: ,254-nm, coupled to the fluorescence
detector. .'••.... . .,-...
4.6.4 Strip-chart recorder: icompatlble with detectors. A data
system for measuring peak areas and retention times 1s recommended.
4.7 Volumetric flasks; 1.0-, 50-, and 100-mL.
5.0 REAGENTS ' , . . i ",-
','"'-. '.' ' •'
,5.1 Reagent water; Reagent water 1s defined as water 1n which an
Interferent Is not observed at the method detection.limit of the compounds of
interest. ,
5.2 Aceton1tr11e; HPLC quality, distilled In glass. . . • •
5.3 Stock standard solutions;
5.3.1 Prepare stock standard solutions at a concentration of 1.00
ug/uL by dissolving 0.0100 g of assayed reference material 1n aceto-
nitrile and diluting to volume In a 10-mL volumetric flask. Larger
volumes can be used at the convenience of the analyst. When compound
purity is assayed to be 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration 1f
they are certified by the manufacturer or by an Independent source.
5.3.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4'C and protect from light. Stock standards
should be checked frequently for, signs of degradation or evaporation,
especially just prior to preparing calibration standards from them.
.1 5.3.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards Indicates a problem.
5.4 Calibration standards; Calibration standards at a minimum of five
concentration levels should be prepared through dilution of the stock
standards with acetonitrile. One of the concentration levels should be at a
concentration near, but above, the method detection limit. The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should;define the working range of the HPLC. Cali-
bration standards must be replaced .after ;six months, or sooner 1f comparison
with check standards indicates a problem.
8310 - 4
Revision 0
Date September 1986
-------
5.5 Internal standards (1f Internal standard calibration 1s used); To
use this approach, the analyst must select one or more Internal standards that
are similar In analytical behavior to the compounds of Interest. The analyst
must further demonstrate that the measurement of the Internal standard 1s not
affected by method or matrix interferences. Because of these limitations, no
Internal standard can be suggested that 1s applicable to all samples.
5.5.1 Prepare calibration standards at a minimum of five
concentration levels for each analyte as described 1n Paragraph 5.4.
5.5.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with acetonltrlle.
5.5.3 Analyze each calibration standard according to Section 7.0.
5.6 Surrogate standards; The analyst should monitor the performance of
the extraction,cleanup(Tf necessary), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g.,
decafluorobiphenyl or other PAHs not expected to be present in the sample)
recommended to encompass the range of the temperature program used in this
method. Deuterated analogs of analytes should not be used as surrogates for
HPLC analysis due to coelution problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1. Extracts must be stored under refrigeration and must be analyzed
within 40 days of extraction.
7.0 PROCEDURE
7.1 Extraction;
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral pH with methylene chloride, using either Method 3510 or 3520.
Solid samples are extracted using either Method 3540 or 3550. To achieve
maximum sensitivity with this method, the extract must be concentrated to
1 mL.
7.1.2 Prior to HPLC analysis, the extraction solvent must be
exchanged to acetonltrlle. The exchange 1s performed during the K-D
procedures listed in all of the extraction methods. The exchange 1s
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to
1 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 m1n.
8310 - 5
Revision 0
Date September 1986
-------
7.1.2.2 Increase the temperature of the hot water bath to 95-
100*C. Momentarily remove the Snyder column, add 4 ml of
acetonltrile, a new boiling chip, and attach a two-ball mlcro-Snyder
column. Concentrate the extract using 1 ml of acetonltrile to
prewet the Snyder column. Place the K-D apparatus on the water bath
so that the concentrator tube 1s partially Immersed 1n the hot
water. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete concentration 1n 15-20 m1n.
At the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 0.5 ml, remove the K-D apparatus
and allow 1t to drain and cool for at least 10 m1n.
7.1.2.3 When the apparatus 1s cool, remove the mlcro-Snyder
column and rinse Us lower joint Into the concentrator tube with
about 0.2 ml of acetonltrile. A 5-mL syringe 1s recommended for
this operation. Adjust the extract volume to 1.0 ml. Stopper the
concentrator tube and store refrigerated at 4'C, 1f further
processing will not be performed Immediately. If the extract will
be stored longer than two days, 1t should be transferred to a
Teflon-sealed screw-cap vial. Proceed with HPLC analysis 1f further
cleanup 1s not required.
7.2 HPLC conditions (Recommended);
7.2.1 Using the column described 1n Paragraph 4.6.2: Isocratlc
elutlon for 5 m1n using aceton1tr1le/water (4:6)(v/v), then linear
gradient elutlon to 100% acetonltrile over 25 m1n at 0.5 mL/m1n flow
rate. If columns having other Internal diameters are used, the flow rate
should be adjusted to maintain a linear velocity of 2 mm/sec.
7.3 Calibration;
7.3.1 Refer to Method 8000 for proper calibration procedures. The
procedure of Internal or external standard calibration may be used. Use
Table 1 and especially Table 2 for guidance on selecting the lowest point
on the calibration curve.
7.3.2 Assemble the necessary HPLC apparatus and establish operating
parameters equivalent to those Indicated 1n Section 7.2.1. By Injecting
calibration standards, establish the sensitivity limit of the detectors
and the linear range of the analytical systems for each compound.
7.3.3 Before using any cleanup procedure, the analyst should
process a series of calibration standards through the procedure to
confirm elutlon patterns and the absence of Interferences from the
reagents.
7.4 HPLC analysis;
7.4.1 Table 1 summarizes the estimate retention times of PAHs
determinable by this method. Figure 1 1s an example of the separation
achievable using the conditions given 1n Paragraph 7.2.1.
8310 - 6
Revision 0
Date September 1986
-------
Column: HC-ODSSIL-X
Mobile Phase: 40% to 100% Acetonitrile in Water
Dectector: Fluorescence
1 S
a
I
IB
I
o>
CD
§
0>
g
I
N
I
i
28
— >
o a
N Jr
C T3
• 5 V
I
o
-------
7.4.2 If Internal standard calibration 1s to be performed, add
10 uL of Internal standard to the sample prior to Injection. Inject
2-5 uL of the sample extract with a high-pressure syringe or sample
Injection loop. Record the volume Injected to the nearest 0.1 uL, and
the resulting peak size, 1n area units or peak heights. Re-equilibrate
the HPLC column at the Initial gradient conditions for at least 10 min
between injections.
7.4.3 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. See Section 7.8 of Method 8000 for calculation
equations.
7.4.4 If the peak area exceeds the linear range of the system,
dilute the extract and .^analyze.
7.4.5 If the peak area measurement is prevented by the presence of
Interferences, further cleanup is required.
7.5 Cleanup;
7.5.1 Cleanup of the acetonltrile extract takes place using Method
3630 (Silica Gel Cleanup). Specific Instructions for cleanup of the
extract for PAHs is given 1n Section 7.1 of Method 3630.
7.5.2 Following cleanup, analyze the samples using HPLC as
described 1n Section 7.4.
8.0 QUALITY CONTROL ',
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction is covered in Method 3500 and 1n
the extraction method used. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Mandatory quality control to validate the HPLC system operation is
found 1n Method 8000, Section 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Section 8.6) should contain each analyte at the following concentrations
in acetonltrile: naphthalene, 100 ug/mL; acenaphthylene, 100 ug/mL;
acenaphthene, 100 ug/mL; fluorene, 100 ug/mL; phenanthrene, 100 ug/mL;
anthracene, 100 ug/mL; benzo(k)fluoranthene, 5 ug/mL; and any other PAH
at 10 ug/mL.
8.2.2 Table 3 indicates the, calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as
functions of concentration for the analytes of interest. The contents of
both Tables should be used to evaluate a laboratory's ability to perform
and generate acceptable data by this method.
8310-8
Revision 0
Date September 1986
-------
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if the recovery 1s within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
8.3.1 If recovery 1s not within limits, the following procedures
are required.
• Check to be sure there are no errors 1n calculations,
surrogate solutions and Internal standards. Also, check
instrument performance.
• Recalculate the data and/or reanalyze the extract 1f any of
the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
9.0 METHOD PERFORMANCE
9.1 The method was tested by 16 laboratories using reagent water,
drinking water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 0.1 to 425 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the analyte and essentially Independent of the sample
matrix. Linear equations to describe these relationships are presented in
Table 4.
9.2 This method has been tested for linearity of spike recovery from
reagent water and has been demonstrated to be applicable over the
concentration range from 8 x MDL to 800 x MDL with the following exception:
benzo(ghi)perylene recovery at 80 x and 800 x MDL were low (35% and 45%,
respectively).
9.3 The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. "Development and Application of Test Procedures for Specific Organic Toxic
Substances 1n Wastewaters, Category 9 - PAHs," Report for EPA Contract 68-03-
2624 (in preparation).
2. Sauter, A.D., L.D. Betowski, T.R. Smith, V.A. Strickler, R.G. Belmer, B.N.
Colby, and J.E. Wilkinson, "Fused Silica Capillary Column GC/MS for the
Analysis of Priority Pollutants," Journal of HRC&CC 4, 366-384, 1981.
3. "Determination of Polynuclear Aromatic Hydrocarbons In Industrial and
Municipal Wastewaters," EPA-600/4-82-025, U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268, September 1982.
8310 - 9
Revision 0
Date September 1986
-------
4. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
5. "EPA Method Validation Study 20, Method 610 (Polynuclear Aromatic
Hydrocarbons)," Report for EPA Contract 68-03-2624 (In preparation).
6. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim Final
Rule and Proposed Rule," October 26, 1984.
7. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
8310 - 10
Revision
Date September 1986
-------
TABLE 3. QC ACCEPTANCE CRITERIA*
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f 1 uoranthene
Benzo (ghl ) peryl ene
Benzo (k) f 1 uoranthene
Chrysene
D1 benzo (a , h) anthracene
Fl uoranthene
Fluorene
Indeno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40.3
45.1
28.7
4.0
4.0
3.1
2.3
2.5
4.2
2.0
3.0
43.0
3.0
40.7
37.7
3.4
Range
for 7
(ug/L)
D-105.7
22.1-112.1
11.2-112.3
3.1-11.6
0.2-11.0
1.8-13.8
D-10.7
D-7.0
D-17.5
0.3-10.0
2.7-11.1
D-119
1.2-10.0
21.5-100.0
8.4-133.7
1.4-12.1
Range
P. Ps
(%)
D-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
s = Standard deviation of four recovery measurements, 1n ug/L.
7 = Average recovery for four recovery measurements, 1n ug/L.
p, ps = Percent recovery measured.
D = Detected; result must be greater than zero.
3Cr1ter1a from 40 CFR Part 136 for Method 610. These criteria are based
directly upon the method performance data In Table 3. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 3.
8310 - 11
Revision
Date September 1986
-------
TABLE 4. METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Benzo (gh1 )peryl ene
Benzo (k) f 1 uoranthene
Chrysene
D1 benzo (a , h) anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene i
Accuracy, as
recovery, x'
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44C+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.287+0.04
0.387-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.327-0.18
0.247+0.02
0.227+0.06
0.447-1.12
0.297+0.02
0.397-0.18
0.297+0.05
0.257+0.14
Overall
precision,
S' (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.537-0.01
0.387-0. 00
0.587+0.10
0.697+0.10
0.667-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
x1 = Expected recovery for one or more measurements of a sample
containing a concentration of C, 1n ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of 7, 1n ug/L.
S1 = Expected Interlaboratory standard deviation of measurements at an
average concentration found of 7, 1n ug/L.
C = True value for the concentration, 1n ug/L.
7 = Average recovery found for measurements of samples containing a
concentration of C, 1n ug/L.
8310 - 12
Revision 0
Date September 1986
-------
METHOD 6310
POLYNUCLEAR AROMATIC HYDROCARBONS
7.1.1
o
Choose
appropriate
extraction
procedure
(see Chapter 2)
7.1.2
7.3.3
Process
a series of
calibration
standards
Exchange
extract-
ion solvent to
•cetonltrlie
during K-D
procedures
7.2
7.4
Perform
HPLC
analysis (see
Method 6000
for calculation
aquations
Set HPLC
conditions
7.3
Refer to
Method 6000
for proper
calibration
techniques
7.5.1
Cleanup using
Method 3630
7.3.2
I Assembla
HPLC apparatus:
establish
operating
parameters
0
8310 - 13
Revision 0
Date September 1986
-------
4.4 MISCELLANEOUS SCREENING METHODS
FOUR - 12
Revision
Date September 1986
-------
METHOD 3810
HEADSPACE
1.0 SCOPE AND APPLICATION
1.1 Method 3810 was formerly Method 5020 In the second edition of this
manual.
1.2 Method 3810 is a static headspace technique for extracting volatile
organic compounds from samples. It is a simple method that allows large
numbers of samples to be screened in a relatively short period of time. It is
ideal for screening samples prior to using the purge-and-trap method.
Detection limits for this method may vary widely among samples because of the
large variability and complicated matrices of waste samples. The method works
best for compounds with boiling points of less than 125°C. The sensitivity of
this method will depend on the equilibria of the various compounds between the
vapor and dissolved phases.
1.3 Due to the variability of this method, this procedure is recommended
for use only as a screening procedure for other, more accurate determinative
methods (Methods 8010, 8015, 8020, 8030, and 8240).
2.0 SUMMARY OF METHOD
2.1 The sample is collected in sealed glass containers and allowed to
equilibrate at 90'C. A sample of the headspace gas is withdrawn with a gas-
tight syringe for screening analysis using the conditions specified in one of
the GC or GC/MS determinative methods (8010, 8015, 8020, 8030, or 8240).
3.0 INTERFERENCES
3.1 Samples can be contaminated by diffusion of volatile organics
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe must be rinsed out between samples with reagent water. Whenever an
unusually concentrated sample is encountered, it should be followed by an
analysis of reagent water. It may be necessary to wash out the syringe with
detergent, rinse with distilled water, and dry in a 105*C oven between
analyses.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the entire
analytical system is interference-free.
3810 - 1
Revision 0
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific determinative method for appropriate apparatus
and materials.
4.2 Vials: 125-mL Hypo-V1als (Pierce Chemical Co., #12995, or
equivalent), four each.
4.3 Septa; Tuf-Bond (Pierce #12720 or equivalent).
4.4 Seals; Aluminum (Pierce #132141 or equivalent).
4.5 Crimper; Hand (Pierce #13212 or equivalent).
4.6 Syringe; 5-mL, gas-tight with shutoff valve and chromatographic
needles.
4.7 Microsyringe; 250- or 500-uL.
4.8 Water bath; Heated, with concentric ring cover, capable of
temperature control (+5*C). The bath should be used in a hood.
5.0 REAGENTS
5.1 Refer to the specific determinative method and Method 8000 for
preparation of calibration standards.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
\
6.1 Refer to the Introductory material to this chapter, Organic
Analytes, Section 4.1.
7.0 PROCEDURE
7.1 Gas chromatographic conditions and Calibration; Refer to the
specific determinative method for GCoperating conditions and to Method 8000,
Section 7.4, for calibration procedures.
7.2 Sample preparation;
7.2.1 Place 10.0 g of a well-mixed waste sample into each of two
separate 125-mL septum-seal vials.
7.2.2 Dose one sample vial through the septum with 200 uL of a
50 ng/uL calibration standard containing the compounds of interest.
Label this "1-ppm spike."
3810 - 2
Revision
Date September 1986
-------
7.2.3 Dose a separate (empty) 125-mL septum seal vial with 200 uL
of the same 50 ng/uL calibration standard. Label this "1-ppm standard."
7.2.4 Place the sample, 1-ppm-spike, and l-;ppm-standard vials into
a 90*C water bath for 1 hr. Store the remaining sample vial at 4.0°C for
possible future analysis.
7.3 Sample analysis:
7.3.1 While maintaining the vials at 90°C, withdraw 2 ml of the
headspace gas with a gas-tight syringe and analyze by direct injection
into a GC. The GC should be operated using the same GC conditions listed
in the method being screened (8010, 8015, 8020, 8030, or 8240).
7.3.2 Analyze the 1-ppm standard and adjust instrument sensitivity
to give a minimum response of at least 2 times the background. Record
retention times (RT) and peak areas of compounds of interest.
7.3.3 Analyze the 1-ppm spiked sample in the same manner. Record
RTs and peak areas.
7.3.4 Analyze the undosed sample as in Paragraph 7.3.3.
7.3.5 Use the results obtained to determine if the sample requires
dilution or methanolic extraction as indicated in Method 5030.
8.0 QUALITY CONTROL
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware and
reagents are interference-free. Each time a set of samples is extracted or
there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Fortified samples should be carried through all stages of sample
preparation and measurement; they should be analyzed to validate the
sensitivity and accuracy of the analysis. If the fortified waste samples do
not indicate sufficient sensitivity to detect less than or equal to 1 ug/g of
sample, then the sensitivity of the instrument should be increased.
9.0 METHOD PERFORMANCE
9.1 No data provided.
3810 - 3
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. Hachenberg, H. and A. Schmidt, Gas Chromatographic Headspace Analysis,
Philadelphia: Hayden &.Sons Inc., 1979.
2. Frlant, S.L. and I.H. Suffet, "Interactive Effects of Temperature, Salt
Concentration and pH on Headspace Analysis for Isolating Volatile Trace
Organlcs 1n Aqueous Environmental Samples," Anal. Chem. 51, 2167-2172, 1979.
3810 - 4
Revision 0
Date September 1986
-------
METHOD 3810
HEAOSPACe METHOD
C
7. 1
Set GC
operating
conoitIons
7.2
Prepare sample
7.3
Analyze
Dy direct
Injection
into a GC
7
3.5
01
II
C
Determine
if sample
required
lutlon or
let Mono 1 ic
xtractlon
I Stop J
3810 - 5
Revision 0
Date September 1986
-------
METHOD 3820
HEXADECANE EXTRACTION AND SCREENING OF PURGEABLE ORGANICS
1.0 SCOPE AND APPLICATION
1.1 This method is a screening procedure for use with purge-and-trap GC
or GC/MS. The results of this analysis are purely qualitative and should not
be used as an alternative to more detailed and accurate quantitation methods.
2.0 SUMMARY OF METHOD
2.1 An aliquot of sample is extracted with hexadecane and then analyzed
by GC/FID. The results of this analysis will indicate whether the sample
requires dilution or methanolic extraction prior to purge-and-trap GC or GC/MS
analysis.
3.0 INTERFERENCES
3.1 Method interferences may be caused by contaminants in solvents,
reagents, and glassware. All these materials must be routinely demonstrated
to be free from contaminants by running laboratory reagent blanks. Matrix
interferences may be caused by contaminants that are coextracted from the
sample. The extent of matrix interferences will vary considerably from sample
to sample depending upon the nature and diversity of the water being sampled.
3.2 The flame ionization detector varies considerably in sensitivity
when comparing aromatics and halogenated methanes and ethanes. Halomethanes
are approximately 20x less sensitive than aromatics and haloethanes
approximately lOx less sensitive. Low-molecular-weight, water-soluble
solvents (e.g., alcohols and ketones) will not extract from the water, and
therefore will not be detected by GC/FID.
4.0 APPARATUS AND MATERIALS
4.1 Balance; Analytical, capable of accurately weighing 0.0001 gm.
4.2 Gas Chromatograph; An analytical system complete with gas
chromatograph suitable for on-column injection and all required accessories
including syringes, analytical columns, gases, detector, and strip-chart
recorder (or equivalent). A data system is recommended for measuring peak
heights and/or peak areas.
4.2.1 Detector: Flame ionization (FID).
4.2.2 GC column: 3-m x 2-mm I.D. glass column packed with
10% OV-101 on 100/120 mesh Chromosorb W-HP (or equivalent). The
column temperature should be programmed from 80*C to 280'C at 16'C/min
and held at 280*C for 10 min.
3820 - 1
Revision 0
Date September 1986
-------
4.3 Centrifuge; Capable of accommodating 50-mL glass tubes.
4.4 Vials and caps; 2-mL for GC autosampler.
4.5 Volumetric flasks; 10- and 50-mL with ground-glass stopper or
Tef1on-11ned screw-cap.
4.6 Centrifuge tubes; 50-mL with ground-glass stopper or Teflon-Hned
screw-cap.
4.7 Pasteur plpets; Disposable.
4.8 Bottles; Teflon-sealed screw-cap.
5.0 REAGENTS
5.1 Hexadecane and methanol; Pesticide quality or equivalent.
5.2 Reagent water; Reagent water 1s defined as water 1n which an
Interference Is not observed at the method detection limit of each parameter
of Interest.
5.3 Stock standard solutions (1.0.0 ug/uL): Stock standard solutions can
be purchased as certifiedsolutions or can be prepared from pure standard
materials.
5.3.1 Prepare stock standard solutions by accurately weighing about
0.0100 grams of pure material. Dissolve the material 1n methanol 1n a
10-mL volumetric flask and dilute to volume (larger volumes may be used
at the convenience of the analyst). If compound purity 1s certified at
96% or greater, the weight can be used without correction to calculate
the concentration of the stock standard. Commercially available stock
standards may be used 1f they are certified by the manufacturer.
5.3.2 Transfer the stock standard solutions Into Teflon-sealed
screw-cap bottles. Store at 4*C and protect from light. These standards
should be checked frequently for signs of degradation or evaporation.
5.4 Standard mixture #1: Standard mixture #1 should contain benzene,
toluene, ethyl benzene, and xylene. Prepare a stock solution containing these
compounds as described in Paragraph 5.3 and then prepare a working standard
(through dilution) 1n which the concentration of each compound 1n the standard
1s 100 ng/uL 1n methanol.
5.5 Standard mixture #2: Standard mixture #2 should contain n-nonane
and n-dodecane. Prepare a stock solution containing these compounds as
described In Paragraph 5.3. Dilute the stock standard with methanol so that
the concentration of each compound 1s 100 ng/uL.
3820 - 2
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Sample preparation;
7.1.1 Water;
7.1.1.1 Allow the contents of the 40-mL sample vial to come to
room temperature. Quickly transfer the contents of the 40-mL vial
to a 50-mL volumetric flask. Immediately add 2.0 mL of hexadecane,
cap the flask, and shake the contents vigorously for 1 min. Let
phases separate. Open the flask and add sufficient reagent water to
bring the hexadecane layer into the neck of the flask.
7.1.1.2 Transfer approximately 1 mL of the hexadecane layer to
a 2.0-mL GC vial. If an emulsion is present after shaking the
sample, break it by:
1. pulling the emulsion through a small plug of Pyrex
glass wool packed in a pi pet, or
2. transferring the emulsion to a centrifuge tube and
centrifuging for several min.
7.1.2 Standards;
7.1.2.1 Add 200 uL of the working standard mixtures #1 and #2
to separate 40-mL portions of reagent water. Follow the
instructions in Sections 7.1.1.1 and 7.1.1.2 with the immediate
addition of 2.0 mL of hexadecane.
7.1.3 Sediment/Soil;
7.1.3.1 Add approximately 10 g of sample (wet weight) to 40 mL
of reagent water in a 50-mL centrifuge tube. Cap and shake
vigorously for 1 min. Centrifuge the sample briefly. Quickly
transfer the supernatant water to a 50-mL volumetric flask.
7.1.3.2 Follow the instructions given in Sections 7.1.1.1 and
7.1.1.2, starting with the addition of 2.0 mL of hexadecane.
7.2 Analysis;
7.2.1 Calibration:
7.2.1.1 External standard calibration: The GC/FID must be
calibrated each 12-hour shiftforhalf of full-scale response when
injecting 1-5 uL of each extracted standard mixture #1 and #2
(Paragraphs 5.4 and 5.5).
3820 - 3
Revision 0
Date September 1986
-------
7.2.2 6C/FID analysis: Inject the same volume of hexadecane
extract for the sample under Investigation as was used to perform the
external standard calibration. The GC conditions used for the standards
analysis must also be the same as those used to analyze the samples.
7.2.3 Interpretation of the GC/FID chromatograms: There are two
options for interpretation of the GC/FID results.
7.2.3.1 Option A; The standard mixture #1 is used to
calculate an approximate concentration of the aromatics in the
sample. Use this information to determine the proper dilution for
purge-and-trap if the sample is a water. If the sample is a
sediment/soil, use this information to determine which GC/MS purge-
and-trap method (low- or high-level) should be used. If aromatics
are absent from the sample or obscured by higher concentrations of
other purgeables, use Option B.
7.2.3.2 Option B; The response of standard mixture #2 is used
to determine which purge-and-trap method should be used for
analyzing a sample. All purgeables of interest have retention times
less than the n-dodecane retention time. A dilution factor
(Paragraph 7.2.4.1.3) may be calculated for water samples, and an X
factor (Paragraph 7.2.4.2.3) for soil/sediment samples, to determine
whether the low- or high-level purge-and-trap procedure should be
used.
7.2.4 Analytical decision point;
7.2.4.1 Water samples; Compare the hexadecane sample extract
chromatograms against an extracted standard chromatogram.
7.2.4.1.1 If no peaks are noted, analyze a 5-mL water
sample by the purge-and-trap method.
7.2.4.1.2 If peaks are present prior to the n-dodecane
peak and aromatics are distinguishable, follow Option A
(Paragraph 7.2.3.1).
7.2.4.1.3 If peaks are present prior to the n-dodecane
but the aromatics are absent or indistinguishable, Option B
should be used as follows: If all peaks (prior to n-dodecane)
are <3% of the n-nonane, analyze 5 ml of water sample by the
purge-and-trap method. If any peak is >3% of the n-nonane,
measure the area of the major peak and calculate the necessary
dilution factor as follows:
dilution factor = 50 x area of major peak in sample
peak area of n-nonane
The water sample should be diluted using the calculated factor
just prior to purge-and-trap GC or GC/MS analysis.
3820 - 4
Revision 0
Date September 1986
-------
7.2.4.2 Soil/sediment samples: Compare the hexadecane sample
extract chromatograms against an extracted standard chromatogram.
7.2.4.2.1 If no peaks are noted, analyze a 5-g sample by
the low-level purge-and-trap procedure.
7.2.4.2.2 If peaks are present prior to the n-dodecane
and aromatics are distinguishable, follow Option A using the
concentration information given in Table 1 to determine whether
to analyze the sample by a low- or high-level purge-and-trap
technique.
7.2.4.2.3 If peaks are present prior to n-dodecane but
aromatics are absent or indistinguishable, use Option B.
Calculate an X factor for the sample using the following
equation:
X factor = area of major peak in sample
area of n-nonane
Use the information provided in Table 1 to determine how the
sample should be handled for GC/MS analysis.
7.2.4.2.4 If a high-level method is indicated, the
information provided in Table 2 can be used to determine the
volume of methanol extract to add to 5 ml of reagent water for
analysis (see Methods 5030 and 8240 for methanol1c extraction
procedure).
8.0 QUALITY CONTROL
8.1 It is recommended that a reagent blank be analyzed by this screening
procedure to ensure that no laboratory contamination exists. A blank should
be performed for each set of samples undergoing extraction and screening.
9.0 METHOD PERFORMANCE
9.1 No data available.
10.0 REFERENCES
1. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
3820 - 5
Revision 0
Date September 1986
-------
TABLE 1. DETERMINATION OF GC/MS PURGE-AND-TRAP METHOD
Approximate
X Factor Concentration.Range a Analyze by
0-1.0 0-1,000 ug/kg Low-level method
>1.0 >1,000 ug/kg High-level method
a This concentration range 1s based upon the response of aromatlcs to
GC/FID. The concentration for halomethanes 1s 20x higher, and haloethanes
lOx higher, when comparing GC/FID responses.
TABLE 2. QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF HIGH-LEVEL
SOIL/SEDIMENTS
Approximate Volume of
X Factor Concentration Range a Methanol Extract &
0.25-5.0 500-10,000 ug/kg 100 ul
0.5-10.0 1,000-20,000 ug/kg 50 ul
2.5-50.0 5,000-100,000 ug/kg 10 ul
12.5-250 25,000-500,000 ug/kg 100 uL of
1/50 dilution c
a Actual concentration ranges could be 10 to 20 times higher than this
1f the compounds are halogenated and the estimates are from GC/FID.
D The volume of methanol added to 5 mL of water being purged should be
100 uL. Therefore 1f the amount of methanol extract required 1s less than 100
uL, additional methanol should be added to maintain the constant 100-uL
volume.
c Dilute an aliquot of the methanol extract and then take 100 uL for
analysis.
3820 - 6
Revision 0
Date September 1986
-------
METHOD 3B20
HEXAOECANE EXTRACTION ANO SCREENING OF PURGEABLE ORGANICS
7. 1
Prepare sample
7.3.1
Calibrate
GC/FIO each
12-hour shift
7.2.2
Perform
GC/FIO analysis
o
3820 - 7
Revision 0
Date September 1986
-------
METHOD 3820
HEXADECANE EXTRACTION AND SCREENING OF PURGEABLE ORGANICS
(Cont Inued)
7 .2.4
Compare chromatograms
of hexadecane sample
extract and extracted
standard
7.2.4
Compare chromatograms
of hexadecane sample
extract ana extracted
1 standard
Are aromatic
distinguishable?
7.2.4.2
Use low-level
purge-and-trap
procedure
7.2.4
Use standard
mixture *1: determine
purge-and-trap method
to be used
ard mixture #2
to determine
purge—and-trap
method to use
7.2.4.1
Use
purge-and-trap
method
Use standard
mixture #1 to
determine
purge-and-trap
method to be used
ard mixture »2
to determine
ipurge-and-trap
method to use
3820 - 8
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 is intended or implied.
Ace Glass Company
1342 N.W. Boulevard
P.O. Box 688
Vlneland, NJ 08360
(609) 692-3333
Aldrich Chemical Company
Department T
P.O. Box 355
Milwaukee, WI 53201
Alpha Products
5570 - T W. 70th Place
Chicago, IL 60638
(312) 586-9810
Barneby and Cheney Company
E. 8th Avenue and N. Cassldy Street
P.O. Box 2526
Columbus, OH 43219
(614) 258-9501
Bio - Rad Laboratories
2200 Wright Avenue
Richmond, CA 94804
(415) 234-4130
Burdick & Jackson Lab Inc.
1953 S. Harvey Street
Muskegon, MO 49442
Calgon Corporation
P.O. Box 717
Pittsburgh, PA 15230
(412) 777-8000
Conostan Division
Conoco Speciality Products, Inc.
P.O. Box 1267
Ponca City, OK 74601
(405) 767-3456
COMPANIES - 1
Revision
Date September 1986
-------
Corning Glass Works
Houghton Park
Corning, NY 14830
(315) 974-9000
Dohrmann, Division of Xertex Corporation
3240 - T Scott Boulevard
Santa Clara, CA 95050
(408) 727-6000
(800) 538-7708
E. M. Laboratories, Inc.
500 Executive Boulevard
Elmsford, NY 10523
Fisher Scientific Co.
203 Fisher Building
Pittsburgh, PA 15219
(412) 562-8300
General Electric Corporation
3135 Easton Turnpike
Fairfield, CT 06431
(203) 373-2211
Graham Manufactory Co., Inc.
20 Florence Avenue
Batavia, NY 14020
(716) 343-2216
Hamilton Industries
1316 18th Street
Two Rivers, WI 54241
(414) 793-1121
ICN Life Sciences Group
3300 Hyland Avenue
Costa Mesa, CA 92626
Johns - Manvllle Corporation
P.O. Box 5108
Denver, CO 80217
Kontes Glass Company
8000 Spruce Street
Vineland, NJ 08360
MilUpore Corporation
80 Ashby Road
Bedford, MA 01730
(617) 275-9200
(800) 225-1380
COMPANIES - 2
Revision
Date September 1986
-------
National Bureau of Standards
U.S. Department of Commerce
Washington, DC 20234
(202) 921-1000
Pierce Chemical Company
Box 117
Rockford, IL 61105
(815) 968-0747
Scientific Glass and Instrument, Inc.
7246 - T Wynnwood
P.O. Box 6
Houston, TX 77001
(713) 868-1481
Scientific Products Company
1430 Waukegon Road
McGaw Park, IL 60085
(312) 689-8410
Spex Industries
3880 - T and Park Avenue
Edison, NJ 08820
Waters Associates
34 - T Maple Street
Mil ford, MA 01757
(617) 478-2000
(800) 252-4752
Whatman Laboratory Products, Inc.
Clifton, NJ 07015
(201) 773-5800
COMPANIES - 3
Revision
Date September 1986
.S. GOVERNMENT PRINTING OFFICE : 1987 O - 169-932
------- |