United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Cincinnati OH 45268
EPA/600/9-87/030
September 1988
Research and Development
Availability, Adequacy, and
Comparability of Testing
Procedures for the Analysis
of Pollutants Established
Under Section 304(h) of the
Federal Water Pollution
Control Act
Report to Congress
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EPA/600/9-87/030
September 1988
AVAILABILITY, ADEQUACY, AND
COMPARABILITY OF TESTING
PROCEDURES FOR THE ANALYSIS OF
POLLUTANTS ESTABLISHED UNDER
SECTION 304(h) OF THE FEDERAL WATER
POLLUTION CONTROL ACT
REPORT TO THE COMMITTEE ON PUBLIC WORKS AND
TRANSPORTATION OF THE HOUSE OF REPRESENTATIVES
THE COMMITTEE ON ENVIRONMENT AND PUBLIC WORKS OF THE
SENATE
United States
Environmental Protection Agency
Office of Research and Development
Environmental Monitoring Systems Laboratory
Cincinnati, Ohio 45268
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NOTICE
This document has been reviewed in accordance with U.S. Environmental Protection Agency
policy and approved for publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
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TABLE OF CONTENTS
VUl
ix
XI
GLOSSARY ;.....:;.;.;....:... .^.......... .^.
EXECUTIVE SUMMARY '...'.'. ^.'„!'., .V....'.'.....:....
PREFACE '!....
ACKNOWLEDGMENT xiii
CHAPTER ONE: Study Findings and Recommendations 1-1
Introduction 1_1
Availability and Adequacy of §304(h) Testing Methods 1-2
Comparability of FWPCA Monitoring Requirements and Testing
Methods With Other Federal and State Programs 1-6
Chapter One References 1-9
CHAPTER TWO: Determination of Testing Requirements Established Under Major
Environmental Programs 2-1
Testing Requirements Established under the FWPCA 2-1
Testing Requirements Established by Other Related Environmental
Legislation 2-16
Evolution of Testing Requirements 2-19
Inventory of Chemical Testing Requirements 2-23
Inventory of Biological Testing Requirements 2-29
Chapter Two References 2-63
CHAPTER THREE: Criteria for Determination of Adequacy
of Testing Methods 3_1
Method Performance Characteristics 3-2
Method Validation and Standardization 3.5
Criteria for Determination of Adequacy of Biological Methods 3-10
Chapter Three References 3_12
CHAPTER FOUR: Availability and Adequacy of Methods
to Support Testing Required Under the Clean Water Act 4-1
Overview of §304(h) Program 4.!
Methods Equivalency Program 4.3
Availability and Adequacy of §304(h) Methods for Measuring
Chemical Analytes 4_6
Availability of Biological Testing Methods 4-42
Adequacy of Biological Testing Methods 4.49
Chapter Four References 4-52
CHAPTER FIVE: Comparability of Testing Methods 5-1
Introduction and Summary 5_1
Background for Comparison of Testing Methods 5-2
Comparison of Testing Methods 5.4
Biological Methods 5_24
Chapter Five References 5-26
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CHAPTER SIX: Adequacy and Comparability of Quality Assurance Programs and
Quality Control Programs and Procedures 6-1
Introduction and Summary 6-1
Quality Assurance Programs 6-2
Laboratory Certification/Laboratory Accreditation 6-3
Other Quality Assurance Support 6-5
Reference Materials • 6-7
Quality Control Requirements • 6-10
Quality Assurance and Quality Control for Biological Methods 6-17
Chapter Six References • 6-18
CHAPTER SEVEN: Immediate and Long-Term Technology and
Testing Methods Needs /7'1
Overview and Summary 7-1
Immediate Methods Needs • 7'2
Long-Term Technology Needs 7'3
Discussion of Emerging Technologies and Methods - 7-5
Chapter Seven References ?~12
APPENDIX A~l
IV
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LIST OF TABLES
Table No. Page No.
II-1 Chemical Parameters Required for Monitoring in Water or with
Water Quality Standards 2-5
II-2 Agencies Submitting Data to STORET , 2-19
II-3 Type of Data Submitted to STORET 2-20
II-4 Examples of Organic Compound Names Used Interchangeably 2-24
II-5 Parameters Identified in Four EPA Regions That Are Required
to be Measured and That Do Not Have a §304(h) Method 2-26
II-6 Poorly Defined Water Quality Criteria Parameters 2-29
II-7 SDWA List 2-30
II-8 Table V of 40 CFR 122, Appendix D 2-31
II-9 Appendix VIII to 40 CFR Part 261 2-32
11-10 Michigan List 2-40
II-ll Sludge Monitoring List '...'.. 2-43
11-12 Pesticide Chemicals 2-43
11-13 Hazardous Substances 2-44
11-14 Examples of Parameters in STORET But Not §304(h) 2-50
11-15 SDWA Priority List 2-51
11-16 Human Pathogens, Parasites, and Indicator Organisms 2-52
II-17 Toxicity Tests 2-52
11-18 Use of Captive Organisms in Bioaccumulation and Toxicity Tests 2-53
11-19 Properties of Indigenous Communities of Aquatic Organisms
Used in Determining the Biological Integrity of Surface Waters 2-54
11-20 List of Required or Recommended Biological Test Parameters or
Species under CWA and SDWA 2-55
11-21 Water Quality Standards for Microbiological Parameters 2-55
11-22 Water Quality Criteria for Microbiological Parameters 2-56
11-23 List of Recommended or Required Species for Acute or Chronic Toxicity
Testing under NPDES Permits Program 2-59
11-24 Summary of NPDES Permits Requiring Biological Toxicity Testing
and States with Biological Testing Programs 2-61
III-l Examples of Detection Limits Definitions 3-3
IV-1 Chemical Parameters Listed in Table II-1 with No CWA Monitoring
Requirements 4-8
IV-2 Chemical Parameters Required for CWA Monitoring with No §304(h)
Methods 4-11
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IV-3 Test Procedures Developed by EMSL-Cincinnati not Promulgated in
40 CFR136 4-12
IV-4 List of Analytes and Methods with Regression Equations in Combined
WS and WP Studies , 4-16
IV-5 List of Analytes and Methods with Regression Equations in Combined
WS and WP Studies 4-23
IV-6 List of Analytes and Methods with Regression Equations in Combined
WS and WP Studies 4-27
IV-7 Method Performance and Comparison with Drinking Water Standards,
Discharge Limitations, and Water Quality Criteria 4-29
IV-8 Method Performance and Comparison with Drinking Water Standards,
Discharge Limitations, and Water Quality Criteria 4-33
IV-9 Method Performance and Comparison with Drinking Water Standards,
Discharge Limitations, and Water Quality Criteria 4-35
IV-10 Method Performance and Comparison with Drinking Water Standards,
Discharge Limitations, and Water Quality Criteria 4-37
IV-11 List of Approved Biological Test Procedures in 40 CFR 136.3, Table 1A 4-40
IV-12 List of Proposed Biological Test Procedures for 40 CFR 136.3, Table 1A 4-44
V-l Methods for Determination of Chlorinated Pesticides and Polychlorinated
Biphenyls (PCB's) in Water by Extraction and Gas Chromatography
with Electron Capture Detection 5-5
V-2 Comparison of Methods for the Determination of Halogenated Volatile
Organics in Water by Purge and Trap Gas Chromatography with
Electrolytic Conductivity Detection 5-9
V-3 Methods for Determination of Volatile Organic Compounds in Water by
Purge and Trap Gas Chromatography/Mass Spectrometry 5-12
V-4 Methods for Determination of Semi volatile Organic Compounds in Water by
Gas Chromatography/Mass Spectrometry , 5-17
V-5 Comparisons of Methods for the Determination of Selenium (SE) in Water by
Graphite Furnace Atomic Absorption Spectrophotometry (GFAAS) 5-20
V-6 Comparison of Methods for the Determination of Metals in Water
by Inductively Coupled Plasma (ICP) Spectroscopy 5-22
V-7 Comparison of Daphnia spp. Acute toxicity test procedure from three sources 5-25
VI-1 Approved EPA Methods in 40 CFR 136 Supported by Formal EMSL-Cincinnati
Method Validation Studies 6-6
VI-2 Method Validation Studies Completed for Other EPA Legislation 6-7
VI-3 Method Validation Studies In Progress for Other EPA Legislation 6-7
VI-4 Frequency of Quality Control Samples 6-12
VII-1 Examples of Immediate FWPC A Methods Development Requirement Needs . 7-4
VII-2 Examples of the Development of Environmental Analytical Instrumentation . 7-4
VII-3 Examples of New Technology for Potential Routine Use 7-6
VI
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LIST OF FIGURES
Figure No. Page No.
II-l Control of industrial waste water discharges in the United States 2-3
IH-1 Hierarchy of Analytical Methods 3-7
VII
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GLOSSARY
Analyte The constituent or characteristic of a sample which can be measured or identified.
Method A set of written directions necessary to perform measurements. A method
includes the analytical procedure as well as associated requirements such as
QA/QC procedures, data reporting, and calibration.
Validate To verify, using an acceptable scientific process, that a method is based on sound
technical principles and has been reduced to practice for routine measurement
purposes.
Protocol A set of definitive directions that includes precise guidance including quality
control and data reporting to meet a specific program or regulatory application.
Monitoring The measurement of chemical, physical, or biological analytes in environmental
samples for any Agency purpose.
VIII
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EXECUTIVE SUMMARY
Congress passed the Water Quality Act of
1987, PL 100-4, on February 4, 1987. Section
518 of the Act directed the United States
Environmental Protection Agency (EPA) to
study the availability and adequacy of field and
laboratory test procedures and methods to
support the provisions of the Act. It also
requested that the Agency study the
comparability of laboratory test procedures
among major federal environmental programs.
This study was conducted in three major
phases. First, the monitoring requirements and
data quality objectives of the Federal Water
Pollution Control Act (FWPCA) and other major
environmental legislation, such as the Resource
Conservation and Recovery Act (RCRA),
Superfund Amendments and Reauthorization
Act (SARA), Safe Drinking Water Act (SDWA),
and the Marine Protection Research and
Sanctuaries Act (MPRSA), were reviewed and
documented. Second, the test procedures
established under the authority of §304(h) and
promulgated in 40 CFR 136 were evaluated to
determine the availability and adequacy of these
test procedures to support FWPCA monitoring
and testing programs. Also in the second phase
of the study, test procedures established by EPA,
and other federal and state programs were
compared. The third phase of the study
evaluated the adequacy and comparability of
quality assurance/quality control programs
(QA/QC) to assure the validity of environmental
data.
This report was distributed widely for
review in the scientific and regulated
community. Representatives from EPA
headquarters and regional offices and
laboratories, as well as other federal and state
agencies, participated in a review of this
document. In addition, representatives from
major trade associations, municipal, commercial
and industrial laboratories also reviewed this
report.
The major findings and recommendations
resulting from this study are summarized below.
A more complete discussion of these topics is
found in Chapter 1.
Major Findings
1. The test procedures established in 40
CFR 136 under the authority of §304(h)
of the FWPCA are adequate for the
chemical analysis of priority toxic
pollutants for technology-based water
pollution controls.
2. The test procedures in 40 CFR 136 are
comparable to test procedures
established in monitoring programs
under SDWA, RCRA and SARA. In fact,
the analytical methods established in 40
CFR 136 for toxic pollutants identified in
§307(a) of the FWPCA served as the
basis for many of the test procedures
prepared in support of subsequent
legislation under several of these Acts.
3. The test procedures in 40 CFR 136 need
to be modified and expanded to respond
to the increased emphasis on human
health risk assessment and water-
quality-based controls and will require
significant expansion in the types and
numbers of test procedures in 40 CFR
136, additional consideration of test
methods for ambient monitoring, and
the development of new analytical
technology.
4. Improved coordination is needed in the
Agency's methods development program
to avoid duplication in the development
and standardization of test procedures
and inconsistencies in quality assurance
and quality control guidelines.
5. No Agency guidance exists for
certification of laboratories performing
analyses under provisions of the
FWPCA. Independent laboratory certifi-
cations for wastewater analyses are
performed by 18 states. Comments
received from representatives of the
regulated community on the draft of this
report strongly supported implemen-
tation of a nationwide, federally-
administered laboratory certification
program.
6. Standardized and validated test
procedures are needed for water-related
matrices, including domestic sludges,
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sediments, drilling muds, and biological
tissues to support regulatory and
monitoring programs under the
FWPCA.
Recommendations
Based on these findings, the Agency should take
the following actions:
1. Proceed expeditiously to establish
standard test procedures for
biomonitoring in 40 CFR 136, and
expand the scope of 40 CFR 136 to
include tests for additional chemical
analytes and for ambient monitoring
necessary to support human health risk
assessment and water-quality-based
controls;
2. Provide standardized and validated test
procedures for domestic sludges,
sediments, drilling muds, and biological
tissues and consider promulgation of
these procedures in 40 CFR 136.
3. Consider the establishment of an
Environmental Monitoring Manage-
ment Group to coordinate the
development of uniform test procedures
and quality assurance/quality control
guidelines within the Agency, to provide
a long-range program for the
development of analytical methods
employing new and emerging technology
and to explore the feasibility of a
uniform, national certification program
for laboratories performing test
procedures.
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PREFACE
Study Mandate
Congress passed the Water Quality Act of
1987, PL 100-4, reauthorizing and amending the
Federal Water Pollution Control Act of 1972, PL
92-500, on February 4, 1987. In §518 of the Act,
Congress directed the Agency to:
(a) STUDY - The Administrator shall study
the testing procedures for analysis of
pollutants established under §304(h) of the
Federal Water Pollution Control Act. Such
study shall include, but not be limited to, an
analysis of the adequacy and standard-
ization of such procedures. In conducting the
analysis of the standardization of such
procedures, the Administrator shall consider
the extent to which such procedures are
consistent with comparable procedures
established under other Federal Laws.
(b) REPORT - Not later than 1 year after
the date of the enactment of this Act, the
Administrator shall submit a report on the
results of the study conducted under this
subsection, together with recommendations
for modifying the test procedures referred to
in subsection (a) to improve their
effectiveness, to the Committee of Public
Works and Transportation of the House of
Representatives and the Committee on
Environment and Public Works of the
Senate."
Study Purpose and Scope
The purpose of this study was to determine
the availability and adequacy of testing methods
to support the testing requirements established
under the Federal Water Pollution Control Act
(FWPCA). To accomplish this, the major
compliance, enforcement and ambient
monitoring programs established under the
FWPCA were evaluated to determine:
• Chemical and biological testing
requirements,
« Data quality objectives,
• Promulgated or recommended tests and
methods, and
• Quality assurance/quality control
(QA/QC) methods.
The availability and adequacy of the testing
methods were examined relative to the needs of
the various FWPCA programs. Also, QA/QC
methods were evaluated to determine their
ability to assure the production of monitoring
data needed to support the goals of the Agency's
FWPCA programs.
The testing requirements established under
other Federal legislatively-mandated environ-
mental programs were also compared. The
consistency of these testing requirements and
methods was compared with corresponding
methods established under FWPCA programs.
The following programs were studied: the Safe
Drinking Water Act (SDWA) of 1974 as
amended in 1986, PL 99-339; the
Comprehensive Environmental Response,
Compensation and Liability Act of 1980
(CERCLA or Superfund) as amended by the
Superfund Amendments and Reauthorization
Act (SARA) of 1986, PL 99-499; the Resource
Conservation Recovery Act of 1976 as amended
by the Hazardous and Solid Waste Amendments
Act of 1984, PL 98-616; as well as programs
managed by the U.S. Geological Survey,
National Oceanic and Atmospheric
Administration, and the U.S. Army Corps of
Engineers.
Study Approach
Staff from major program offices in
•headquarters and regional offices and state
agencies were interviewed. Instrument
manufacturers were interviewed to determine
the status of new technology and availability of
new instrumentation. Methods manuals and
quality assurance documents were collected and
reviewed, and major databases were surveyed to
determine the data routinely being generated
using these methods. The study was conducted
in three phases.
In the first phase, the testing requirements
established by the various program offices were
catalogued. Common terminology was estab-
lished when necessary so that the specific suites
XI
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of analytes could be compared, among
corresponding programs. Data quality
objectives, when available and well-defined,
were also catalogued.
Phase two of the study consisted of
assembling available, testing methods for the
determination of chemical and biological
analytes. The testing methods established under
§304(h) of the FWPCA, promulgated in 40 CFR
136, were reviewed to determine their
availability and adequacy to support all FWPCA
testing requirements. Methods established to
support other FWPCA monitoring programs, but
not promulgated in §304(h) were also reviewed.
Testing methods established and promulgated
under other regulations were assembled and
reviewed to determine the comparability of
testing and QA/QC methods.
The third phase of the study was a review of
the Agency's FWPCA quality assurance
program and the quality control requirements in
each testing method to determine the ability of
these methods to produce data of sufficient
quality to achieve the monitoring objectives
established under the various FWPCA
programs. The QA/QC methods established
under the FWPCA were compared to
corresponding methods established by other
programs.
This report was distributed widely for
review in the scientific and regulated
community. Representatives from EPA
headquarters and regional offices and
laboratories, as well as other federal and state
agencies, participated in a review of this
document. In addition, representatives from
major trade associations, municipal, commercial
and industrial laboratories also reviewed this
report.
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ACKNOWLEDGMENT
The information in this report was prepared
with the assistance of Enseco, Inc. under
Contract No. 68-01-3410. To prepare this report,
published regulations, manuals, and data bases
of the U. S. Environmental Protection Agency
were reviewed. Interviews were conducted with
State water pollution staff, Federal agency
personnel, research foundations, and
representatives of a variety of national
organizations. Preliminary findings were
identified and presented to a workgroup at the
Environmental Monitoring Systems Laboratory,
Cincinnati, for comments and revision. A draft
of this report was widely distributed to
representatives of the regulating and regulated
communities. The information in this final
report reflects an attempt to present a balanced
and representative analysis of current
information on availability and adequacy of test
procedures for measuring pollutants under the
provisions of the Federal Water Pollution
Control Act.
XIII
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CHAPTER ONE
STUDY FINDINGS AND RECOMMENDATIONS
Introduction
Latest figures from the Department of
Commerce estimated that in 1985,
manufacturing establishments in the United
States expended $2.8 and $11.7 billion in capital
improvements and operating costs, respectively,
for pollution abatement (1-1). Since the study
only included environmental programs at
manufacturing facilities, Resource Conservation
and Recovery Act (RCRA) and Superfund
activities occurring off-site and federal and state
Superfund activities were not considered.
Therefore, the total expenditure in the United
States for pollution control is significantly
larger. Considering the additional requirements
established recently under the Federal Water
Pollution Control Act (FWPCA), Safe Drinking
Water Act (SDWA), RCRA, and Comprehensive
Environmental Response Compensation and
Liability Act (CERCLA), these annual
expenditures are projected to increase in the
future. Approximately 7-10% of the total
expenditure for pollution control is used for
planning and conducting studies and analyzing
the data from environmental programs (1-2). Of
this total monitoring expenditure, one-third to
one-half is used for laboratory testing (1-3),
which amounts to about a billion dollars. The
adequacy and accuracy of these laboratory tests
are critical to establishing efficient and cost-
effective pollution control programs.
Over the last decade, there has been
explosive growth in the requirements to collect
environmental monitoring data. Until 1976, the
majority of chemical monitoring was performed
for a few conventional analytes (e.g., minerals,
demand analyses, nutrients, and oil/grease) in
ambient waters and industrial and municipal
effluents. Biomonitoring consisted of effluent
toxicity tests and field surveys of phytoplankton,
zooplankton, macroinvertebrates and fish in
both stressed and natural ecosystems. As a
result of a 1976 consent decree (Natural
Resources Defense Council, Inc. et al. v. Train, 8
ERC 2120 (D.D.C. 1976)), and the 1977 Clean
Water Act Amendments to the FWPCA, there
was a dramatic shift in emphasis to the control
of and monitoring for priority toxic pollutants.
In addition, EPA and state agencies broadened
their monitoring programs from a focus
principally on the analyses of chemical
constituents of surface waters and wastewaters
to the analyses of biological toxicity, as well as
sediments and biological tissues. The Agency
realized that technology-based controls and
chemical monitoring alone would not achieve
the goals of the FWPCA, and in 1984 adopted
toxicity testing as a key component of its toxics
control strategy (1-4).
Over the same time period, new monitoring
programs were established by EPA under the
SDWA, the RCRA, Superfund,. Toxic Substances
Control Act (TSCA), Federal Insecticide,
Fungicide and Rodenticide Act (FIFRA), and by
other federal and state agencies with emphasis
on control of and monitoring for toxic pollutants.
Including all environmental monitoring
programs, the number of chemical and biological
analytes has increased more than ten-fold in the
last decade and may increase by another order of
magnitude in the next decade.
In addition to the significant growth in the
size and complexity of testing requirements,
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there is the need to measure environmental
pollutants at lower concentration levels. In the
early 1970's, measurement of conventional
pollutants was required at the part per million
level. In the late 1970's and the early 1980's,
some toxic priority pollutants were regulated to
the part per billion level. Future monitoring in
some cases may require the measurement of
some toxic chemicals to the part per trillion
level.
While the complexity of the chemical and
biological testing requirements has increased,
the scrutiny of the results has increased in equal
measure. In the early 1970's and before, the vast
majority of testing was required to support
ambient air and water monitoring studies in
which testing methods and QA/QC were rarely
an issue. Today, due to the much greater
emphasis on pollution control and the costs
associated with waste treatment, laboratory
methods and data quality are carefully
scrutinized as a matter of routine.
Testing methods promulgated in 40 CFR 136
under the provisions of §304(h) have grown in
number, complexity, and degree of validation
correspondingly with the monitoring
requirements of the FWPCA. When introduced
in 1973, 40 CFR 136 contained approved
methods for 71 analytes. Including the proposal
for additional testing methods in September,
1987,40 CFR 136 now contains 262 analytes and
over 500 test methods. Additional biological
parameters and test methods are soon to be
proposed to support the toxicity testing
requirements established under the toxics
control strategy.
This report responds to the request by the
Congress for a review of the test procedures
established under §304(h) of the FWPCA. The
methods for priority toxic pollutants developed
in response to §307(a) of the 1977 Clean Water
Act Amendments to the FWPCA were examined
in detail to evaluate the availability and
adequacy of the FWPCA methods and to
compare these methods to similar methods
established under other environmental
legislation. The report identifies current method
needs for the support of FWPCA regulations and
monitoring requirements, describes steps EPA
will take to manage the development and
standardization of methods, and identifies areas
where EPA could further standardize test
procedures and QA/QC practices over time.
The findings and recommendations
presented in this chapter were based on
information obtained as described in the Study
Approach. The subsequent chapters of this
report present detailed information relating to
these findings as summarized below:
Issue Discussion
Availability and Adequacy of Chapter 4
§304(h) Methods (Findings 1-9)
Comparability of §304(h) Methods Chapter 5
(Findings 10-14)
Quality Control / Quality Chapter 6
Assurance (Findings 4,13, and 14)
Emerging Technologies Chapter?
Availability and Adequacy of §304(h)
Testing Methods
1) Finding: Testing methods established to
date under §304(h) of the FWPCA are
substantially adequate to meet the
chemical testing requirements of the
Industrial Pretreatment and National
Pollutant Discharge Elimination System
(NPDES) programs to monitor
compliance for priority pollutants. The
Agency has made significant progress in
defining method performance for the Agency
methods for priority toxic pollutants
promulgated in 40 CFR 136 and
incorporating these data into QC
performance criteria. The results of
additional validation studies are being
incorporated into 40 CFR 136 methods as
they become available. However, such
studies are recognized to be costly and time
consuming.
Recommendation: The Agency should
establish sound, realistic priorities and a
joint OW/ORD action plan for
incorporating method validation data
into promulgated methods and
1-2
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establishing additional performance
criteria for other EPA chemical methods
promulgated in 40 CFR 136. Other
additional appropriate test methods which
have been validated and contain method
performance statistics should be
promulgated under 40 CFR 136.
2) Finding: The methods in 40 CFR 136 are
not completely adequate to fully support
the implementation of controls for
pollutants beyond the priority
pollutants, including effluent toxicity, or
for certain pollutants requiring low
detection levels. The primary reason for
this is that the methods standardization and
promulgation process under Part 136 has
lagged behind the development and
availability of adequate methods for these
areas. The Agency is taking action to correct
the problem by incorporating toxicity test
procedures in 40 CFR 136 to support
biomonitoring programs, as the biological
test methods in 40 CFR 136 are presently
limited to five microbiological indicator
tests. It is necessary, however, to measure
some priority toxic pollutants at detection
levels below the capability of some of the
currently promulgated methods. In addition,
the implementation of some water quality-
based controls requires analyses of specific
chemical pollutants which are not currently
included in 40 CFR 136. Finally, the
adequacy of point source controls will be
judged in part based on ambient
measurements.
A review of the data in EPA's STORET
environmental data base shows that many
state agencies routinely monitor for more
analytes than are found on the list of §307(a)
toxic pollutants. In the future, methods will
be required to measure an expanded list of
toxic chemicals and new, additional methods
will be needed to screen for toxic inorganic
and organic pollutants that are not on
current Agency target compound lists. As
biomonitoring is used to identify toxic
discharges and stream segments with water
quality problems, toxicity reduction
evaluation (TRE) programs need to be
performed to identify the source of the
toxicity. Numerous TRE studies have shown
that the causative chemical is often not a
toxic pollutant established under §307.
Recommendation: The action plan
should establish a schedule for
promulgating biomonitoring methods as
soon as possible. In addition, OW and
ORD should agree on ways to improve
the process for developing and
standardizing test procedures. The
process should set priorities for
expanding the applicability of existing
§304(h) chemical and biological test
methods for FWPCA compliance and,
where appropriate, to ambient
monitoring programs by modifying
existing methods and adding new
methods. New chemical methods need to be
developed and standardized over time in a
priority sequence to measure an expanded
list of toxic pollutants and to measure at
concentration levels to support water
quality-based controls. Existing methods to
measure inorganic and organic chemicals
will need to be modified to achieve better
sensitivity. Many chemicals beyond the
priority toxic pollutant list, such as water-
soluble polar organics, are also toxic but are
not measurable using the methods currently
approved in 40 CFR 136. Therefore, the plan
should set priorities for research efforts to
develop liquid chromatography methods
with mass spectrometry detection.
Similarly, if measurements for the analysis
of toxic metals are to be performed at the
concentration levels of water quality
standards, efforts to develop inductively
coupled plasma/mass spectrometry detection
techniques should be considered. The pace of
development, documentation and
standardization of biomonitoring methods
needs to be accelerated to support the toxics
program initiatives which will rely heavily
on such methods to complement chemical
monitoring.
3) Finding: For each chemical analyte in 40
CFR 136, there are typically multiple
analytical methods approved for use,
and these methods often have different
(or unstated ) detection limits, precision,
1-3
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4)
and accuracy. As the data quality needs of
each FWPCA monitoring program become
more demanding, there will be a need to
differentiate the use of multiple methods
promulgated for each test analyte. For some
of the methods approved in 40 CFR 136, one
or more of the principal descriptors of
method capability (detection limits,
precision and accuracy) is not published in
the method or in readily-accessible
background documents. In addition, a
survey of the use of §304(h) methods showed
that over a hundred of the test methods are
apparently not being used by government,
commercial, and industrial laboratories.
Recommendation: The action plan
should consider the differing data
quality needs of the National Pollutant
Discharge Elimination System,
Industrial Pretreatment, and other
FWPCA monitoring programs so that
the correct testing can be identified for
differing monitoring applications. The
action plan should then determine the
degree to which detection limits, precision,
and accuracy achieved with each test
method approved in 40 CFR 136 should be
established and documented in the method.
The Agency should consider deleting any
test methods that are causing confusion or
detrimental program results. The Agency
should continue close coordination with
other methods standardization groups such
as Standard Methods, American Society for
Testing and Materials, Association for
Official Analytical Chemists and the U.S.
Geological Survey.
Finding: The Agency's current
mandatory quality assurance program
under the FWPCA is not intended to
fully document the quality of
enforcement, compliance and ambient
monitoring data produced by
government, commercial and industrial
laboratories. Specific laboratory quality
control requirements and criteria have been
incorporated into 15 test methods for
priority toxic pollutants promulgated in 40
CFR 136. The Discharge Monitoring Report-
Quality Assurance (DMR-QA) annual
performance evaluation (PE) study, which
includes data from over 7000 major NPDES
dischargers, is used most effectively by the
Office of Water Enforcement in improving
the quality of data being generated by the
regulated community. However, due to
budget restrictions, the study collects data
for only 29 chemical and no biological
analytes out of 262 promulgated at 40 CFR
136. EPA has not established a formal
laboratory certification program to validate
the capability of laboratories performing
monitoring for NPDES permittees.
Recommendation: The Agency should
develop quality control data
requirements for all test methods in Part
136 which are used in the NPDES and
industrial pretreatment programs as
well as for laboratories performing
ambient monitoring. These data would
enable the Agency to verify that the
required QC methods were followed and to
evaluate the quality of data produced. The
Agency should study the feasibility of a
laboratory certification program
incorporating such performance evaluation
studies for all laboratories performing
testing required by the FWPCA.
5) Finding: Not all analytical methods for
sediments and biological tissues for
ambient monitoring under the FWPCA
toxics control program have been
standardized and validated.
Furthermore, since 40 CFR 136 analytical
methods and equivalency procedures are not
provided for ambient monitoring, there is no
assurance that comparable data are being
obtained from various programs, such as
state monitoring programs. An examination
of the data in STORET shows that data are
collected and stored for every state resulting
from monitoring of surface waters, bottom
sediments and biological tissues. As these
media are the primary receptors of toxic
pollutants, the analysis of bottom sediments
and biological tissues is becoming
increasingly important in the determination
of the extent of historical contamination and
the effectiveness of current environmental
controls.
1-4
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Recommendation: The action plan
should set priorities for research to
develop, standardize and validate
methods for the analysis of toxic
pollutants in bottom sediments and
biological tissues, and should consider
ambient toxics monitoring and effluent
toxicity methods for promulgation in 40
CFR 136. Existing §304(h) technology and
methods can be applied to the analyses of
sediments and biological tissues with the
inclusion of appropriate sample extraction
and cleanup and quality control methods.
6) Finding: EPA is developing rulemaking
providing guidelines for disposal of
sewage sludge and will be conducting a
national sewage sludge survey. Ana-
lytical methods for the analysis of pollutants
in sludge are available for five categories of
pollutants (organics, pesticides/ herbicides,
dioxins/ furans, metals, and classicals) and
are in various stages of standardization. To
date, methods for analysis of metals and
classicals in sludge have been fully
standardized and published. Methods for the
other categories are now undergoing intra-
and inter-laboratory studies.
Recommendation: The joint OW/ORD
work plan to be developed should
provide a schedule for completing the
standardization of analytical methods
for sewage sludge for promulgation in 40
CFR 136.
7) Finding: There is a significant difference
between §404 dredge spoil material
monitoring requirements established by
various Corps of Engineers (COE)
district offices and the bottom sediment
monitoring programs of state agencies.
Methods developed to support the §404
program under the FWPCA and §301 under
the Marine Protection, Research and
Sanctuaries Act (MPRSA), while developed
jointly by the EPA and COE have not been
incorporated into 40 CFR 136. A spot check
of several COE district office programs
indicates that while districts rely to some
extent on the methods developed by the COE
Waterways Experiment Station, each COE
district office is free to specify different
testing methods. As a result, valid
comparisons of sediment data from EPA,
COE and state programs can be difficult.
Recommendation: The EPA and COE
should coordinate incorporation of
sediment methods into 40 CFR 136 to
insure that they meet the §404 program
requirements. This would ensure that
monitoring data generated from analyses of
sediments required under EPA and COE
programs and by state agencies are
comparable.
8) Finding: Extensive additional
development, standardization and
validation of biological monitoring
methods needs to be performed to
support the FWPCA toxics control and
field monitoring programs. The Agency
will soon propose to amend 40 CFR 136 to
include various biomonitoring methods
required to support the NPDES permit
program and related programs. These
toxicity test methods (e.g., acute and
chronic) have been standardized and
subjected to single and multiple laboratory
evaluations. Still other important toxicity
test methods and many of the important
biological field monitoring methods are still
under development or require further
standardization and validation. Biological
test methods, particularly field and
laboratory methods requiring the culturing
of test organisms, are difficult to
standardize. Rigid methods cannot address
the specifics of each field and laboratory
situation.
Recommendation: The OW/ORD action
plan should prioritize FWPCA
biomonitoring program needs so that
the method development and
standardization efforts can focus on the
most important needs first. As
recommended by the EPA Science Advisory
Board, additional studies of the basic biology
of designated test species or indicator
organisms should be undertaken. The plan
should also establish QA/QC program
guidance and provide QA support for
biomonitoring laboratories and augment
training programs on the use of biological
1-5
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test methods. EPA should evaluate the
feasibility of a laboratory evaluation or
certification program similar to the EPA
program for evaluating and certifying
drinking water chemistry and microbiology
laboratories.
9) Finding: The continuing growth in
monitoring programs and methods
requires a responsive mechanism for
adding or changing methods
promulgated under §304(h). It typically
takes several years from proposal to final
rule to add new testing technologies to 40
CFR 136. Because of the continued
development of new and better technology
by laboratory research and instrument
manufacturers, the methods promulgated
for priority toxic organic pollutants in 1984
substituted performance criteria for detailed
specifications in non-critical areas of the
method that were undergoing rapid
development.
With the rapid advances of technology and
improvements in test methods, it is also
clear that many new approaches are
emerging that may produce data that are
equivalent to or better than data produced
by the methods currently approved in 40
CFR 136. The current method equivalency
program in 40 CFR 136 effectively controls
the use of new methods proposed by
monitoring laboratories for the
measurement of analytes which are
currently promulgated. However, as
biomonitoring and chemical methods are
added to measure a broader range of sample
matrices and analytes at lower levels, it may
be difficult to apply the current statistical
protocols of the existing method equivalency
protocol. Requirements for method
equivalency may need to be altered for
biological methods.
Recommendation: The action plan
should set a realistic schedule for
defining explicit performance criteria in
each §304(h) method so that minor
improvements in technology and
methods can be validated by the analyst
by collection of data to meet these
criteria. This would considerably speed the
adoption of minor improvements and
technology and yet control changes to the
standardized analytical methods. In
addition, the Agency should reevaluate its
current statistical protocols for evaluating
method equivalency to allow for the
approval of methods which considerably
expand the capability or improve the quality
of data of existing §304(h) methods.
Comparability of FWPCA
Monitoring Requirements and
Testing Methods with Other Federal
and State Programs
10) Finding: An evaluation of the
monitoring programs established under
the authority of major environmental
laws, demonstrates that the analytical
methods are sometimes unnecessarily
different, as they relate to similar sample
matrices, target analytes, and data
quality objectives. Monitoring programs
established under FWPCA, SDWA, RCRA,
Superfund, TSCA and FIFRA are
increasingly concerned with the same
sample media. Different program objectives
have resulted in differences in the specific
monitoring requirements and lists of
analytes. This has resulted in parallel
programs for developing and standardizing
analytical methods and has led to confusion
for those performing the required
monitoring. The past attempts by the
Agency to streamline analytical methods
used by different programs have not been
successful.
Recommendation: The Agency should
establish a workgroup to compile and
evaluate monitoring requirements
including target analytes and the data
quality objectives in each Agency
program. Eventually, representatives of
other federal agencies such as Department of
the Interior-U.S. Geological Survey,
Department of Commerce-National Oceanic
and Atmospheric Administration and the
Department of Defense- Corps of Engineers
as well as state agencies could be included.
The goal would be to integrate, when
1-6
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appropriate, the monitoring requirements,
target analytes and data quality objectives,
as well as clarifying needed distinctions
among programs. Significant efforts are
ongoing in each program office to rank the
importance of chemicals according to
toxicity, production/use, physical properties,
bioaccumulation in the environment,
carcinogenicity, and several other factors.
Program offices could combine their ranking
systems into one common system where
possible. A master list of chemicals could
then be developed, reviewed, and prioritized.
While measurement of every chemical on
this list would not be required in every
sample matrix by every Agency program,
the list would contain chemicals which are
common to all program offices. The
Industrial Technology Division presently
maintains such a list to track substances
that are on the major regulatory lists from
all of the program offices. This "List of Lists"
could serve as a basis for the list to be
studied by the work group. The work group
could meet on an infrequent basis to refine
and, if necessary, reprioritize the target
substances and biological monitoring
analytes as well as review the data quality
objectives for each of the Agency's
monitoring programs. The end result would
be a master list of chemical and biological
monitoring analytes and sample matrices for
the whole or subset of this master list of
chemicals, the required detection levels by
chemical or by sample matrix, and the
precision and accuracy goals to support each
Agency monitoring program. This effort
would precede the selection of methods from
among those currently available and the
development of new testing methods by the
combined task group.
11) Finding: Nomenclature for toxic
chemicals and definitions of common
method performance criteria are not
standardized. This compromises the
Agency's ability to develop consistent
monitoring requirements and methods.
Recommendation: The Agency should
adopt standardized nomenclature
including the use of Chemical Abstract
Service (CAS) numbers to assure that
each target chemical is unambiguously
identified. Furthermore, insofar as
practical, the Agency should adopt common
statements of method performance criteria
and expressions of data quality objectives
throughout all offices and monitoring
programs.
12) Finding: Duplication of methods and
methods manuals by Agency program
offices and other federal and state
agencies has resulted in confusion in the
regulated community. Almost all of the
chemical methods promulgated or
recommended for EPA programs, as well as
those of other federal and state agencies,
rely on the technology standardized for the
measurement of toxic pollutants under the
FWPCA. There are some legitimate
differences among programs since not all
monitoring requirements are developed from
the same criteria. However, a careful review
of selected high-use methods shows that
differences are often superficial and
unnecessary, and that some program offices
have adopted out-of-date 40 CFR 136
methods or made changes which degraded
rather than improved the methods.
As monitoring programs become driven by
criteria developed to protect human health
and aquatic life, the requirements for the
analyses of a particular matrix such as
water, sediment, biological tissue, and air
samples may be the same whether
established under FWPCA, SDWA, RCRA or
Superfund programs. The apparent
duplicative efforts involved in developing
separate methods manuals to accomplish the
same purpose seem to be difficult to justify.
At the same time, gaps remain in the
availability and adequacy of methods
required to control many other toxic
pollutants.
Recommendation: An Environmental
Methods Management Group should be
formed to coordinate common analytical
methods and methods manuals
throughout the Agency. A first objective
should be the establishment of a
computerized catalogue of the availability,
1-7
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applicability, and degree of standardization
of methods currently in use in the Agency.
Experts who would coordinate the exchange
of information, should be identified as focal
points in each major scientific or technical
area.
Methods used in special environmental
monitoring studies performed or funded by
federal and state agencies should be
included where possible in the method
tabulations. This data base could be tied into
other existing data bases in the scientific
community. Then, any investigator with the
responsibility for developing an
environmental monitoring program could
search this data base to determine the
availability and adequacy of methods to
support the subject study. This would tend to
eliminate duplicative efforts among
investigators.
A second objective of the Group would be to
annually review and coordinate all Agency
methods development and validation
activities to assure that the Agency's
resources are efficiently directed towards
solving the methods development and
validation problems of greatest priority.
Again, interagency coordination at the
federal level should follow to minimize
replicative efforts on the part of the other
federal agencies who are performing
environmental monitoring.
The Group could also consider over the long
term the feasibility of the development of a
common methods manual for all programs.
Although this would be a difficult task and
require a long-term commitment, a single
manual is technically feasible because the
majority of methods in use today employ
common technology. Such a methods manual
would consist of a description, in detail, of
the technology, specific directions as to how
each method must be modified to achieve the
required detection limits, and precision and
accuracy on each sample matrix type. The
exact group of chemicals and sample
matrices for which a method has been
standardized and validated should be listed
in the method. However, there are numerous
questions of manageability and usefulness
that need to be addressed.
13) Finding: Although the EPA has a
national quality assurance program
which provides a range of QA supports
and guidance, the mandatory quality
assurance programs and specific quality
control methods established within the
Agency's operating programs and in
other federal and state programs are
often inconsistent, sometimes
inadequate, and not always cost-
effective. There are literally dozens of
different federal and state laboratory
evaluation programs and different QA
requirements that must be met by
commercial and industrial environmental
laboratories operating interstate. The
majority of the program requirements are
based on sound rationale but responses to
these separate and uncoordinated federal
and state regulatory programs are costly,
repetitive and do not necessarily improve
data quality.
Environmental data generated in one state
may be scrutinized in detail, while the data
can go nearly unchecked and uncontrolled in
a neighboring state. In addition to being an
inequitable burden both on the laboratories
and those funding the work, this diversity of
quality assurance makes data comparisons
difficult.
Recommendation: The Administrator
should establish a task force of the
Environmental Methods Management
Group to coordinate the development of
uniform QA/QC requirements within
methods, and a tiered structure of
minimal QA/QC requirements across all
Agency monitoring programs. The
Administrator should consider discussions
with other federal agencies toward
developing uniform methods and quality
assurance requirements across all federal
environmental programs.
14) Finding: Because of the increased
reliance upon complex laboratory
measurements performed under
carefully controlled conditions, EPA
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should determine whether there is a
need for a uniform laboratory
certification program for the FWPCA
programs. The Agency has a formal
program of certification of drinking water
laboratories. The Agency also has two water
laboratory approval programs based largely
on study performance: 1) the Discharge
Monitoring Report - Quality Assurance
(DMR-QA) studies for major dischargers
under the National Pollutant Discharge
Elimination System (NPDES) who must
perform satisfactorily on a group of basic
analytes, once per year, and 2) the Water
Pollution (WP) Studies conducted
semiannually for all wastewater and
ambient monitoring laboratories. In the non-
water areas, performance evaluation (PE)
studies are conducted quarterly for the
Resource Conservation Recovery Act
(RCRA) and Comprehensive Environmental
Response Compensation and Liability
Act/Superfund Amendments and
Reauthorization Act of 1986
(CERCLA/SARA) laboratories.
These five program areas for laboratory
evaluation/approval in the EPA are
compounded by the state studies conducted
by most primary states in three or more of
these areas. Consequently, any laboratory
operating interstate may be required to
operate according to varying but
overlapping QA/QC requirements and
performance requirements for a number of
state and federal programs.
Recommendation: A task force should be
created, which consists of representatives
from ORD and EPA program offices, and
other federal and state agencies and
interested parties to evaluate the feasibility
of a nationally coordinated environmental
laboratory certification program. The task
force should consider whether criteria should be
developed requiring routine review of QC
documentation of laboratories performing
environmental analyses.
Chapter One References
1. U.S. Department of Commerce, Bureau of
Census, 1985. Pollution Abatement Costs
and Expenditures.
2. Klein, J.A. and Sulam, M.H., 1986. Waste
Services Industry, Analytical Services
Sector.
3. Carter, M.J., 1987. Confidential Market
Analysis.
4. U.S. Environmental Protection Agency,
1984. Development of water quality-based
permit limitations for toxic pollutants. 49
Federal Register: 9016, March 9,1984.
1-9
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CHAPTER TWO
DETERMINATION OF TESTING REQUIREMENTS
ESTABLISHED UNDER MAJOR ENVIRONMENTAL
PROGRAMS
As the first part of this study, a detailed
assessment was performed to determine the
monitoring requirements and data quality
objectives established under major
environmental legislation. Specifically, an
assessment was performed to: 1) determine the
chemical and biological measurements that are
required by various Federal Water Pollution
Control Act (FWPCA) programs; 2) assess the
monitoring requirements established under
other environmental legislation; and 3)
determine the relationship of the monitoring
requirements among the various regulatory
programs.
Testing Requirements Established
Under the FWPCA
Congress enacted the Federal Water
Pollution Control Act Amendments in 1972 (PL
92-500), replacing several previously enacted
but uncoordinated water pollution control acts,
such as the Water Quality Act of 1965, Clean
Water Restoration Act of 1966, the Water
Quality Improvement Act of 1970, all of which
were amendments to the original Federal Water
Pollution Control Acts of 1948 and 1956 (2-1).
The 1972 FWPCA is the basic water pollution
control statute for most of EPA's current water
regulations and programs requiring monitoring.
The FWPCA was amended in 1977 (PL 95-217),
in 1978 (PL 95-576), and again recently with the
Water Quality Act of 1987 (PL 100-4).
The broad goals of the FWPCA are to: (1)
achieve adequate water quality to protect fish,
shellfish and wildlife and for recreational
purposes (fishable, swimmable standard); and
(2) eliminate the discharge of pollutants in toxic
amounts to the Nation's waters. The FWPCA
established a comprehensive regulatory
program to be carried out by the Environmental
Protection Agency (EPA) and the states. The
basic elements of the program, relative to
monitoring, include the following:
• A system of technology-based effluent
limits establishing base-level or minimum
treatment which must be achieved by
direct industrial dischargers (existing and
new sources) and publicly-owned
treatment works (POTW's), and a
complementary system of pretreatment
requirements applicable to discharges to
POTW's.
• A program for imposing more stringent
limits where such limits are necessary for
achieving water quality standards or
objectives.
• A permit program (the National Pollutant
Discharge Elimination System - NPDES)
requiring dischargers to disclose the
volume and nature of their discharges;
authorizing EPA to specify the limitations
to be imposed on such discharges; imposing
on permittees an obligation to monitor and
report as to their compliance or non-
compliance with the permit limits; and
authorizing EPA enforcement in the event
of non- compliance.
• Specific provisions for accidental
discharges of toxic chemicals (e.g.,
accidental oil spills).
• Extensive environmental monitoring
programs, such as outlined in Section
106(e), were required to identify problems
and judge the effectiveness of the water
pollution control program.
2-1
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A detailed review of the FWPCA and
associated EPA regulations is beyond the scope
of this study. However, a brief synopsis of the
major programs that require monitoring is
useful to understanding the need for
standardized monitoring methods for all
programs so that data can be easily and
meaningfully compared. Figure 2-1 outlines the
overall scheme for controlling wastewater
discharges under the FWPCA.
Technology-Based Limits
The first of the four major FWPCA
regulatory mechanisms is the system of
technology-based limits which must be adopted
pursuant to §§301,304, and 307. Consistent with
"the goal of eliminating toxic substances in toxic
amounts", these technology-based standards are
to be achieved regardless of whether
uncontrolled discharges would have an impact
on water quality. There are three basic types of
technology-based limits:
(1) §301(b) establishes limits for Direct
Industrial Dischargers on an industry-by-
industry basis that are of the following
types:
• Best Practicable Technology (BPT) is
defined as the average of the best existing
performance by well-operated plants
within each industrial category. BPT
emphasizes end-of-pipe treatment for toxic
chemicals rather than in-plant control
measures and considers cost versus
benefits.
• Best Conventional Pollutant Control
Technology (BCT) is designed to limit
"conventional" pollutants (e.g.,
biochemical oxygen demand, suspended
solids, fecal coliform bacteria, and pH).
• Effluent Limits for 'Nonconventional,
Nontoxic Pollutants control the remaining
pollutants (e.g., chlorine, phenol).
• New Source Direct Discharges are
controlled differently than those
discharges in operation at the passage of
the act. EPA is compelled to look at plant
operations, various alternative production
processes or other aspects of the operation
in order to reduce discharges, regardless of
cost or availability of technology.
• Best Available Economically Achievable
Control Technology (BAT) is the most
stringent of the technology-based
limitations. Rather than using the average
of the best technology most widely used
within an industry category (BPT), BAT is
based on the best technology in existence
regardless of its usage. This limit typically
forces adoption of better technology by
industry as the technology develops
through time.
(2) Limits for Publicly Owned Treatment Works
(POTW's). POTW's are also required to
obtain NPDES discharge permits and
achieve technology-based effluent
limitations, but the standards are different
than for industrial facilities. Secondary
treatment and eventually Best Practicable
Waste Treatment Technology (BPWTT) are
required, although the emphasis has largely
been on conventional pollutants.
(3) Pretreatment Limits for Indirect
Discharges. Industrial facilities that
discharge into publicly owned treatment
works, and thus are not subject to standards
applicable to direct discharges, are subject to
categorical pretreatment standards under
§307(b). Under the pretreatment
regulations, the release of certain pollutants
is prohibited, such as those that could
interfere with the operation of the POTW, or
pass through the treatment system without
a reduction in concentration. To date, EPA
has identified six pollutants under the
NRDC, et al., Consent Decree (Paragraph
4(c)) that should be prohibited from
discharge to POTW's. (2-2). Treatment
requirements were also adopted, industry-
by-industry, for treating wastes,
particularly toxics. In the 1987 amendments
to the FWPCA, the EPA was mandated to
study the adequacy of pretreatment
technology for toxics in POTW
discharges(§519).
The approximately 100,000 manufacturing
facilities discharging into the 1500 POTW's with
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Effluent Limitation* Guidelines
and Standards for Industrial
Discharges
Technology-Based Regulations for
each Subcategory within an Industry
Developed by EPA's Industrial
Technology Division
1 Direct Dischargers
I Indirect Dischargers j
BPT:
Best Practicable Control
Technology Currently Available
BCT:
Best Conventional Pollutant
Technology Currently Available
BAT:
Best Available Technology
Economically Achievable
NSP&
New Source Performance
Standards
IMPLEMENTATION AND ENFORCEMENT
Municipal Permit
Regulations and General
Pretreatment Regulations
Direct Discharge Permit Application
Submitted by Industry
Approved State and EPA
Regional Water Enforcement Offices
POTW:-
Publically Owned Treatment Works
POTW Signs Pretruatment Agreement
with Industry and Applies for
Municipal Discharge Permit
4
NPDES Permit:
National Pollutant Discharge
Elimination System
I Industrial NPDES Permit 4-
—M Municipal NPDES Permit
Figure H-l. Control of industrial waste water discharges in the United States.
2-3
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approved industrial pretreatment programs are
required to monitor for the chemicals
established by the Agency. These chemicals are
listed in Table II-l. ( A complete description of
Table II-l begins on page 2-23.) While no data
base exists today to indicate which chemicals are
being monitored, a data base is in the process of
being established to track the monitoring being
performed in this program. It is very likely
where POTW's effluents are determined to be
toxic by biomonitoring, that additional
monitoring in the industrial pretreatment
program will be required.
Water-Quality-Based Limits
The technology-based limits discussed above
are independent of the quality of the receiving
water. If these limits are considered inadequate
to achieve "fishable, swimmable" water quality,
the FWPCA mandates more stringent limits.
The States have a key role in this process. As a
result of the FWPCA and the Water Quality Act
of 1987, each state must establish water quality
standards (WQS) based on water quality criteria
(WQC) published by EPA. The state water
quality standards established to date are
summarized in Table II-l.
EPA has developed or is in the process of
developing water quality criteria under §304 (a)
for the priority toxic pollutants to protect
humans, animals, and aquatic organisms. These
criteria are used to establish the WQS in most
cases, although a state may adopt a different
site-specific standard based on EPA
methodological guidance. In addition to numeric
standards, all states have adopted narrative
standards (i.e., "no toxic pollutants may be
discharged in toxic amounts") which may be
implemented by numerical methods such as
biomonitoring.
Ambient monitoring (water quality and
biomonitoring) is principally done by state
agencies (2-3,4,5) under §106(e), EPA, and
several other federal agencies, such as the U.S.
Geological Survey, U.S. Forest Service, and U.S.
Fish and Wildlife Service, to determine the
presence of conventional and toxic pollutants in
ambient surface waters. The data collected are
used to identify problems, to help develop
controls, and to judge the effectiveness of the
controls. States are required to develop
maximum daily pollutant loads for stream
segments that consider the WQS. Effluent
limitations are then set to ensure attainment of
the WQS.
As each state monitors its waters, methods
are required to measure the chemicals at
detection levels low enough to determine
compliance with the water quality standards.
Water quality criteria and state standards
established to date indicate that improvements
in the detection levels of some methods .
established under §304(h) would be required to
support future ambient monitoring
requirements. However, §304(h) methods are
not currently required to be used to perform any
ambient monitoring required under the
FWPCA.
There is an increasing emphasis by state
agencies on monitoring stream and lake
sediments and fish or shellfish tissue to
determine the impact of historical discharges of
toxic pollutants and the effectiveness of current
controls. Data entered into STORET indicate
that data are being collected in every state on
these sample matrices. There is no
comprehensive information, however, on the
adequacy of the methods that state agencies are
currently using, or the comparability of data
supplied by the various states.
The NPDES Permit Program
The primary regulatory mechanism for
controlling pollution is the National Pollutant
Discharge Elimination System (NPDES). Under
the NPDES program, any person who wishes to
discharge pollutants into the waters of the
United States from any point source must first
apply for and obtain a permit. EPA is the
responsible agency for issuing permits unless a
state has an approved permit program (39 do as
of January 1988). Each state without an
approved program is still required to certify that
the permitted discharge will meet with
applicable state laws and standards. The permit,
when issued, sets effluent limitations and other
control requirements, schedules of compliance,
and monitoring requirements. Currently, there
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are approximately 65,000 'major and minor
NPDES permits established for industrial and
municipal dischargers.
Extensive monitoring requirements were
promulgated along with the establishment of the
NPDES program as a result of the 1972
amendments to the FWPCA. From that time
until 1977, the vast majority of effluent
monitoring was for conventional and
nonconventional contaminants. As a result of a
1976 consent decree (Natural Resource Defense
Council, et al., v. Train, 8 ERG 2120 (D.D.C.
1976)), as well as amendments to the FWPCA in
1977, there has been an increased emphasis on
the control of and extensive monitoring for toxic
pollutants. The list of 129 priority pollutants
established under Section 307(a), which was
subsequently reduced to 126, was designed to be
a good indicator of the extent of discharge of
toxic pollutants. The monitoring analytes
established by the effluent guideline process for
51 industrial categories are shown in Table II-l.
However, as the NRDC, the Agency and
Congress recognized, the list of priority
pollutants was not believed to be an all inclusive
list of toxic pollutants which could be possibly
discharged by industrial facilities and publicly
owned treatment works (POTW's). The purpose
of a study performed by the Agency as a result of
paragraph 4(C) in the NRDC consent decree was
to determine if additional non-priority pollutant
chemicals were being discharged (2-6). In that
study, EPA collected -and analyzed
approximately 40,000 samples, taken from 40
POTW's and facilities in 43 different industries.
Of 433 chemicals positively identified in the
study, 48 were priority pollutants and 385 were
not.
Monitoring requirements established in all
major NPDES permits were reviewed in July,
1986. At that time, an average of 10 and 12
analytes were required to be monitored in
municipal and industrial permits, respectively.
These monitoring requirements were
established as a result of the effluent guideline
process as well as monitoring of the NPDES
permitted effluents for priority pollutants in the
permit application process. Based on the 4(C)
study, there are additional toxic chemicals being
discharged for which monitoring requirements
may be necessary in the future.
The major initiative underway to control the
discharge of toxic pollutants will rely heavily on
whole effluent toxicity permit limits to identify
effluents where the current chemical-by-
chemical monitoring requirements have been
inadequate to identify toxic discharges.
Dischargers suspected of discharging toxic
pollutants will be required to perform toxicity
testing. When toxicity is found, a toxicity
reduction evaluation (TRE) program may be
required. Part of the TRE study is to determine
the chemicals that are causing toxicity. In many
of the studies performed to date by the EPA
Regions and states, the toxic agent was not a
priority toxic pollutant. It is anticipated as a
result of the biomonitoring program, that the
list of toxic chemicals for which monitoring will
be required will extend beyond the list of toxic
priority chemicals established under §307.
Therefore, reliable methods will be required to
measure the presence of a much broader suite of
toxic chemicals and also to detect pollutants that
are not on a target list.
The specific monitoring requirements in an
NPDES permit are therefore critical to
achieving this goal. Specific requirements are
governed by §122.16 and §§122.20-122.25 of the
NPDES regulations, such as the requirements
for maintaining and installing monitoring
equipment, monitoring methods and
frequencies, and test methodologies. The
NPDES regulations leave some aspects of
monitoring requirements to the discretion of the
permit writer. In these cases, the permit writer
relies on policy documents, technical support
documents, and other permits to develop specific
permit monitoring requirements.
Additional FWPCA Programs That
Require Monitoring
Section 403 of the FWPCA establishes the
Ocean Discharge Criteria Program. Regulations
developed under this section give guidance to
§402 permit writers for discharges into the ocean
2-14
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or territorial waters. Under this program,
methods for predicting the impact of discharges
to the environment were developed, including
toxicity test methods and biomonitoring
requirements.
Section 404 of the FWPCA governs the
issuance of permits by the Corps of Engineers
(COE) for disposal of dredged or fill material into
navigable waters. In December, 1980, the COE
and EPA proposed chemical and biological
methods for predicting the impact of dredged
material and for monitoring these activities in
the field. Testing protocols jointly developed by
the EPA and COE have not been incorporated
into §304(h). Monitoring requirements for each
dredge and fill permit are established by the
individual district COE offices. To date, a
limited suite of chemical and biological
monitoring analytes are usually required.
Judging by the data in STORET, there is a
significant difference in monitoring being
performed on sediments analyzed by state
agencies to determine the extent of sediment
contamination and the list of analytes commonly
specified by COE to control the discharge of
pollutants through dredge and fill activities.
Section 405 of the FWPCA governs the
disposal of sewage sludge in addition to §402 of
the act. Regulations for governing the issuance
of permits under §§405 and 402 are to include
specifications on criteria, requirements, and
methods. As a result of the domestic sewage
sludge study, initially chemical monitoring will
be required of POTW sludges for 32 chemicals.
This list will be expanded within two years by an
additional 20 to 30 chemicals. While methods
established in 40 CFR 136 under the authority of
§304(h) do not currently apply to sludge
monitoring, methods will be promulgated in the
sludge regulations with the intent of
incorporating these methods into 40 CFR 136.
The EPA has until 1988 to finalize the
regulations under Section 405 that deal
specifically with toxic materials (including
pathogens) in sewage sludges.
Required FWPCA Monitoring and
§304(h) Methods
In summary, the implementation of the
FWPCA requires many sample analyses to be
performed in support of various monitoring
programs. Methods are generally available for
each of these programs, although not all of these
methods have been standarized and
promulgated under 40 CFR 136. In addition,
usage of the methods authorized under §304(h)
and codified in 40 CFR 136 has been required
only for the analysis of process waters and
treated effluents under the National Pollutant
Discharge Elimination System (NPDES) and
industrial pretreatment programs. The use of
§304(h) methods is not required for ambient
surface water monitoring. In addition, the use of
methods in 40 CFR 136 is not required for the
analysis of sediments and biological tissues,
which are increasingly being tested because
they are commonly regarded as the ultimate
receptors of toxic pollutants.
While few biological testing methods have
been included in 40 CFR 136 to date, methods
will soon be proposed for acute and chronic
toxicity testing to support the water quality
based approach to permit writing being
implemented by the Agency. Also not included
under §304(h) are the chemical and biological
testing methods used to test dredge and fill
material required to be analyzed under §404.
The Army Corps of Engineers, with concurrence
of the EPA, has published but not promulgated
separate testing methodology for these purposes
The end result is that there are numerous
monitoring programs required by various
sections of the FWPCA that use methods that
have not been promulgated in to CFR 136 or
subjected to a comparable standardization
process.
Testing Requirements Established
by Other Related Environmental
Legislation
With the recognition of the problems
associated with toxics, various recent
environmental legislation has focused on
controlling the release of basically the same
suite of toxic chemicals in the same
2-15
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environmental media. For example, concern
over contamination of groundwater with volatile
organic chemicals is addressed in four major
pieces of environmental legislation. Th'e
consequence of this widespread concern for
toxics has resulted in the promulgation of
monitoring requirements by other programs
which are similar to and yet different from
FWPCA requirements. For example, primary
drinking water standards can be applied to
assess the impact of an effluent discharge into a
surface water used for a drinking water supply.
The major pieces of environmental legislation
which have monitoring requirements which
directly overlap those under the FWPCA are:
• CERCLA, the Comprehensive Environ-
mental Response, Compensa-tion, and
Liability Act (Superfund)
• SDWA, the Safe Drinking Water Act
• RCRA, the Resource Conservation and
Recovery Act
• MPRSA, the Marine Protection,
Research and Sanctuaries Act
Monitoring requirements under these four
acts as recently amended, combined with
requirements under FWPCA, form the basis for
most of the monitoring of waters, soils, wastes,
and biological tissues. The basic monitoring
requirements of each of these Acts as they relate
to FWPCA programs are briefly summarized
below. The recent amendments to these Acts
have consistently directed the Agency to expand
the monitoring requirements to include more
toxic chemicals. While many of these changes
will not be finalized for years, it is obvious that
the trend is towards the development of larger
lists of monitoring analytes. The Agency does
not have the resources and the regulated
community does not have the capability to
support totally different monitoring
requirements and methods for each regulatory
program.
Comprehensive Environmental
Response, Compensation and Liability
Act (CERCLA)
From the onset, the focus of the CERCLA
monitoring program was to collect data for toxic
chemicals from Superfund sites. It was
imperative that the data be consistent and
legally defensible. The CERCLA program
therefore established a target list of analytes
patterned after the toxic priority pollutant list.
The initial list consisted of the priority
pollutants plus additional organic compounds
and metals which could be measured using
essentially the §304(h) test procedures for
priority pollutants. Over the years, the list has
been revised to delete compounds for which the
analytical protocols have been deemed to be
inappropriate based on method performance
data.
The current target list of analytes includes
127 organic compounds (including 2,3,7,8-
TCDD), 23 metals and cyanide. The majority of
analytical efforts at Superfund sites involve the
analysis of waste, soil, and water samples for
these 151 target analytes using rigid protocols
established by the Contract Laboratory Program
(CLP). Recognizing that a target list does not
always detect every compound that may be of
concern, the program has specified methods to
tentatively identify and estimate the
concentration of additional organic chemicals
that may be present. Among the requirements
of the Superfund Amendments and
Reauthorization Act (SARA) is a mandate to
prepare an initial list of at least 100 hazardous
substances commonly found at Superfund sites.
This list was published April 17, 1987 (52 FR
12866). SARA has mandated that this list will
ultimately grow to 275 chemicals. While most of
the substances contained in this initial list are
target analytes in the CLP monitoring program,
additional substances were listed that may be
the focus of future monitoring requirements.
Two additional significant changes made by
SARA are the requirement to perform health
assessments at all National Priority List (NPL)
sites, and the provision of applicable, relevant,
and appropriate regulations (ARAR's). To
properly perform the health and biological
effects studies, animal and plant tissue as well
as air samples will require analysis. The CLP
list of analytes will have to be expanded
considerably and the analytical methods will
have to be modified to achieve lower detection
limits to test compliance with all ARAR's.
2-16
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Safe Drinking Water Act (SDWA)
The SDWA authorizes the Agency to set
national primary drinking water regulations
(NPDWR's) for public water suppliers. Public
water suppliers are required to perform routine
monitoring to demonstrate compliance with the
regulations. The 1986 amendments to the
SDWA specified 83 contaminants that must be
regulated by July 1989. The first phase of
regulation (52 FR 25690) was promulgated on
JulyS, 1987.
The current NPDWR's contain substances
that have regulated limits termed maximum
contaminant levels (MCL's) as well as
substances that do not have regulated limits, but
for which monitoring is required (unregulated
contaminants). Including the contaminants for
which regulations were promulgated on July 8,
1987, MCL's have been established in 40 CFR
141 for 33 contaminants:
• 11 inorganics and metals.
• 6 chlorinated hydrocarbon pesticides and
herbicides.
• 12 volatile organic chemicals, including
trihalo me thane s.
• 3 radiological analytes.
• 1 microbiological analyte
Monitoring requirements have also been
established for 51 unregulated volatile organic
, chemicals. These unregulated contaminants
have been separated into three lists for
monitoring purposes. The 34 contaminants
listed in 40 CFR Part 141.40(c) must be
measured by all water suppliers. Measurement
of the two chemicals listed in 40 CFR Part
141.40(f) is required only by those suppliers
vulnerable to contamination by these chemicals.
Monitoring for the 15 chemicals listed in 40 CFR
Part 141.40(i) would be at a state's discretion.
By July 19, 1989, NPDWR's must be
established for 83 contaminants referenced in
the Act. This list of 83 contaminants includes
volatile organic chemicals, inorganics and
metals, synthetic organic chemicals,
microbiological contaminants, and
radionuclides. In addition to the list of 83
contaminants, the Agency must compile a
priority list of contaminants and develop
NPDWR's for contaminants on this list. The
Agency has developed a candidate list of priority
chemicals which include:
• 7 contaminants removed from the original
list of 83 contaminants,
• 24 disinfectants and disinfection by-
products,
• 17 substances from the SARA §110
Priority List,
• 45 pesticides registered under FIFRA, and
• 18 volatile organic chemicals.
In addition to the NPDWR's, the Agency has
also specified secondary drinking water
standards. These standards relate to aesthetic
qualities of water (e.g., taste, odor and color).
The standards are not enforceable limits, but
rather guidance values. Secondary standards
have been established for twelve contaminants.
Resource Conservation and Recovery Act
(RCRA)
The Subtitle C RCRA program, designed to
manage hazardous wastes from "cradle to
grave", has implemented a series of complex
monitoring requirements which extend into
other programs. The primary focus of many of
these requirements pertains to preventing or
remediating groundwater contamination The
RCRA program has promulgated various
monitoring requirements relating to this issue,
including analyses to determine if a waste is
hazardous, what waste treatment must be used,
and the extent of contamination at a waste site.
While it is beyond the scope of this study to
define all of the RCRA monitoring
requirements, certain requirements directly
overlap FWPCA monitoring requirements.
For example, the concern over contaminants
that could migrate from a land disposal site into
the surrounding environment has resulted in
the development of a leaching method to
simulate this disposal scenario (Extraction
Method Toxicity). Wastes which have specific
"hazardous constituents" above specified levels
in the leachate are defined as hazardous wastes
2-17
-------
and must be managed to specified standards.
The Agency is in the process of expanding the
list of contaminants that must be measured in
leachates to determine if the waste is hazardous
and changing the test method to allow for the
measurement of toxic organic chemicals
(Toxicity Characteristic Leaching Method).
In a related area, a company can petition the
Agency to delist a waste from a specific facility
that is classified (listed) as a hazardous waste.
This delisting petition involves demonstrating
that the waste does not contain "hazardous
constituents" at concentrations that would
result in groundwater contamination above
specified health criteria.
Groundwater monitoring is required at
hazardous waste disposal facilities These
requirements have two separate goals. The first
goal is associated with demonstrating that
contamination is not occurring and is termed
detection monitoring. Under detection
monitoring, facilities with interim status (40
CFR 265) must monitor for indicators of
groundwater contamination and analytes which
have primary and secondary standards
promulgated under SDWA. Detection
monitoring at facilities with Part B permits (40
CFR 264) is established in the permit.
If contamination is suspected, facilities must
demonstrate that hazardous constituents are not
present. A list of hazardous constituents was
developed by the Agency to assess whether a
waste should be designated (listed) as
hazardous. This list was promulgated as
Appendix VIII to 40 CFR 261 and contains
approximately 375 compounds, salts, classes of
compounds, mixtures, and other "constituents"
which were shown in studies to have toxic,
carcinogenic, mutagenic, or teratogenic effects.
The Agency may also require that biological
testing be performed to determine the extent and
type of damage possible with a waste. A suite of
test procedures has been developed for site
assessment.
Thus, many of the RCRA programs have
been oriented towards measurement of the
constituents contained in Appendix VIII.
Because of the nature of the Appendix VIII list,
the development of a well-defined, measurable
monitoring list is impossible. For example, it
was shown that methods to measure all
constituents contained in this list are currently
not available. Therefore, the Agency developed a
related list for groundwater monitoring. This
list, promulgated in Appendix IX to 40 CFR 264,
contains all Appendix VIII constituents that can
be measured in water along with compounds
measured at Superfund sites using CLP
protocols which were not listed in Appendix
VIII.
Marine Protection, Research, and
Sanctuaries Act (MPRSA)
The Marine Protection, Research, and
Sanctuaries Act (PL 92-532) of 1972 requires
monitoring in several sections of the Act to
determine if dumping of industrial wastes,
sewage, or dredged and fill material adversely
impacts the quality of the marine and estuarine
environment, human health, and the economic
potential of the ocean. Title I discusses the
Ocean Dumping Permits Program requirements
which are to be administered by the EPA (§102)
and the Corps of Engineers (§103).
For permits, monitoring and surveillance of
dumping is required (§104(a)(5)) using both
chemical and biological methods. Furthermore,
under Title II (Ocean Dumping Research
Program), "the development and assessment of
scientific techniques to define and quantify the
degradation of the marine environment" are
specifically mandated in order to conduct the
research program. Monitoring programs are to
include but not be limited to bottom oxygen
concentrations; contaminant levels in biota,
sediments, and the water column; diseases in
fish and shellfish; and changes in types and
abundance of indicator species (§ 202(2) (Q). The
Act specifically requires cooperation between
EPA, the Corps of Engineers, and the
Department of Commerce in these programs.
Evolution of Testing Requirements
The Agency views "monitoring" in its
broadest sense, incorporating much more than
the act of extracting and analyzing water
samples or measuring biological impacts. The
monitoring process begins with the
2-18
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identification of information needs and ends
with the actual use of monitoring results in
decision making. A comprehensive monitoring
strategy must address the entire process,
identifying the actions to be taken with respect
to each step to ensure effective support for
program objectives.
The purpose of monitoring in the Office of
Water is to develop information to help State
and EPA managers perform their regulatory
and programmatic functions for protection of
surface water quality and associated aquatic
resources. These activities are carried out by a
variety of programmatic offices in EPA.
Trends in Monitoring Strategy
To determine the scope and magnitude of the
monitoring effort performed under the FWPCA,
the data.in the STORET system were reviewed.
Over 2000 agencies or offices of different
agencies have submitted data to STORET. There
are over 650,000 monitoring stations across the
U.S. and 106,000,000 pieces of data within
STORET. Table II-2 shows the type of agencies
which have submitted data to STORET and
Table II-3 shows the type of data which have
been entered in STORET. Only a small fraction
of the biomonitoring data collected by most
federal and state programs (e. g., ecological data)
for ambient monitoring have been entered into
STORET (2-5) because the system was not
originally designed to accommodate the
hierachical structure of these data. However, a
new biological data management system (BIOS)
has. been developed by the Agency to handle
these data. Based on analysis of the data
submitted, the following trends in monitoring
strategy were detected.
Since the enactment of the 1972
Amendments to FWPCA, the strategy for water
quality monitoring in the Office of Water has
changed considerably. In developing the system
of limitations required by the 1972 Amendments
to FWPCA, EPA focused in the early 1970's on
developing a chemical database indicative of
water quality. Discharges were regulated
principally for gross or "conventional" measures
of pollution. Conventional pollutants included
biochemical oxygen demand (BOD), dissolved
Table II-2 Agencies Submitting Data to
STORET
Sewage Treatment Districts
Army Arsenals
Bureau of Reclamation
EPA Headquarters
Corps of Engineers
Universities (Public and Private)
Fish & Wildlife Service
NOAA
Private Contractors
Electric Power Research Institute
EPA Regional Offices
U.S. Geological Survey
U. S. Air Force
Bureau of Sport Fisheries & Wildlife
U. S. Forest Service
Various State Agencies (all 50 states)
Bureau of Land Management
Cities
Department of Energy
County Agencies
Water and Power Resources
River Basin Commissions
Federal Highway Administration
EPA Research Laboratories
Tennessee Valley Authority
Office of Surface Mining
EPA National Enforcement Center
EPA and Canada Cooperative '
oxygen (DO), suspended and dissolved solids,
bacteria, nutrients, pH, and temperature. This
surrogate approach, while appropriate for the
control of pollutants of greatest concern at that
time, failed to account for other pollutants (e.g.,
organics, pesticides, metals) that presented the
risk of toxicity to aquatic life and humans.
This situation precipitated litigation (2-6)
that resulted in a Consent Decree (Natural
Resources Defense Council, Inc., et al. v. Train, 8
ERC 2120 (D.D.C. 1976)), mandating
identification of the "priority pollutants." EPA
identified 65 priority pollutants (129 specific
chemicals, later reduced to 126 chemicals) of
concern to 21 industrial categories. There are
now 51 major industrial categories which
include over 700 subcategories and greater than
70% of all industries (2-7). The Consent Decree,
2-19
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Table K-3 Type of Data Submitted to STORET
1 Conventional and priority pollutants in
effluents (discharge permit, compliance
monitoring)
2 Effluent toxicity to aquatic organisms
(discharge permit compliance monitoring)
3 Chemical data for acid mine drainage
4 Ambient surface water hydrological,
chemical, priority pollutant, and biological
integrity data from Federal and state surface
water monitoring programs (§106[e] Basic
Monitoring Program)
5 Priority pollutants in freshwater fish tissue
and sediments (§106[e] Basic Water
Monitoring Program)
6 Nutrients, pH, and alkalinity of lakes (Clean
Lakes Program)
7 Pesticides and toxic chemicals in marine
mussels (Mussel Watch Program)
8 Dioxin data (National Dioxin Study)
9 Chemical and biological integrity data from
the Chesapeake Bay and other major bays
(National pprogram)
10 Water quality, priority pollutants, and
biological integrity data from the Great
Lakes
11 Toxic chemicals in leachate and ground water
beneath landfills
12 Priority pollutants in ground water supplies
13 Contaminants in drinking water
slightly modified, was adopted into the language
of the 1977 Amendments to FWPCA.
During the period, 1976-1984, the EPA
emphasized a chemical-by-chemical approach to
monitoring activities and developed effluent
guidelines and pretreatment standards. This
resulted in a significant increase in the total
number of chemical measurements made on
each sample. During this time, the number of
chemicals routinely measured increased by over
an order of magnitude. Methods for chemical
analyses were greatly improved due to the
introduction of new analytical technology for the
priority pollutants.
Intensive surveys were performed on surface
waters, and numerous studies were completed
on bioaccumulation, toxicity, acid deposition,
and ecosystem surveys. As with the monitoring
programs developed under RCRA and
Superfund, additional sample matrices became
of concern. For all programs, the number of
sample matrices of concern has increased three
to four-fold from a focus almost exclusively on
air and surface water samples to a much larger
and difficult to analyze suite of sample matrices.
These new matrices include 43 uncontaminated
and contaminated soil, sediment, waste,,sludge,
groundwater, marine water, drinking water,
and tissue (human, fish, and plant) samples.
Using the chemical-by-chemical approach,
the Agency kept significant amounts of toxic
compounds out of surface waters during the
1970's. However, by 1984, it became apparent
that a chemical-by-chemical approach, by itself,
could not adequately protect all surface waters
for the following reasons:
• existing lists of target analytes do not
contain all chemicals which are toxic,
• many toxic compounds at toxic levels
cannot be measured by available methods,
• toxicological data are not available to
support the development of water quality
criteria for the thousands of compounds
which are toxic,
• chemical specific approaches cannot
account for possible interactions among
pollutants that may occur in complex
effluents (2-8), and
• complete chemical analyses are
prohibitively extensive.
As a result of this recognition, EPA adopted
a national policy in 1984 (2- 9) to include toxicity
in the development of water quality-based
permit limitations. This approach is consistent
with the original intent of Congress and
authorized in the FWPCA (§§301 & 303) and is
necessary to implement State derived water
quality standards (2-10) and determine stream
segment wasteload allocations.
The term "toxic pollutants" is defined in the
FWPCA as,
those pollutants, or combination of
pollutants, including disease-causing agents,
which after discharge and upon exposure,
ingestipn, inhalation or assimilation into any
organisms, either directly from the
environment or indirectly by ingestion
through food chains, will, on the Basis of
information available to the Administrator,
2-20
-------
cause death, disease, behavioral
1 1*1* J * 1 A *
reproduction) or phys
deformations, in such organisms or their
offspring (2-11).
The key phrase from the FWPCA, "toxic
pollutants in toxic amounts" (2-12), when
adopted as a national policy, required a very
significant change in monitoring strategy.
Particularly, this has resulted in increased
ambient monitoring to identify water quality-
limited bodies of water and to develop
appropriate source and nonpoint source
pollution controls.
As health-based criteria are used to
establish monitoring standards, there will be a
need to detect lower and lower levels of
pollutants. During the 1960's, it was necessary
to detect conventional pollutants at the parts per
million level. During the 1970's, it was
necessary to measure toxic pollutants at the part
per billion level, and in the 1980's and ongoing,
it will be necessary to measure some toxic
chemicals at the part per trillion level to
determine compliance with health-based
standards.
A toxics orientation has begun to pervade all
FWPCA related regulations and has caused a
greater emphasis to be placed on biomonitoring
techniques. This approach, reflected in the third
round of NPDES permits, has resulted in the
increased use of whole effluent toxicity testing
in establishing permit limitations. This
approach is being applied to major and selected
minor industrial and municipal dischargers on a
case-by-case basis.
The Domestic Sewage Study and effluent
testing of POTW's in a number of states has
demonstrated that municipal dischargers could
have significant toxicity due to the presence of
toxic chemicals that are not covered by existing
pretreatment standards. The toxics control
strategy has resulted in the need for significant
improvements in chemical monitoring methods,
including lower detection limits and new
analytical tests. Additional emphasis has been
placed on monitoring at the ecosystem level,
including numerous fate and biological effects
studies. As the Agency continues to shift
monitoring concern from emphasis on
conventional analytes to a focus principally on
toxic pollutants, the number of analytes will
likely grow another order of magnitude in the
next decade.
Future Monitoring Needs
To determine priorities for future monitor-
ing, and to address continuing concerns that
EPA HQ had not been providing sufficient
program direction and technical guidance to the
states and regions on surface water monitoring,
the Office of Water initiated a major study of the
Agency's surface water monitoring activities in
December 1985. The study, Surface Water
Monitoring: A Framework for Change, was
completed in September 1987. The study
identified numerous deficiencies in past
approaches to monitoring and recommended
that EPA and states:
• develop guidance on designing
scientifically sound, cost-effective
assessment programs that make use of new
and emerging approaches such as
ecoregions, volunteer monitoring, and
biological monitoring methods to
complement traditional water chemistry
techniques;
• accelerate the development and
application of promising biological
monitoring techniques and evaluate the
role that biological methods should play in
monitoring programs;
• analyze the feasibility of requiring NPDES
permittees to conduct ambient monitoring;
• improve their ability to document progress
in water pollution control;
• centrally coordinate EPA activities to
integrate water-related data; and
• make existing monitoring data more
accessible and useful to water qualities
managers.
EPA's Office of Water has begun a number of
projects to implement recommendations
made in the study and to fulfill new
2-21
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requirements resulting from the Water
Quality Act of 1987. These efforts include:
• a guidance document on volunteer
monitoring directed to state program
administrators;
• the preparation of profiles of state
monitoring programs assessing current
state monitoring and assessment activities
and resources available to states;
• a study of monitoring objectives and
approaches analyzing the usefulness and
status of existing and emerging
monitoring and assessment methods;
• a study of assessment criteria and
methodologies;
• the development of monitoring program
guidance to improve the scope and
effectiveness of state monitoring and
assessment programs;
• the development of "Rapid Bioassessment
Protocols," which provide field methods for
conducting qualitative biological
assessments using fish and
macroinvertebrates;
• a national policy on the role of ecological
risk assessment in the water program;
• development of the "Waterbody System," a
data system which provides a waterbody-
specific format for storing 305(b) water
quality assessment information;
• the "Water Quality Data Systems Steering
Committee," which was established to
provide management direction for water
quality data systems.
A ground water monitoring strategy was
developed in 1985 which provided a cross agency
analysis of the need for and use of ground water
monitoring data. Within this approach,
individual program monitoring strategies such
as RCRA, Superfund, and Pesticides focus on
their program's specific interrelationships
between programs and the overall direction of
the Agency's ground water monitoring effort.
Amendments to the Safe Drinking Water Act
(SDWA), passed in June, 1986, call for a major
expansion in the scope and authorities of the
Public Water Supply (PWS) and Underground
Injection Control (UIC) programs. These SDWA
revisions require EPA to promulgate drinking
water standards for at least 83 new
contaminants on a three year schedule and to
develop a priority list of at least 25 more
contaminants for future regulation every three
years. The Office of Drinking Water must
initiate a monitoring program to include
unregulated contaminants and start developing
new ground-water monitoring methods for
governing waste disposal injection wells.
To add further complexity to the monitoring
requirements previously discussed, the number
of EPA programs with their own requirements
and distinct technical methods has also
increased significantly over the last decade.
Until the early 1970's, all monitoring was
conducted or required by the air and water
program offices. As a result of different program
emphasis, there was no overlap in monitoring
requirements or methods in the air and water
programs. Since then, major monitoring
programs and requirements have been
established by the Superfund, RCRA, TCSA,
FIFRA and Drinking Water offices. Each
program office, operating under separate
legislative mandates, has established distinct
monitoring requirements and methods. While
the number of programs with monitoring
requirements has increased three to four-fold,
the actual complexity and scope of monitoring
requirements has increased more than fifteen-
fold due principally to the complexity of the
RCRA and Superfund programs. A significant
future need will be to achieve consistency
between these various programs.
Another aspect of the significant changes in
monitoring requirements during the last decade,
is the tremendous increase in scrutiny that data
generated today receive compared to during the
1970's. During the early 1970's and before, most
data were collected to provide trend information
on the effectiveness of environmental controls.
Data were not routinely used in enforcement
actions or in litigation. As a result, the technical
methods did not have to be as well defined or as
carefully followed. Now, data routinely undergo
legal scrutiny and as a result, the methods must
2-22
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be documented more completely and ,the
methods followed more carefully by a laboratory.
Better QA/QC methods are needed to
demonstrate adherence to testing protocols.
As more responsibility to collect
environmental data was transferred from state
and federal agencies to the private sector, the
number and size of commercial and industrial
laboratories increased three to five-fold during
the past decade. The task of these laboratories is
much greater than ever before as they typically
receive requests to analyze virtually any sample
for any analyte required by any regulation using
a wide array of methods, instrumental
techniques, and quality control methods.
Therefore, for the Agency to ensure the integrity
of the database used to make important
monitoring, cleanup, and enforcement decisions,
it must be able to rely on the data determined by
the testing methods established by the Agency.
Again, this suggests that a strong QA/QC
program is necessary. Subsequent sections
address the issue of the availability and
adequacy of testing methodology and the
comparability of FWPCA testing and QA/QC
methods with those established by other major
EPA programs as well as other federal and state
agencies.
Inventory of Chemical Testing
Requirements
The chemicals that must be measured to
support various monitoring programs constitute
a diverse and extensive list of organic
compounds, metals, anions and radiological
analytes. To assess the adequacy of the test
methods, the analytes to be measured must first
be defined.
The previous sections of this chapter
described in general terms the monitoring
requirements under FWPCA, CERCLA, SDWA,
RCRA and MPRSA. This section of the report
contains an inventory of chemical analytes that
can be considered to represent a core list of
current, and to some degree, future monitoring
analytes. This list, presented in Table II-1,
contains all analytes that could be readily
identified as: 1) analytes required for monitoring
under FWPCA programs; and 2) analytes
required for monitoring under other Agency
programs.
Due to the dynamic and evolving nature of
monitoring requirements for chemical analytes,
it is almost impossible to completely define all
analytes that must be measured in a given
program. The table prepared for this section
contains a comprehensive listing of chemical
analytes that are used later in this report as the
basis for the assessment of the adequacy and
availability of test methods. It is likely that
analytes will be added to or deleted from the lists
used to compile Table II-l before this report is
completed.
New monitoring requirements which may be
implemented in the next two to three years were
determined by reviewing regulations that are in
a preliminary, developmental, stage. These
analytes were not included in the core list, but
are discussed in the latter part of this section.
The information presented in Table II-l was
obtained from a review of the following:
• Point source effluent guideline and
industrial pretreatment standards
promulgated in 40 CFR 400-454
• NPDES permit discharge monitoring
requirements as recorded in the Permit
Compliance System (PCS)
• Health-based water quality criteria
• State promulgated water quality
standards
• NPDES permit application requirements
•STORET
• Other FWPCA programs
• SDWA requirements
• RCRA requirements
• CERCLA requirements
While the table prepared from the review of
the monitoring programs is an attempt to
present an inclusive list of FWPCA monitoring
requirements, it should be noted that one
significant factor, nomenclature, complicated
this review Most organic compounds have two or
more names that are commonly used. (Table II-
2-23
-------
4). In addition, groups of isomers (e.g., xylenes,
dinitrotoluenes) are sometimes specified in the
requirements. Another example of a problem is
the designation of classes of compounds, e.g.,
chloroalkyl ethers. Current methods are
available for measuring specific compounds, not
isomeric groups and classes.
Table II-4 Examples of Organic Compound Names
Used Interchangeably
Acetone
Bromomethane
2-Butanone
Chloromethane
Methylene chloride
4-Methyl-2-
pentanone
Tetrachloroothene
Trichloroethene
Methyl phenol
1,2-Dibromoethane
1,2-Dichloroethane
Lindane
2-Propanone
Methyl bromide
Methyl ethyl ketone
Methyl chloride
Dichloromethane
Methyl isobutyl
ketone
Tetrachloroethylene
Trichloroethylene
Cresol
Ethylene dibromide
Ethylenedichloride
gamma-BHC
An example of this problem is documented in
the development of the "priority pollutant" list
The original toxic pollutant list specified in the
1976 NRDC Consent Decree contained 65
entries (classes of compounds, metabolites, etc.)
which were transformed into the 129 priority
pollutants for monitoring purposes. This
transformation of a regulatory list to a practical
list for monitoring purposes has not been
performed for some of the lists under
development.
To minimize problems associated with
nomenclature, the approach used for this
assessment was as follows:
• A name for each analyte was selected
based on common usage considering
citations in both analytical methods and
regulations.
• Isomer groups were segregated into the
individual compounds.
• Where possible, the individual compounds
associated with a class were listed. Where
this was not possible because the category
was too broad (e.g., PNA's), the informa-
tion was deleted in the primary table and
presented separately.
The list of analytes in Table II-1 is presented
from an analytical chemist's perspective.
Furthermore, an attempt was made to
consolidate the information as much as possible.
Thus, each analyte is listed once, using a name
that is recognizable by an analytical chemist.
Due to the confusion regarding nomenclature,
some analytes may not be listed by the name
appearing in some specific program. For
example, ethylene dibromide, a contaminant
listed under SDWA, is shown in the table as 1,2-
dibromoe thane.
Based on the review of the information
described above, a total of 323 analytes were
identified. These analytes and the detailed
information obtained on each, are presented.
This table contains an alphabetical listing of
chemical analytes and an inventory of
information contained under major headings as
summarized below:
• Effluent Guidelines and Standards.
• NPDES Monitoring Requirements.
• Water Quality Criteria.
• Water Quality Standards.
• NPDES Permits.
• Other FWPCA Lists.
• SDWA Requirements.
• RCRA Requirements.
• CERCLA Requirements.
An asterisk by a analyte indicates that an
approved method has been promulgated in
§304(h). Alternate names and Chemical
Abstracts Registry names for these compounds
are available in literature (2-13,14,15). The
analyte list does not include the pesticides listed
under the remanded regulation in 40 CFR 455
unless they were also required for monitoring in
2-24
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some other area. Due to their complex nature,
these analytes have been considered separately.
Effluent Guideline and Industrial
Pretreatment Standards
The Agency has promulgated effluent
guidelines and industrial pretreatment
standards for 51 point source industrial
categories (2-21,33 & 35). These effluent
guidelines and standards were reviewed to
determine the specific chemical analytes for
which standards have been promulgated.
Each point source category represents a
broad industrial category such as "inorganic
chemicals." This category is then divided into
subparts (e.g., aluminum chloride, calcium
carbide, sodium fluoride, etc.). Effluent
guidelines and standards are established for
each subpart. For the purposes of this study, the
information contained in each subpart was
consolidated to determine what analytes are
measured in each category.
This information was then used to assess the
frequency distribution of the analytes. Two
numbers appear in Table II-l under the heading
"Effluent Guidelines and Pretreatment
Standards." The first number represents the
frequency for which the analyte has an
established standard, calculated by dividing the
number of times the analyte appeared by the
major industrial categories.
The effluent guidelines and standards have
numeric discharge limitations for each
regulated analyte. Although most of these
guidelines and standards are promulgated as
mass discharges of a pollutant per unit of
manufacturing production or raw material use,
concentrations based on the minimum pollutant
discharge limitations can be calculated. These
values represent the most stringent
requirements that would be expected to be
achieved by an analytical method related to
technology-based controls. The second number
in this column is this limit, expressed as g/L.
As indicated previously, the pesticide
manufacturing effluent guidelines were not
included. Pesticides which are monitored for
other reasons are contained in the analyte list.
NPDES Monitoring Requirements
A survey of four regions (II, III, V, IX) was
performed to determine NPDES permit
monitoring requirements. This survey was
designed to 1) identify the chemical analytes
which were specified in the permits and 2)
quantify the frequency at which these analytes
were specified.
The values presented in the table represent
the number of times the analyte is cited in
permits in these four regions. Many analytes
listed in NPDES permits were not included in
this table due to the problem of correctly
identifying the analyte. Examples of this
problem included analytes such as "pesticides,
general", "mercaptans", "combined metals sum",
"chlorinated organic compounds" and "resin
acids".
In addition, the determination of the
detection frequency was also complicated by the
nomenclature. Multiple entries were frequently
listed for the same analyte e.g., "ethyl benzene"
and "ethylbenzene". In a review of permits in
one region, the following names were listed:
lindane, benzene hexachloride, hexachloro-
cyclohexane, delta benzene hexachloride, G-
BHC-Delta(sic). These names all refer to one or
more of the BHC pesticide isomers. Up to 15
different citations were noted for BOD.
Because of these complicating factors, the
information contained in Table II-l should be
used only to provide an estimation of the
monitoring requirements. However, it appears
that methods have been promulgated for most
analytes for which monitoring is required.
However, there is still a significant number of
analytes for which no methods have been
promulgated. For example, Table II-5 lists 35
analytes that were identified in this review that
did not appear as monitoring analytes in any
other area reviewed and that do not have
§304(h) methods. Standard nomenclature should
be a significant priority for the NPDES permit
program.
2-25
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Water Quality Criteria
Ambient water quality criteria, which are
based on the results of toxicity tests and other
biological data, have been developed for many
analytes (2-36,37). These criteria provide
guidance to the states, relating to: 1) human and
non-human acute and chronic toxicity of
analytes; and 2) carcinogenic and organoleptic
properties. For non-carcinogens, the criteria
represent estimate concentrations which
prevent adverse health effects. For carcinogens,
the criteria represent levels of incremental
cancer risk. The "criteria" are therefore
designed to represent a concentration for a given
constituent that, when not exceeded, will
provide an adequate degree of safety.
The science of establishing health-based
criteria is not fully developed. However, the
numbers that have been established in the water
quality criteria documents are increasingly
being cited in regulations or used as a basis for
developing state water quality standards. Thus,
these criteria are important from the perspective
of evaluating the adequacy of a testing method.
Numeric values in ug/L are shown for the
specific compounds for which water quality
criteria have been developed. The value shown is
the lowest value as provided in the Water
Quality Criteria Summary dated September 2,
1986, incorporating both the aquatic toxicity
and human health criteria. Also, water quality
criteria have been established for classes of
compounds, e.g., chloroalkyl ethers. These
values were not included.
Water Quality Standards.
Water quality criteria are used to establish
water quality standards. Water quality
standards are established by the states to protect
water uses (2-17,19-27,31 & 35). Standards are
established based on water use (e.g., aquatic life
protection, recreational, agricultural, drinking
water supply, etc.). Both narrative and numeric
standards have been established. Narrative
standards are general statements concerning
important environmental conditions. Numeric
standards are the concentration levels that will
be protective of the designated use. Numeric
Table H-5 Parameters Identified in Four
EPA Regions that are Required to be
Measured and that do not have a §304(h)
Method
Parameters Frequency*
Benzisothiazole
Carbaryl
Carbofuran
Chlorendic Acid
Diazinon
Dichlorobenzyltrifluoride
Difolalan
Ferricyanide
Ferrocyanide
Formaldehyde
Glyphosate
Hydrazine
Iodide
Iodine 129
Isothiazolone
Lithium
Palladium
PhthalicAcid
Polonium 210
RDX
Samarium
Sevin
Sodium Nitrite
Strontium 90
Sulfur dioxide
Tellerium
Tetrahydrofuran
Thiocyanate
Thiosulfate
Triethanolamine
Trifluralin
Trinitrotoluene
Tritium
Urea
Zirconium
1
1
1
1
1
2
1
1
1
13
1
13
1
4
1
2
1
1
9
15
2
2
1
1
3
1
2
1
1
1
1
25
3
3
1
'Number of times the parameter was listed.
standards have been established for both
conventional analytes and toxics. Of the 57
states and territories, 39 have adopted at least
one numeric standard for toxics.
Two sets of numbers are shown under the
general heading Water Quality Standards. The
first number is the number of states and
territories that have established a numeric
2-26
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standard for the analyte indicated. The second
number is the lowest concentration that has
been established by any state. As in the previous
areas, water quality standards have been
established for generic categories ("pesticides",
"biocides", "petroleum"). Furthermore, different
names are used for what are presumably the
same analytes, e.g., phenols, phenolics, and
phenolic compounds.
As with the water quality criteria, the
numeric standards are an important indicator as
to the adequacy of a test method. The values
shown in Table II-l indicate the best
performance required of a method, not
necessarily what would be required for most
uses.
Other FWPCA Lists
Although many of the water programs are
well established, there are many other programs
which are in the process of being developed.
While many of these programs are oriented
toward establishing monitoring requirements
which are in many ways similar to the existing
requirement, e.g., development of effluent
guidelines for additional point source categories,
some programs are involved in defining new
requirements.
For example, the program to develop
regulations to implement recommendations of
the Domestic Sewage Study is considering the
analytes monitored under RCRA. In reviewing
the monitoring requirements under
consideration, two groups of analytes were noted
that are currently being used in the
development of baseline data. These two groups
were the "Appendix C" and "Paragraph 4(c)"
analytes, both derived from the 1976 Settlement
Agreement (2-16).
The Appendix C list is a list of 26 organic
compounds derived from a list of classes of
compounds, contained in Appendix C of the
Settlement Agreement. The Paragraph 4(c)
analytes were derived from an intensive study of
other toxics which were identified in industrial
effluents pursuant to requirements specified in
the Settlement Agreement.
SDWA Requirements
As described previously, 40 CFR 141 has
specified 33 NPDWR's (national primary
drinking water regulations) and monitoring
requirements for 52 volatile organic compounds .
In addition, 12 contaminants are subject to
maximum contamination levels in 40 CFR 143
as secondary standards (SMCL's). For those
contaminants that have regulated levels
(NPDWR's) or secondary standards (SMCL's),
the level of concern is shown in concentration
units of ug/L. The SMCL levels are further noted
by the post script "S". The 52 volatile organic
compounds designated as unregulated
contaminants were categorized into three
groups. Each group of contaminants has
different monitoring requirements. The
classification of a specific contaminant into one
of these three groups is shown in Table II-l with
the following codes:
• ALL - Contaminants required to be
measured by all water supply systems
• VUL - Contaminants required to be
measured by vulnerable systems
• DISC - Contaminants required to be
measured at the state's discretion
In addition, analytes which are under
consideration for development of NPDWR's are
shown with the following designations:
• CON - Contained in the list of 83
contaminants, including the proposed
changes, as noticed in the July 8, 1987
Federal Register
• DWPL - Draft contained in Drinking
Water Priority List for 1988
Table II-l does not contain all of the analytes
in these two lists due to the general problems
described previously, which were associated
with defining a list for monitoring purposes.
RCRA Monitoring Requirements
The RCRA program has developed a number
of monitoring requirements associated with the
multitude' of issues surrounding the
2-27
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management of hazardous waste. Among these
requirements are groundwater monitoring
requirements for the group of hazardous
constituents contained in Appendix IX to 40
CPR 264. The 250 analytes contained in
Appendix IX include virtually all of the analytes
contained in the other RCRA programs. Because
of the comprehensive and easily definable
nature of the Appendix IX list, all analytes
contained in Appendix IX are shown in Table II-
1 as part of the core list.
Other analytes contained in the core list
which are referenced in FWPCA programs are
noted with the following conventions:
• GWM - Routine detection monitoring
analytes specified in 40 CFR 265
• OTC - Analytes contained in the proposed
organic toxicity characteristic (51 FR
21648)
• Appendix VIII - Analytes contained in
Appendix VIII that were deleted in the
development of Appendix IX due to
concerns.over the adequacy of the test
methods.
CERCLA Lists
As discussed previously, 151 analytes are
monitored at Superfund sites by laboratories
under contract to the Agency. These analytes
are designated by the term CLP under the
CERCLA Lists column of Table II-l, indicating
that the analytes are measured in the Contract
Lab Program.
The list of analytes in the CLP was based on
the priority pollutant list. Since the inception of
the program in 1980, 11 analytes have been
deleted based on the performance of the method.
These analytes are listed below:
In addition to the CLP analytes listed in the
CERCLA column in Table II-l are those
analytes contained in the priority list of 100
hazardous substances listed in the April 17,
1987 Federal Register, designated by the term
HSL.
Bis(2-chloromethyl) ether Acrolein
Aniline
Benzidine
1,2-Diphenylhydrazine
Dichlorodifluoromethane
Tin
Acrylonitrile
2-Chloroethyl vinyl ether
Trichlorofluoromethane
Endrin aldehyde
N-Nitrosodimethylamine
Of the 11 analytes indicated by the term
HSL that are not CLP analytes, 7 were
originally contained in the CLP analyte list but
were subsequently deleted based on poor method
performance data. Note that some of those
compounds are still listed as priority pollutants.
Additional Analytes
As stated previously, Table II-l presents a
core list of analytes for which monitoring is
readily defined.Tables II-6 through 11-14 contain
lists of substances for which monitoring
requirements are not fully defined. However,
substances contained in these lists may be added
to the existing requirements. A brief description
of these lists is summarized below.
Table II-6: Water Quality Criteria
This list contains substances that have
established water quality criteria, but could not
be defined from a laboratory perspective.
Table II-7: SDWA List
The amended SDWA specified the
development of NPDWR's for a list of 83
contaminants. This list, shown in Table II-7
contains substances that could not be clearly
defined, i.e., adipates, viruses. Furthermore,
monitoring requirements for many of the
analytes on this list have not been established.
Table II-8: Table V of 40 CFR 122, Appendix D
This list contains substances which "must be
identified if expected to be present" in industrial
2-28
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Table H-6 Poorly Defined Water Quality Criteria
Parameters
Parameters
Comment
BHC
Chloroalkyl ethers
Chlorinated benzenes
Chlorinated ethanes
Chlorinated ethenes
Chlorinated naphthalenes
Chlorophenols
Chlorophenoxy herbicides
Diamine toluene
All isomers listed
separately
Class
Class
Class
Class
Class
Class
Class
Class
discharges. Some of these analytes are contained
in NPDES permits. Others are poorly defined.
Table II-9: Appendix VIII to 40 CFR 261
The list contains many poorly defined and
immeasurable analytes.
Table II-10: Michigan List
The State of Michigan petitioned the Agency
to expand the Appendix VIII list by the addition
of 120 substances.
Table 11-11: Sludge Monitoring List
This table contains a list of analytes to be
measured in the POTW sludge monitoring
program.
Table 11-12: Pesticide Chemicals
On December 15, 1986, the Agency
remanded 40 CFR 455, the effluent limitations
guidelines, pretreatment standards, and new
source performance standards, for the pesticide
chemicals category. This action deleted a list of
61 pesticides, and 14 methods developed to
measure these pesticides. The, pesticides and
methods that were effected by this action are
shown in Table 11-12.
Table II-13: Hazardous Substances
Under 40 CFR 116, 299 inorganic salts and
organic compounds are listed in Table 116.4A as
hazardous substances. In 40 CFR 117, reportable
quantities have been established for each
substance, ranging from 1 to 5,000 pounds. This
regulation set forth the quantity that requires
reporting of a discharge to EPA.
This table contains a list of analytes to be
promulgated to be measured in the POTW
sludge monitoring program.
Table 11-14: STORET Analytes
STORET is a database established by the
Agency which contains environmental data
submitted by various groups. A survey of the
data submitted by California revealed a number
of analytes for which data are being generated
and for which §304(h) methods do not exist.
Examples of those analytes are included in
Table 11-14. A review of data submitted by nine
other states showed that many additional
analytes are being measured for which there are
no §304(h) methods.
Table 11-15: SDWA Priority List
The SDWA requires EPA to compile a
priority list of contaminants by 1988. To meet
this goal, the EPA has defined seven groups of
contaminants which are being considered in the
development of the first priority list (52 FR
25720). These seven groups and substances
contained in these groups are shown in Table II-
15. These substances will form the basis for
adding additional contaminants to drinking
water monitoring requirements.
Inventory of Biological Testing
Requirements
The biological analytes that must be
measured in support of various monitoring
programs constitute a diverse and largely
nonspecific list that is applicable to various
media (drinking water, ambient waters,
ground water, waste water, leachates, sludge,
and soils). Overall, FWPCA analytes can be
divided into two broad groups: 1) human health
2-29
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Table II-7 Drinking Water Analytes and Tests
Volatile Organic Chemicals
TrichloroQthytene
Telraehloroethytene
Carbon tetrachloride
l,l,t*Trichloroe thane
1,2-Dichloroethane
Vinyl chloride
Methyiene chloride
Bensene
Chlorobeniene
Dichlorobeniane(s)
Trichtorobonzenefs)
1,1-DichIoroethyleae
trani-l,2-Dichloroethylene
cil4,2 Dich'oroothyleno
Mlcrobloloav and Turbidity
ToUlcotifornu
Turbidity
Qiardia famofta
Vinssei
Standard plate count
Legianella
Inorganic*
Anenic
Barium
Cadmium
Chromium
Lead
Mercury
Nitrate
Selenium
Silver
Fluoride
Aluminum
Antimony
Molybdenum
Aibeitai
Sulfata
Copper
Vanadium
Sodium
Nickel
Zinc
Thallium
Beryllium
Cyanide
Organlcs Q
Endrin 8
Lindana F
Methoxychlor s
Toxaphene £
2,4-D
2,4,5-TP „
Aldicarb j
Chlordane 4
Dalapon 'J
Diquat g
Endothall J
Glyphosate r
Carbofuran C
Alachlor i
Epichlorohydrin V
Toluene
Adipates g
2,3,7,8-TCDD (Dioxin) 0
1,1,2-Trichloroethane g
Vydate i
Simazine r
Poly micloar aromatic hydrocarbons i
(PAHs) •{]
Polychlorinated biphenyls .p
Atrazine i^
Phthalates : _
Acrylamide g
Dibromochloropropane (DBCP) J
1,2-Dichloropropane t y.
Pentachlorophenol g
Ficloram . \^
Dinoseb g
Ethylene dibromide i'.
Dibromomethane C
Xylene P
T
Hexachlorocyclopentadiane
Radlonuclldes
Hadium226and228 r.
Beta particle and photon radioactivity (•
Uranium Q
Gross alpha particle activity i;
Radon I
r
a
r
r
related, and 2) ecosystem related. Unlike the
inventory of chemical analytes previously
discussed, the various sections of the FWPCA
and related statutes, and the regulations
promulgated under these statutes, seldom
specify the biological characteristics or
properties to be monitored within these two
broad types. Biological monitoring requirements
are generally described in broad terms such as
'biological integrity," which depends on the
diversity, stability, and productivity of
indigenous populations of fish and aquatic life.
There are thousands of species of common
estuarine, marine, and freshwater organisms.
Much is known about the environmental
requirements and pollution tolerance of the
common species, but no list of essential or
indicator species has been promulgated for the
various saline and freshwater habitats.
The success of the Agency's pollution
abatement and control program must be based
on the absence of toxicity in point and non-point
sources, and the maintenance of the biological
integrity of communities of organisms in
receiving waters.To provide support for the
implementation of the FWPCA, and to
determine if the mandated goal of "swimmable,
fishable waters" has been achieved, the Agency
has developed biological field and laboratory
methods for waters, wastewaters, sludges, and
sediments, which: 1) detect and quantify
disease-causing agents (human pathogens); 2)
measure the toxicity of pure compounds,
effluents, and surface waters; 3) determine the
bioaccumulation of toxic pollutants (toxic
substances in tissues); and 4) determine the
integrated effects of all toxic pollutants on the
biological integrity (diversity, stability, and
productivity) of communities of fish and aquatic
life.
Microbiological analytes related to human
health include disease-causing agents
(pathogens) such as viruses, bacteria, protozoa,
and parasites, and nonpathogens that are
indicators of the presence of pathogens or fecal
materials. The microbiological analytes
required or recommended under the FWPCA
and SDWA are listed in Table 11-16, and
methods to determine mammalian toxicity and
mutagenicity are listed in Table II-17.
2-30
-------
Table H-8 Table V of 40 CFR 122, Appendix D
Acetaldehyde
Allyl alcohol
Allyl chloride
Amyl acetate
Aniline
Benzonitrile
Benzyl chloride
Butyl acetate
Butylamine
Captan
Carbaryl
Carbofuran
Carbon disulfide
Chlorpyrifos
Coumaphos
Cresol
Crotonaldehyde
Cyclohexane
2,4-D (2,4-Dichloropheynoxy acetic acid)
Diazinon
Dicamba
Dichlobenil
Dichlone
2,2-Dichloropropionic acid
Dichlorvos
Diethylamine
Dimethylamine
Dinitrobenzene
Diquat
Disulfoton
Diuron
Dodecylbenzenesulfonate
Epichlorohydrin
Ethion
Ethylene diamine
Ethylene dibromide
Formaldehyde
Furfural
Guthion
Isoprene
Isopropanolamine
Kelthane
Kepone
Malathion
Mercaptodimethur
Methoxychlor
Methyl mercaptan
Methyl methacrylate
Methyl parathipn
Mevinphos
Mexacarbate
Monoethyl amine
Monomethyl amine
Naled
Napthenic acid
Nitrotoluene
Parathion
Phenolsulfonate
Phosgene
Propargite
Propylene oxide
Pyrethrins
Quinoline
Resorcinol
Strontium
Strychnine
Styrene
2,4,5-T(2,4,5-Trichlorophenoxy acetic acid)
TDE(Tetrachlorodiphenylethane)
2,4,5-TP(2-(2,4,5-Trichlorophenoxy) propanoic acid)
Trichlorofan
Triethanolamine
Triethylamine
Trimethylamine
Uranium
Vanadium
Vinyl acetate
Xylene
Xylenol
Zirconium
2-31
-------
Table H-9 Appendix VHI to 40 CFR Part 261
75058 Acetonitrile
98862 Ethanone, 1-phenyl
53963 Acetamide, N-9H-fluoren-2-yl
75365 Acetyl chloride
591082 Acetamide, N-(aminothioxymethyl)-
107028 2-Propenal
79061 2-Propenamide
107131 2-Propenenitrile
1402682 Aflatoxins
116063 Propanal, 2-methyl-2-(methylthio)-, O-[(methylamino)
309002 l,4:5,8-Dimethanonaphthalene, 1,2,3,4,10,10-hexachloro-
107186 2-Propen-l-ol
107051 1-Propene, 3-chloro-
20859738 Aluminum phosphide (A1P)
92671 [l,l'-Biphenyl]-4-amine
2763964 3(2H)-Isoxazolone, 5-(aminomethyl)-
504245 4-Pyridinamine
61825 lH-l,2,4-Triazol-3-amine
7803556 Vanadic acid, ammonium salt of
62533 Benzenamine
7440360 Antimony
140578 Sulfurous acid, 2-chloroethyl-, 2-[4-(l,l-dimethylethyl)
7440382 Arsenic
7778394 Arsenic acid (AsH3O4)
1303282 Arsenic oxide (As2O5)
1327533 Arsenic oxide (As203)
492808 Benzamine, 4,4'carbonimidoylbis[N,N-dimethyl-
115026 L-Serine, diazoacetate (ester)
7440393 Barium
542621 Barium cyanide
225514 Benz(c)acridine
56553 Benzo(a)anthracene
98873 Benzene, (dichloromethyl)-
71432 Benzene
98055 Arsonic acid, phenyl-
92875 Benzidine
205992 Benzo(b)fluoranthene
205823 Benzo(j)fluoranthene
50328 Benzo(a)pyrene
106514 2,5-Cyclohexadiene-l,4-dione
98077 Benzene, (trichloromethyl)-
100447 Benzene, (chloromethyl)-
7440417 Beryllium
111911 bis(2-Chloroethoxy)methane
111444 bis(2-Chloroethyl) ether
108601 bis(2-Chloroisopropyl) ether
542881 Bis(chloromethyl)ether
117817 bis(2-Ethylhexyl) phthalate
598312 2-Propanone, 1-bromo
75252 Tribromomethane
101553 4-Bromophenyl phenyl ether
357573 Strychnidin-10-one, 2,3-dimethoxy
(Continued)
2-32
-------
Table H-9 (Continued)
85687 Butyl benzyl phthalate
75605 Arsenic acid, dimethyl
7440439 Cadmium
13765190 Chromic acid, calcium salt
592018 Calcium cyanide
75150 Carbon disulfide
353504 Carbonic difluoride
56235 Tetrachloromethane
75876 Acetaldehyde, trichloro
305033 Benzenebutanoic acid, 4-[bis(2-chloroethyl)amino-
57749 4,7-Methano-lH-indene l,2,4,5,6,7,8,8-octachloro-2,3,3a,
1_064 Chlorinated benzenes, NOS
1_065 Chlorinated ethane, NOS
1 066 Chlorinated fluorocarbons, NOS
1_067 Chlorinated naphthalene, NOS
1_068 Chlorinated phenol, NOS
494031 2-Naphthaleneamine, N,N-bis(2-chloroethyl)
107200 Acetaldehyde, chloro-
1_070 Chloroalkylethers,NOS
106478 Benzenamine, 4-chloro-
108907 Chlorobenzene
510156 Benzeneacetic acid, 4-chloro-alpha-(4-chlorophenyl)-
59507 4-Chloro-3-methylphenol
106898 l-Chloro-2,3-epoxypropane
110758 2-Chloroethylvinyl ether
67663 Chloroform
107302 Chloromethyl methyl ether
91587 2-Chloronaphthalene
95578 2-Chlorophenol
5344821 1 -(o-Chlorophenyl)thiourea
126998 2-Chloro-l,3-butadiene
542767 Propanenitrile, 3-chloro
7440473 Chromium
218019 Chrysene
6358538 2-Naphthalenol, l-[(2,5-dimethoxyphenyl)azo]-
8007452 Coal tars
544923 Copper cyanide (CuCN)
8001589 Creosote
106445 p-Cresol
95487 o-Cresol
108394 m-Cresol
1319773 Phenol, methyl
4170303 2-Butenal
57125 Cyanides (soluble salts and complexes) NOS
460195 Ethanedinitrile
506683 Cyanogen bromide
506774 Cyanogen chloride
14901087 beta-D-Glucopyranoside, (methyl-ONN-azoxy)methyl
131895 Phenol, 2-cyclohexyl-4,6-dinitro-
50180 2H-l,3,2-Oxazaphosphorin-2-amine, N,N-bis(2-chloroethyl)
94757 2,4-Dichlorophenoxyacetic acid, salts and esters
20830813 5,12-Naphthacenedione, 8-acetyl-10-[(3-amino-2,3,6-tri
(Continued)
2-33
-------
Table II-9 (Continued)
72548 4,4'-DDD
72559 4,4'-DDE
50293 4,4'-DDT
' 2303164 Carbamothioic acid, bis(l-methylethyl)-S-(2,3-dichloro
226368 Dibenz(a,h)acridine
224420 Dibenz(aj)acridine
53703 Dibenzo(a,h)anthracene
194592 7H-Dibenzo(c,g)carbazole
192654 Naphtho[l,2,3,4-deflchrysene
189640 Dibenzo[b,deflchrysene
189559 Benzo(rst)pentaphene
96128 Propane, l,2-dibromo-3-chloro-
84742 1,2-Benzenedicarboxylic acid, dibutyl ester
95501 1,2-Dichlorobenzene
541731 1,3-Dichlorobenzene
106467 1,4-Dichlorobenzene
25321226 Dichlorobenzenes
91941 3,3'-Dichlorobenzidine
110576 trans-l,4-Dichloro-2-butene
764410 2-Butene, 1,4-dichloro (mixture of cis and trans) ,
75718 Dichlorodifluoromethane
156605 trans-l,2-Dichloroethene
25323302 Dichloroethylene, NOS
75354 1,1-Dichloroethene
120832 2,4-Dichlorophenol
87650 2,6-Dichlorophenol
696286 Arsonous dichloride, phenyl-
142289 1,3-Dichloropropane
26638197 Dichloropropane, NOS
96231 l,3-Dichloro-2-propanol
26545733 Dichloropropanol, NOS
26952238 Dichloropropene, NOS
10061015 cis-l,3-Dichloropropene
10061026 trans-1,3-Dichloropropene
542756 1,3-Dichloropropene
60571 2,7:3,6-Dimethanonaphth(2,3-b)oxirene, 3,4,5,6,9,9-hexa
1464535 l,2:3,4-Dlepoxybutane
692422 Arsine.diethyl
123911 1,4-Dioxane
1615801 Hydrazine, 1,2-diethyl-
3288582 O,O-Diethyl S-methyl ester of phosphorodithioic acid
311455 Phosphoric acid, diethyl-4-nitrophenyI ester
84662 Diethylphthalate
297972 O,0-Diethyl-O-(2-pyrazinyl)phosphorothioate
56531 Phenol, 4,4'-(l,2-diethyl-l,2-ethenediyl)bis,(E)-
94586 1,3-Benzodioxole, 5-propyl
329657 3.4-Dihydroxy-alpha-(methylamino)methyl benzyl alcohol
55914 Diisopropylfluorophosphate
60515 Phosphorodithioic acid, O,O-dimethyl s-[2-(methylamino)-
119904 l,l'-Biphenyl-4,4'-diamine,3,3'-dimethoxy
60117 Benzenamine, N,N-dimethyl-4-(pehnylazo)-
57976 7,12-Dimethylbenz(a)anthracene
(Continued)
2-34
-------
Table H-9 (Continued)
119937 [l,l'-Biphenyl]-4,4'-diamme,3,3'-dimethyl-
79447 Carbamic chloride, dimethyl-
57147 Hydrazine, 1,1-dimethyl
540738 Hydrazine, 1,2-dimethyl
122098 Benzeneethanamine, alpha, alpha-dimethyl-
105679 2,4-Dimethylphenol
131113 1,2-Benzenedicarboxylic acid, dimethyl ester
77781 Sulfuric acid, dimethyl ester
100254 1,4-Dinitrobenzene
25154545 Dinitrobenzene, NOS .
534521 Phenol, 2-methyl-4,6-dinitro-
51285 2,4-Dinitrophenol
121142 2,4-Dinitrotoluene
606202 2,6-Dinitrotoluene
88857 Phenol, 2-(l-methylpropyl)-4,6-dinitro-
117840 Di-n-octyl phthalate
122394 Diphenylamine
122667 1,2-Diphenylhydrazine
621647 Di-n-propylnitrosamine
298044 Phosphorodithioicacid,O,O-diethylS-[2-(ethylthio)
541537 2,4-Dithiobiuret
959988 Endosulfan-I
33213659 Endosulfan-II
115297 6,9-Methano-2,4,3-benzodioxathiepen, 6,7,8,9,10,10-
145733 7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylicacid,
53494705 Endrinketone
72208 l,4:5,8-Dimethanonaphthalene, 1,2,3,4,10,10-hexachloro-
51796 Carbamic acid, ethyl ester
107120 Ethyl cyanide
142596 Ethylenebisdithiocarbamic acid,-sodium salt
111546 Carbamodithioic acid, 1,2-ethanediylbis-, salts and
106934 1,2-Dibromoethane
107062 1,2-Dichloroethane
110805 2-Ethoxyethanol
151564 Aziridine
75218 Ethylene oxide
96457 Ethylenethiourea
75343 1,1-Dichloroethane
97632 Ethyl methacrylate
62500 Methanesulfonic acid, ethyl ester
52857 Phosphorothioic acid, O,O-dimethyl O-[p-[(dimethylamino)
206440 Fluoranthene
7782414 Fluorine
640197 Acetamide, 2-fluoro
62748 Fluoroacetic acid, sodium salt
50000 Formaldehyde
765344 Oxiranecarboxyaldehyde
1_193 Halomethane, NOS
76448 4,7-Methano-lH-indene, l,4,5,6,7,8,8-heptachloro-da,4,7,
1024573 2,5-Methano-2H-indeno[l,2b]oxirene,2,3,4,5,6,7,7-hepta
118741 Hexachlorobenzene
87683 Hexachlorobutadiene '
~~~~~(Continued)
2-35
-------
Table II-9 (Continued)
77474 1,3-CycIopentadiene, 1,2,3,4,5,5-hexachloro- "~
1 200 Hexachlorodibenzo-p-dioxins
1 201 Hexachlorodibenzofurans
67721 Hexachloroethane
70304 Hexachlorophene
1888717 Hexachloropropene
757584 Tetraphosphoric acid, hexaethyl ester
302012 Hydrazine
74908 Hydrocyanic acid
7664393 Hydrofluoric acid
7783064 Hydrogen sulfide
193395 Indeno(l,2,3-cd)pyrene
9004664 Irondextran
78831 Isobutyl alcohol
465736 l,2,3,4,10,10-Hexachloro-l,4,4a,5,8,8a-hexahydro-l,4:5)
120581 1,3-Benzodioxole, 5-(l-propenyl)-
143500 l,3,4-Metheno-2H-cyclobuta(cd)pentalen-2-one, l,la,3,3a,
303344 2-Butenoic acid, 2-methyl- 7-[(2,3-dihydroxy-2-(l-
7439921 Lead
301042 Acetic acid, lead (2 + ) salt
7446277 Phosphoric acid, lead (2 +) salt
1335326 Lead,bis(acetato-O)tetrahydroxytri-
58899 Cyclohexane, 1,2,3,4,5,6-hexachloro-, (1-alpha, 2-alpha,
108316 Maleic anhydride
123331 3,6-Pyridazinedione, 1,2-dihydro-
109773 Propanedinitrile
148823 L-Phenylalanine, 4-[bis(2-chIoroethyl)amino]-
628864 Fulminic acid, mercury (2 +) salt
7439976 Mercury
126987 2-Propenenitrile, 2-methyl-
91805 1,2-Ethanediamine, N,N-dimethyl-N'-2pyridinyl-N'-(2-
16752775 Ethanimidothioic acid, N-[[(methylamino)carbonyl]oxy]-,
72435 Benzene, l,l'-(2,2,2-trichloroethylidene)bis[4-
74839 Bromomethane
74873 Chloromethane
79221 Carbonchloridic acid, methyl ester
71556 1,1,1-Trichloroethane
56495 Benz[j]aceanthrylene, l,2-dihydro-3-methyl-
101144 4,4'-Methylenebis(2-chloroaniline)
74953 Dibromomethane
75092 Methylene chloride
78933 2-Butanone
1338234 2-Butanone peroxide
60344 Hydrazine, methyl-
74884 lodomethane
624839 Isocyanic acid, methyl ester
75865 Propanenitrile, 2-hydroxy-2-methyl-
80626 Methyl methacrylate
66273 Methyl methanesulfonate
298000 Phosphorothioic acid, O,O-dimethyl O-(4-nitrophenyl)
56042 4(lH)-Pyrimidinone, 2,3-dihydro-6-methyl-2-thioxo-
50077 6-Amino-l,la,2,8,8a,8b-hexahydro-8-(hydroxymethyl)-8a-
(Continued)
2-36
-------
Table H-9 (Continued)
70257 Guanidine, N-methyl-N'nitro-N-Nitroso-
505602 Ethane, l,l'-thiobis[2-chloro-
91203 Naphthalene
130154 1,4-Naphthoquinone
134327 1-Naphthylamine
91598 beta-Naphthylamine
86884 Thiourea, 1-naphthalenyl-
7440020 Nickel
13463393 Nickel carbonyl [Ni(CO)4], (T-4)-
557197 Nickel cyanide
54115 Pyridine, 3-(l-methyl-2-pyrrolidmyl)-, (S)-, and salts
10102439 Nitrogen oxide (NO)
100016 p-Nitroaniline
98953 Nitrobenzene
10102440 Nitrogen oxide (NO2)
51752 Ethanamine, 2-chloro-N-(2-chloroethyl)-N-methyl-
302705 Ethanamine, 2-chloro-N-(2-chloroethyl)-N-methyl, N-oxide
126852 Ethanamine, 2-chloro-N-(2-chloroethyl-N-methyl-
55630 l,2,3-Propanetriol,trinitrate
100027 4-Nitrophenol
79469 Propane, 2-nitro-
56575 Quinoline, 4-nitro-l-oxide-
35576911 Nitrosamine, NOS
924163 N-Nitrosodi-n-butylamine
1116547 Ethanol, 2,2'-nitrosoimino)bis-
55185 N-Nitrosodiethylamine
62759 N-Nitrosodimethylamine
759739 Urea, N-ethyl-N-nitroso-
10595956 N-Nitrosomethylethylamine
684935 Urea, N-methyl-N-nitroso-
615532 Carbamic acid, methylnitroso-, ethyl ester
4549400 Vinylamine, N-methyl-N-nitroso-
59892 N-Nitrosomorpholine
16543558 N-Nitrosonornicotine
100754 N-Nitrosopiperidine
930552 N-Nitrosopyrrolidine
13256229 Glycine, N-methyl-N-nitroso-
99558 5-Nitro-o-toluidine
152169 Diphosphoramide, octamethyl-
20816120 Osmium oxide (OsO4), (T-4)-
123637 1,3,5-Trioxane, 2,4,5-trimethyl-
56382 Phosphorothioic acid, O,O-diethyl O-(4-nitrophenyl)
608935 Pentachlorobenzene
1 289 Pentachlorodibenzo-p-dioxins
1 290 Pentachlorodibenzofurans
76017 Ethane, pentachloro-
82688 Pentachloronitrobenzene
87865 Pentachlorophenol
62442 Acetamide, N-(4-ethoxyphenyl)-
108952 Phenol
25265763 Benzenediamine
62384 Mercury, (acetato-O)phenyl-
(Continued)
2-37
-------
Table H-9 (Continued)
103855 Thiourea, phenyl-
75445 Carbonic dichloride
7803512 Phosphine
298022 Phosphorodithioic acid, O,O-diethyl S-[(ethylthio)
1_3Q3 Phthalic acid esters, NOS
85449 1,3-Isobenzofurandione
109068 2-Picoline
12674112 PCB-1016
11104282 PCB-1221
11141165 PCB-1232
53469219 PCB-1242
12672296 PCB-1248
11097691 PCB-1254
11096825 PCB-1260
1336363 Polychlorinated biphenyl, NOS
151508 Potassium cyanide
506616 Potassium silver cyanide
23950585 Benzamide, 3,5-dichloro-N-(l,l-dimethyl-2-propynyl)-
1120714 1,2-Oxathiolane, 2,2-dioxide
107108 n-Propylamine
107197 2-Propyn-l-ol
78875 1,2-Dichloropropane
75558 2-Methylaziridine
51525 4(lH)-Pyrimidinone, 2,3-dihydro-6-propyl-2-thioxo-
110861 Pyridine
50555 Yohimban-16-carboxylicacid, ll,17-Dimethoxy-18-[(3,4,5-
108463 Resorcinol
81072 l,2-Benzisothiazol-3(2H)-one, 1,1-dioxide and salts
94597 Safrole
7783008 Seleniousacid(H2SeO3)
7782492 Selenium
7446346 Selenium sulfide
630104 Selenourea
7440224 Silver
506649 Silver cyanide (AgCN)
93721 Propanoic acid, 2-(2,4,5-trichlorophenoxy)-
143339 Sodium cyanide (NaCN)
18883664 D-Glucopyranose, 2-deoxy-2-(3-methyl-3-nitrosoureido)-
1314961 Strontium sulfide (SrS)
57249 Strychnine and salts
1746016 Dibenzo[b,e][l,4]dioxin, 2,3,7,8-tetrachloro-
95943 1,2,4,5-Tetrachlorobenzene
1 331 Tetrachlorodibenzo-p-dioxins
1 332 Tetrachlorodibenzofurans
25322207 Tetrachloroethane, NOS
630206 1,1,1,2-Tetrachloroethane
79345 1,1,2,2-Tetrachloroethane
127184 Tetrachloroethene
58902 2,3,4,6-Tetrachlorophenol
3689245 Thiopyrophosphoric acid ([(HO)2P(S)]2O), tetraethyl
78002 Plumbane, tetraethyl-
107493 Tetraethylpyrophosphate
(Continued)
2-38
-------
Table II-9 (Continued)
509148 Methane, tetranitro-
7440280 Thallium
1314325 Thallium (III) oxide
563688 Acetic acid, thallium (1+) salt
6533739 Thallium (I) carbonate
7791120 Thallium (I) chloride
10102451 Nitric acid, thallium (1 + ) salt
12039520 Thallium selenide
10031591 Sulfuric acid, thallium salt
62555 Ethanethioamide
39196184 2-Butanone, 3,3-dimethyl-l-(methylthio)-, O-[(methyl
74931 Methanethiol
108985 Benzenethiol
79196 Hydrazinecarbothioamide
62566 Thiourea
137268 Thioperoxydicarbonic diamide, tetramethyl
108883 Toluene
25376458 Benzenediamine, ar-methyl-
95807 1,3-Benzenediamine, 4-methyl-
823405 1,3-Benzenediamine, 2-methyl-
496720 1,2-Benzenediamine, 4-methyl-
584849 Benzene, 2,4-diisocyanato-l-methyl-
106490 Benzenamine, 4-methyl-
636215 Benzenamine, 2-methyl-, hydrochloride
8001352 Toxaphene
120821 1,2,4-Trichlorobenzene.
79005 1,1,2-Trichloroethane
79016 Trichloroethene
75707 Trichloromethanethiol
75694 Trichlorofluoromethane
95954 2,4,5-Trichlorophenol
88062 2,4,6-Trichlorophenol
93765 2,4,5-Trichlorophenoxyacetic acid
25735299 Trichloropropane, NOS
96184 1,2,3-Trichloropropane
126681 O,O,O-Triethylphosphorothioate
99354 sym-Trinitrobenzene
52244 Tris(l-aziridinyl)phosphine sulfide
126727 Tris(2,3-dibromopropyl)phosphate
72571 2,7-Naphthalendisulfonic acid, 3,3'-[(3,3'dimethyltl,l1-
66751 2,4(lH,3H)-Pyrimidinedione, 5-[bis(2-chloroethyl)amino]-
2056259 Undecamethylenediamine, N,N'-bis(2-chlorobenzyl),-
1314621 Vanadium oxide (V205)
75014 Vinyl chloride
81812 2-H-l-Benzopyran-2-one, 4-hydroxy-3-(3-oxo-l-phenyl
557211 Zinc cyanide
1314847 Zinc phosphide (Zn3P2)
2-39
-------
Table 11-10 Michigan List
602879 Acenaphthene, 5-nitro
531828 Acetamide N-(4-(5-nitro-2-furyl)-thiazolyl)
3546109 Acetic acid, (4-[bis(2-chloroelhyl)amino]phenyl)-
50760 Actinomycin D
132321 3-Amino-9-ethyl carbazole
569642 Ammonium, (4-(p-(dimethylamino)-alpha-phenylbenzyli
838880 Aniline, 4,4'-raethylenebis (2-methyl)-
60093 Aniline, p-(phenylazo)-
139651 Aniline, 4,4'-thiodi-
137177 Aniline, 2,4,5-trimethyl-
90040 o-Anisidine
134292 o-Anisidine hydrochloride
120718 o-Anisidine, 5-methyl
99592 o-Anisidine, 5-nitro
117793 Anthraquinone, 2-amino
82280 Anthraquinone, l-amino-2-methyl
129157 Anthraquinone, 2-methyl-l-nitro
1332214 Asbestos
50066 Barbituric acid, 5-ethyl-5-phenyl
142041 Benzenamine hydrochloride
120627 Benzene, l,2-(methylenedioxy)-4-(2-(octylsulfinyl)
531862 Benzidine sulfate
17804352 Benzimidazolecarbamic acid, l-(butylcarba
1689845 Benzonitrile, 3,5-dibromo-4-hydroxy-
83794 (l)-Benzopyrano(3,4-b)furo(2,3-h)(l)benzopyran-6(6aH)
92933 Biphenyl, 4-nitro
1910425 4,4'"Bipyridinium, l,l'-dimethyl-,dichloride
126998 2-Chloro-l,3-butadiene
3817116 l-Butanol,4-(butylnitrosoamino)-
95067 Carbamic acid, diethyldithio-, 2-chloroallyl ester
1563662 Carbamic acid, methyl-, 2,3-dihydro-2,2-dimethyl-7-
315184 Carbamic acid, methyl-, 4-dimethylamino-3,5-xylyl ester
22781233 Carbamic acid, methyl-, 2,3-(dimethylmethylenedioxy)
63252 Carbamic acid, methyl-, 1-naphthyl ester
101279 Carbamic acid, m-chloro, 4-chloro-2-butynyl ester
7782505 Chlorine
7440484 Cobalt
7646799 Cobalt (II) chloride
56724 Coumarin, 3-chloro-7-hydroxy-4-methyl-, O-ester with O,
7700176 Crotonic acid, 3-hydroxy, alpha-methylbenzyl ester, di
7786347 Crotonic acid, 3-hydroxy-, methyl ester, dimethyl phos
2425061 4-Cyclohexene-l,2-dicarboximide N-((l,l,2,2-tetrachloro
133062 4-Cyclohexene-l,2-dicarboximide N-(trichloromethyl)thio-
156105 Diphenylamine, 4-nitroso-
107073 Ethanol,2-chloro-
1836755 Ether, 2,4-dichlorophenyl p-nitrophenyl-
3570750 Formic acid, 2-(4-(5-nitro-2-furyl)-2-thiazolyl)
66819 Glutarimide, 3-[2-(3,5-dimethyl-2-oxocyclohexyl)-2-
(Continued)
2-40
-------
Table 11-10 (Continued)
1024573 2,5-Methano-2H-indeno[l,2b]oxirene, 2,3,4,5,6,7,7-hepta
57410 Hydantoin, 5,5-diphenyl-
630933 Hydantoin, 5,5-diphenyl-monosodium salt
123319 Hydroquinone
1072522 N-(2-hydroxyethyl)ethyleneimine
135206 Hydroxy lamine, N-nitroso-N-pheny 1-, ammonium salt
7778543 Hypochlorous acid, calcium salt
7681529 Hypochlorous acid, sodium salt
61574 2-Imidazolidinone, l-(5-nitro-2-thiazolyl)-
54853 Isonicotinic acid hydrazide
463514 Ketene
7439932 Lithium
2385855 l,3,4-Metheno-lH-cyclobuta[cd]pentalene, l,la,2,2,3,3a,
2243621 1,5-Naphthalenediamine
117806 1,4-Naphthoquinone, 2,3-dichloro-
72333 17-alpha-19-Norpregna-l,3,5(10)-trien-20-yn-17-ol, 3-
57578 2-Oxetanone
101804 4,4'-Oxydianiline
5131602 m-Phenylenediamine, 4-chloro-
95830 o-Phenylenediamine, 4-chloro-
39156417 m-Phenylenediamine, 4-methoxy-, sulfate
52686 Phosphoric acid, (2,2,2-trichloro-l-hydroxyethyl)-,
21609905 Phosphorothioic acid, phenyl, O-(4-bromo-2,5-dichloro
2104645 Phosphorothioic acid, phenyl-, O-ethyl O-(p-nitro
4104147 Phosphoramidothioic acid, acetamidoyl, O,O-bis(p-
470906 Phosphoric acid, 2-chloro-l-(2,4-dichlorophenyl)vinyl di
961115 Phosphoric acid, 2-chloro-l-(2,4,5-trichlorophenyl)
300765 Phosphoric acid, l,2-dibromo-2,2-dichloroethyl di
62737 Phosphoric acid, 2,2-dichlorovinyl dimethyl ester
13171216 Phosphoric acid, dimethyl ester, ester with 2-chloro-N-
141662 Phosphoric acid, dimethyl ester, ester with (E)-3-
6923224 Phosphoric acid, dimethyl ester, ester with (E)-3-
512561 Phosphoric acid, trimethyl ester
78308 Phosphoric acid, tri-o-tolyl ester
680319 Phosphoric triamide, hexamethyl-
786196 Phosphorodithioic acid, s(((p-chlorophenyl)thio)
13071799 Phosphorodithioic acid, O,O-diethyl-S-(((l ,1-dimethyl
2642719 Phosphorodithioic acid, O,O-diethyl ester, S-ester with
86500 Phosphorodithioic acid, O,O-dimethyl ester, S-ester with
732116 Phosphorodithioic acid, O,O-dimethyl ester, S-ester with
78342 Phosphorodithioic acid, S,S'-p-dioxane-2,3-dryl O,O,O',
563122 Phosphorodithioic acid, S,S'-methylene O,O,O',O'-tetra .
8065483 Phosphorodithioic acid, O,O-diethyl O-(2-(ethylthio)
333415 Phosphorodithioic acid, O,O-diethyl O-(2-isopropyl-6-
115902 Phosphorodithioic acid, O,O-diethyl O-(p-(methylsul
2921882 Phosphorodithioic acid, O,O-diethyl O-(3,5,6-trichloro-
55389 Phosphorodithioic acid, O,O-dimethyl-, O-(4-methylthio)-
301122 Phosphorodithioic acid, S-(2-(ethylsulfmyl)ethyl) O, __
(Continued)
2-41
-------
Table 11-10 (Continued)
59636651 Polybrominated biphenyls, NOS
107051 1-Propene, 3-chloro-
78977 Propionitrile, 2-hydroxy-
6959484 Pyridine, 3-chloromethyl-, hydrochloride
136403 Pyridine, 2,6-diamino-3-(phenylazo)-, monohydrochloride
315220 (2,3,4-gh)Pyrrolizine-2,6(3H)dione, (4,5,8,10,12,13,13a,
1420048 Salicylanilide, 2',5-dichloro-4'-nitro, compound with 2-
57567 Semicarbazide
100425 Styrene
121755 Succinic acid, mercapto-, diethyl ester, S-ester with O,
64675 Sulfuric acid, diethyl ester
95807 1,3-Behzenediamine, 4-methyl-
95534 o-Toluidine
95794 o-Toluidine, 5-chloro-
33245395 p-Toluidine, N-(2-chloroethyl)-2,6-dinitro-N-propyl-
97563 o-Toluidine, 4-(o-tolylazo)-
1582098 p-Toluidine, alpha, alpha, alpha-trifluoro-2,6-dinitro-
7203909 Triazene, 3,3-dimethyl-l-(p-chlorophenyl)-
101053 s-Triazine, 2,4-dichloro-6-(o-chloroanilino)-
51525 4(lH)-Pyrimidinone, 2,3-dihydro-6-propyl-2-thioxo-
139946 Urea, l-ethyl-3-(5-nitro-2-thiazolyl)-
137304 Zinc bis(dimethyldithiocarbamato)-
39300453 Crotonic acid, 2-(l-methylheptyl)-4,6-dinitro
2-42
-------
Table 11-11 Sludge Monitoring List
Aldrin/Dieldrin
Arsenic
Benzene
Benzidine
Benzo(a)pyrene
Beryllium
Bis(2-ethylhexyl)phthalate
Cadmium
Carbon tetrachloride
Chlordane
Chloroform
Chromium
Copper
DDT/DDD/DDE
N,N-dimethyl nitrosamine
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
Lead
Lindane
Mercury
Molybdenum
Nickel
PCBs
Selenium
Toxaphene
Trichloroethylene
Vinyl chloride
Zinc
LA, I, CD
I
LA.LF
OD
LA.LP.I,
I
LF, I; OD
LA, LF, I,
I
LA.LF.I,
I
LA, I
LA.LF
OD
OD
OD
LA.LF.OD
LA,LF
OD
LA
LA
LA.LF, I
LA, LF
LA, LF, I,
LA
LA,LF,I
LA, LF, I,
LA
LA, LF, I,
LF
I
LA
OD
OD
OD
Table 11-12 Pesticide Chemicals
Key: LA refers to land application and distribution
and marketing
KF refers to landfilling I refers to incineration
OD refers to ocean dumping
Alachlor
AOP
Benfluralin
Benomyl
Bentazon
Bolstar
Bromacil
Busan 40
Busan 85
Butachlor
Carbam-S
Carbendazim
Carbofuran
Chlorbenzilate
Chloropyrifos
Chloropyrifos
methyl
Coumaphos
Cyanazine
2,4-DB
2,4-DB isobutyl ester
Glyphosate
Hexazinon
Isopropalin
KN Methyl
Mancozeb
Maneb
Mephosfolan
Metham
Methomyl
Metribuzin
Mevinphos
Nabam
Naled
Niacide
'Oxamyl
Phorate
Profluralin
Propachlor
Ronnel
Simetryne
2,4-DB isooctyl ester Stirophos
DBCP Terbacil
DEBT Terbufos
Dichlorvos Terbutryne
Dinoseb Triadimephon
Ethalfluralin Trichloronate
Etridiazole Tricyclazole
Fensulfothion ZAC
Fenthion Zineb
Ferbam Ziram
Fluometuron
Source:40 CFE 455 (Remanded)
2-43
-------
Table 11-13 Hazardous Substances
Common name
Acelaldehyde
Acetic acid
Acetic anhydride
Acetone cyanohydrin
Acotyl bromide
Acetyl chloride
Acfotoin «..»«.
Acrylonitrile « . .
Adipic acid
AkJrin
Allyl alcohol „
Altyl chloride
Aluminum sulfate
Ammonia,..-
Ammonium acetate
Ammonium benzoate
Ammonium bicarbonate
Ammonium bichromate
Ammonium bifluoride
Ammonium bisulfite
Ammonium carbamate
Ammonium carbonate
Ammonium chloride
Ammonium chromate
Ammonium citrate dibasic
Ammonium 1 luoborate
Ammonium fluoride
Ammonium oxalate
Ammonium silicofluoride
Ammonium sulfamate
Ammonium sulfide
Ammonium sulfite
Ammonium tartrate ......
Ammonium thiocyanate..
Ammonium thiosutfate
Amry acetate
Aniline....™ »..«
Antimony pentachloride
Antimony potassium tartrate
Antimony tribromide
Antimony trichloride
Antimony tnoxide
Arsenic disutfide
Arsenic pentoxide „
Arsenic trichloride
Banum cyanide
Benzene.» „
CAS No.
75070
64197
108247
75865
506967
79367
107028
107131
124049
309002
107186
107051
10043013
7664417
631618
1663634
1066337
7789095
1341497
10192300
1111780
506876
12125029
7766989
3012655
13826830
12125018
1336216
6009707
5972736
14258492
16919190
7773060
12135761
10196040
10192300
3164292
14307438
1762954
7783188
628637
62533
7647189
28300745
7789619
10025919
7783564
1309644
1303328
1303282
7784341
1327533
1303339
542621
71432
Synonyms
Glacial acetic acid, vinegar acid
Acetic oxide, acetyl oxide
2-methyllactanitrile, alpha-hydroxyisobutyr-
onitrile.
2-propenal, acrylic aldehyde, acrylaldehyde.
acraldehyde.
eitrile, vinyl cyanide.
Hexanedioic acid
Octalene, HHDN
2-propen-1-ol, 1-propenol-3, vinyl carbinol
3-chloropropene, S-chloropropylene, Chlor-
allylene.
Alum
Acetic acid ammonium, salt
Acid ammonium carbonate, ammonium hy-
drogen carbonate.
gen fluoride.
Ammonium aminoformate/.
miac, Amchlor.
ium salt.
fluoride.
Neutral ammonium fluoride
Ammate, AMS, ammonium amidosulfate
Tartaric'acid ammonium salt
cyanate, ammonium sulfocyanide.
Aniline oil, phenylamine, aminobenzene,
aminophen, kyanol.
antimony, potassium antimonyltartrate.
Diantimony trioxide, (lowers of antimony
ous chloride, butter of arsenic.
senic.
Cvclohexatriene. benzol
Isomers
isc-
tert-
CAS No.
123922
626360
625161
2-44
-------
Table 11-13 (Continued)
Common name
Benzoyl chloride
Beryllium chloride .
Butyl acetate .
Butylamine
n/butyl phthalate
Butyric acid
Calcium dodecylbenzenesulfonate ..
Chi°r°f-f Ze
~h •
Cobaltous "jo11" e
r h it if
X° ous su
r tt
up c ac .
\
Cupnc oxa a e
oupnc su iaie '"*"ri
Cupnc p"'1816' ammoniatea
CAS No.
65850
100470
98884
100447
7787475
7787497
7787555
13597994
123864
109739
84742
107926
543908
7789426
10108642
7778441
52740166
75207
13765190
592018
26264062
7778543
133062
63252
1563662
75150
56235
57749
75003
108907
67663
2921882
7790945
1066304
11115745
10101538
10049055
7789437
544183
14017415
56724
1319773
4170303
142712
12002038
7447394
3251238
• 5893663
, 7758987
10380297
815827
506774
110827
94757
94111
94791
94804
1320189
1928387
1928616
1929733
2971382
25168267
53467111
Synonyms
Benzenecarboxylic acid, phenylformic acid,
dracylic acid.
1.2-benzenedicarboxylic acid, dibutyl ester,
dibutyl phthalate.
Calcium chrome yellow, gablin, yellow ul-
tramarine.
Orthocide-406 SR-406, Vancide-89
Carbon bisulfide, dithiocarbonic anhydride
Co-Ral
Copper acetoarsenite, copper acetate ar-
senite, Paris green.
Hexahydrobenzene. hexamethylene. hexan-
aphthene.
Isomers
sec-
tert-
tert-
m-
o_
CAS No.
110190
105464
540885
78819
513495
13952846
75649
79312
108394
95487
106445
2-45
-------
Table 11-13 (Continued)
Common name
DOT _
Diazinon ....
Dicamba
Otchtobenll m
Dichlone .
Dichlorobenzene
Dichloropropane ........
Dichloropropene. „
Dichloroprapono-dichloropropane
(mixture).
2,2-Dichtotopropionic acid
Dichlorvos
Dieldrin
Diethyfarrune
Dimethylamine
Dimtrobenzene (mixed)
Dinilrophenol. ........
nj« nl
Oisulfoton .
rvrfon
podecylbenzenesulfonic acid
Pndosulfan « . .. . .. ..... . >
Endnn - *
Epicniorohydrin
Etnton . «•««« «....«
Etnylenediamine „
Elhylenediamine-telraacelie acid
(EDTA),
Elhylene dibromide _ _
Ethylane dichloride
Feme ammonium citrate
Feme ammonium oxalate
Feme chloride
Feme fluoride
Feme nitrate
Fernc sulfate
Ferrous ammonium sulfate
Ferrous chloride
Ferrous sulfate _..
Formaldehyde «
Formic acid
Fumaric acid »
Furfural .. .»
Gulhion~. ••
HeptacMor
H«xachlorocyclopentadiene
Hydrochloric acid
Hydrofluoric acid
Hydrogon cyanide
Hydrogen gutfjde
Isopreno
CAS No.
50293
333415
1918009
1194656
117806
25321226
26638197
26952238
8003198
75990
62737
60571
109897
124403
25154545
51285
25321146
85007
2764729
298044
330541
27176870
115297
72208
106898
563122
100414
107153
60004
106934
107062
1185575
2944674
55488874
7705080
7763508
10421484
10028225
10045893
7758943
7720787
7782630
50000
64186
110178
38011
86500
76448
77474
7647010
7664393
74908
7783064
78795
Synonyms
p.p'-DDT
Dipofene, Diazitol, Basudin. Spectracide
2-methoxy-3,6-dichlorobenzoic acid
2,6-dichlorobenzonitrile. 2,6-DBN
Phygon, dichloronaphthoquinone.
Di-chloricide
Paramoth (Para)
Propylene dichloride
D-D mixture Vidden D
Dalapon
2,2-dichlorovinyt dimethyl phosphate
Vapona.
AMI... .
Dinitrobenzol
Aldifen
DNT
Dextrone. Reglone. Diquat dibromide
Dt-syston .
DCMU, DMU
Thiodan .. .
Mendrin. Compound 269
•chloropropylene oxide
Nialate. ethyl methylene phosphorodith-
ioale.
Phenylethane
1,2*diaminoethane
Edetic acid, Havidote, (ethytenedinitrilo)-te-
traacetic acid.
1,2-dibromoelhane acetylene dibromide
sym-dibromoelhytene.
1 ,2*dichlOfoethane sym-bichloroethane
Ammonium ferric citrate
Ammonium ferric oxalate
Flores martis, iron trichloride....
Iron nitrate
:- . ''ale.
Mohr's salt, iron ammonium sulfate
Iron chloride, iron dichloride, iron protoch-
toride.
Green vitriol
Iron vitriol, iron sulfate, iron protosulfate
Methyl aldehyde, melhanal. fcxmalin
Methanote acid
Trans-butenedioic acid, trans-* 2-ethylene-
dicarboxylic acid, botelic acid, allomaleic
acid.
2-furaldehyde, pyromucic aldehyde
Gusathion. azinphos-methyl
Velsicol-104 Drinox Heptagran
Perchlorocyctopentadiene
Hydrogen chloride, muriatic acid
Fluohydric acid
Hydrocyanic acid
Hydrosutfuric acid sulfur hydride
2-methyl-1,3-butadiene
Isomers
Ortho
Para
1.1
1,2
1,3
1 3
2.3
0- .
p.
(2 5-1
(24-)
(2,6-) ,
2 4
26
3.4
CAS No.
95501
106467
78999
78875
142289
542756
78886
528290
100254
573568
121142
606202
610399
2-46
-------
Table 11-13 (Continued)
Common name
Isopropanolamine dodecylbenzen-
esulfonate.
Kelthane
Kepone
Lead acetate
Lead arsenate
Lead chloride
Lead fluoborate
Lead fluoride
Lead iodide
Lead nitrate
Lead stearate
Lead sullate
Lead sulfide
Lead thiocyanate
Lindane
Lithium chromate
Malathton
Maleic acid
Maleic anhydride
Mercaptodimethur
Mercuric cyanide
Mercuric nitrate
Mercuric sullate
Mercuric thiocyanate
Mercurous nitrate
Methoxychlor
Methyl mercaptan
Methyl methacrylate
Methyl parathion
Mevinphos
Mexacarbate....,
Monoethylamine
Monomethylamine
Naled
Naphthalene
Naphthenic acid
Nickel ammonium sulfate
Nickel chloride
Nickel hydroxide
Nickel nitrate
Nickel sulfate
Nitric acid
Nitrobenzene
Nitrogen dioxide
Nitrophenol (mixed)
Nitrotoluene
Paraformaldehyde
Parathion
Pentachlorophenol
Phenol
CAS No.
42504461
115322
143500
301042
7784409
7645252
10102484
7758954
.13814965
7783462
10101630
10099748
7428480
1072351
52652592
7446142
1314870
592870
58899
14307358
121755
110167
108316
203657
592041
10045940
7783359
592858
7782867
10415755
72435
74931
80626
298000
7786347
315184
75047
74895
300765
91203
1338245
15699180
37211055
7718549
12054487
14216752
7786814
7697372
98953
10102440
25154556
1321126
30525894
56382
87865
108952
Synonyms
Di(p-chtorophenyl)-trtchloromethylcarbinol
DTMC. dicofol.
cachlorooctahydro-1 ,3,4-metheno-2H-
cyclobuta(cd)pentalen-2-one.
Sugar of -lead
Lead fluoroborate
Lead difluoride, plumbous fluoride
Stearic acid lead salt
Galena
Lead sulfocyanate
We.
Phospothion
Cis-butenedioic acid, cis-1,2-ethylenedicar-
boxylic acid, toxilic acid.
toxilic anhydride.
Mesurol
Mercury cyanide ;
Mercury suHate, mercufy persulfate
ate, mercuric sullocyanide.
Mercury prolonitrate
DMDT, methoxy-DDT. .
sulfhydrate, thiomethyl alcohol.
Methacn/tic acid methyl ester methyl-2-
methyl-2-propenoate.
Nitrox-60
Phosdrin „
Zectran
Ethylamine, aminoethane *
Methylamine, aminomethane
White tar, tar camphor, naphthalin
zoic acid.
Ammonium nickel sulfate
Nickelous chloride
Nickelous hydroxide
Nickelous sulfate
Nitrobenzol, oil of mirbane
Mononrtrophenol
ized formaldehyde, polyoxymethylene.
DNTP, Niran
PCP, Penta
benzene, oxybenzene.
Isomers
o-
Ortho
Meta
Para
CAS No.
.
554847
88755
10O027
88722
99081
99990
2-47
-------
Table 11-13 (Continued)
Common name
Phosgene „.„.»...„..„.......
Phosphoric acid... ....
Phosphorus...... „.„ ....
Phosphorus oxychloride.... ....
Phosphorus pentasulfide -
Phosphorus trichloride.............
Potychorinated biphenyts «
Potassium arsenate
Potassium arsenile
Potassium bichromate
Potassium chromate ,
Potassium cyanide....
Potassium hydroxide
Potassium permanganate
Propargite
Sodium phosphate, dibasic
Sulfuric acid . , ...
2.* 5-T acid... ,
CAS No.
75445
7664382
7723140
10025873
1314803
7719122
1336363
7784410
10124502
7778509
7789006
151508
1310583
7722647
2312358
79094
123626
75569
121299
121211
91225
108463
7446084
7761888
7440235
7631892
7784465
10588019
1333831
7631905
7775113
143339
25155300
7681494
16721805
1310732
7681529
10022705
124414
7632000
7558794
10039324
10140655
7785844
7601549
10101890
10361894
7758294
10124568
10102188
7782823
7789062
57249
100425
7664939
12771083
93765
6369966
6369977
1319728
3813147
Synonyms
Diphosgene, carfoonyl chloride, chlorofor-
my) chloride.
Black phosphorus, red phosphorus white
phosphorus, yellow phosphorus.
Phospnoryl chloride, phosphorus chloride
dride. phosphorus persullide.
Phosphorous chloride
PCB, Aroctor, polychlorinated diphenyls
Potassium metaarsenite
Potassium dichromate
Chameleon mineral
Omite
mic acid.
dride.
chinoleine, leucol.
benzene.
We.
Viliiaumite , . . ...
Bleach
lene, cinnamene, cinnarnol.
pound with N.N-dimethylmethanamine
(1:1).
pound with N-methylmethanamine (1:1).
pound with 1 -amino-2-propanol (1:1).
pound with 2,2'2"-nitrilotris [ethanol]
(1:1).
Isomers
CAS No.
2-48
-------
Table n-13 (Continued)
Common name
2 4 5-T esters
2.4,5-T salts
TDE
2.4.5-TP acid
2.4.5-TP esters
Telraethyl lead
Tetraethyl pyrophosphate
Thallium sulfate
Toluene
Toxaphene
Trichlorfon
Trichlorethylene
Trichlorophenol
Triethanolamine dodecylbenzene-
sulfonate.
Triethylamine
Trimethylamine
Uranyl acetate
Uranyl nitrate
Vanadium pentoxide
Vanadyl sulfate
Vinylidene chloride
Xylene (mixed)....
Xylenol
Zinc acetate
Zinc ammonium chloride
Zinc borate
Zinc bromide
Zinc carbo'nate
Zinc chloride
Zinc cyanide
Zinc lluoride
Zinc formate
Zinc hydrosulfite
Zinc nitrate
Zinc phenolsulfonate
Zinc phosphide
Zinc silicofluoride
Zinc sulfate
Zirconium nitrate
Zirconium potassium fluoride
Zirconium sulfate
Zirconium tetrachloride
CAS No
2545597
93798
61792072
1928478
25168154
13560991
72548
93721
32534955
78002
107493
10031591
7446186
108883
8001352
52686
79016
25167822
27323417
121448
75503
541093
10102064
36478769
1314621
27774136
108054
75354
1330207
1300716
557346
14639975
14639986
52628258
1332076
7699458
3486359
7646857
557211
7783495
557415
7779864
7779886
127822
1314847
16871719
7733020
13746899
16923958
14644612
10026116
Synonyms
Acetic acid (2,4,5-trichlorophenoxy)-sodium
salt.
ODD
Propanoic acid. 2-{2,4,5-trichlorophenoxy)-
isooctyl ester.
Lead tetraethyl, TEL
TEPP
Methacide.
Camphechlor
Dylox
Ethylene trichloride
achior.
TMA
1,1-dichlorethylene
1,1-dichloroethene
Dimethylbenzene
Xylol
Zinc sulfocarbolate
Isomers
(2 3 4-)
(2,3 5-)
(2 3 6-)
(2.4.5-)
(2,4.6-) .
(3 4 5-)
p.
CAS No.
15950660
933788
933755
95954
88062
609198
108383
95476
106423
•
2-49
-------
Table 11-14 Examples of Param-
eters in STORET but not §304(h)
Atrazine
Bidrin
Caffeine
Cesium
Diethenylether
Disyston
Dursban
Fenthion
Gallium
Germanium
Kelthane
Lanthanium
Methyl myristate
Methyl palmitate
Perthane
Phorate
Phosdrin
Propazin
Ronnel
Rubidium
Simazine
Zirconium
Ecosystem-related measurements include
toxicity of wastes, wastewaters, surface waters,
and sediments to aquatic life, and the properties
of indigenous communities in receiving waters.
Toxicity tests applicable to biomonitoring
include tests for acute and chronic toxicity to
fish, invertebrates, and other aquatic life, and
mutagenicity are listed in Tables II-17 and 11-18.
Measurements of the biological integrity of
communities of aquatic organisms involve
detailed studies of the free living organisms such
as the native aquatic bacteria, microscopic
plants and animals, the flowering aquatic plants
(aquatic weeds), invertebrates, and fish. The
biological integrity of aquatic ecosystems is
related to questions such as:
• Are the expected kinds (species) of
organisms present in the expected
numbers and diversity, carrying out life
functions, such as growth and.
reproduction, at normal rates, free of
disease and other pollution-related effects?
• Are the organisms free of toxic substances?
• Is suitable habitat available?
To answer these questions the organisms
present in aquatic ecosystems must be identified
to species, and estimates must be made of the
abundance (standing crop), diversity, and the
condition of the organisms. Some of the basic
biological measurements that are made in
monitoring the biological integrity of surface
waters are listed in Table 11-19. A
comprehensive guidance manual for field
studies on biological integrity was prepared by
the Agency (2-40).
Specific analytes included in the SDWA and
FWPCA regulations are listed in Table 11-20.
Table 11-21 lists the microbiological standards
and criteria under the SDWA and FWPCA. EPA
has published a list of recommended species for
use in tests for the acute toxicity of effluents
under the NPDES permits program (2-16), and
recommends the use of only three species for
chronic toxicity tests (2-17). The recommended
species for effluent acute and chronic toxicity
tests are tabulated in Table II-22.
The biological analytes that are typically
required in the NPDES permit regulations and
technical support documents are "acute or
chronic toxicity". Yet, listing acute or chronic
toxicity without reference to the species which
are required or recommended by EPA and the
states for performing acute or chronic toxicity
testing is incomplete. It must be understood,
however, that listing "recommended" species
does not mean that all species must be tested or
that another species which are uniquely
important to a specific body of water could not
also be required. These species are recommended
because of their wide distribution throughout
the Nation's waters, sensitivity to pollutants, or
ease of culturing in the lab.
The point to be made is that the degree of
specificity that is present in listing chemical
analytes, even with the problems with
nomenclature previously discussed, is far
greater than the degree of specificity for
biological analytes. Because of the need for
tailoring monitoring requirements to the
specific body of water being protected or
investigated, it is not probable that the
specificity in biological analytes will ever reach
the level demonstrated for chemical analytes.
Although this lack of specificity would appear to
2-50
-------
Table 11-15 SDWA Priority List
Disinfectants and Disinfection
By-Products
Substance on the SARA
110 Priority List (From the
First Two Priority
Subgroups) Not Otherwise
Required to be Regulated
by the SDWA
NPS Design-Analytes List,
With Substance Already
Scheduled for Regulation,
or Otherwise Covered in
This Notice, Deleted
(Continued)
Monitoring Contaminants
Proposed for Inclusion on
the First DWPL
A. Disinfectants
Chlorine
Hypochlorite ion
Chlorine dioxide
Chlorite
Chlorate
Chloramine
Ammonia
Ozone
B. Trihalomethanes
Chloroform
Bromoform
Bromodichloromethane
Dibromochloromethane
Dichloroiodomethane
C. Halonitriles
Bromochloroacetonitrile
Dichloroacetonitrile
Dibromoacetonitrile
D. Halogenated Acids
Alcohols, Aldehydes, and Ketones
Monochloroacetic acid
Dichloroacetic acid
Trichloroacetic acid
Chloralhydrate
2,4-dichlorophenol
E. Others
. Chloropicrin
Cyanogen chloride
3-chloro-4-dichloromethyl)-5-
hydroxy-2(5H)furanone (MX)
Dieldrin/Aldrin
Chloroform
Heptachlor/
Heptachlorepoxide
N-nitrosodiphenylamine
N-nitrosodimethylamine
4,4'-DDE)DDT,DDD
Chloroethane
Bromodichloromethane
Isophorone
1,1,2,2-Tetrachloroethane
3,3'-Dichlorobenzidine
Benzidine
Phenol
Bis(2-chloroethyl)ether
2,4-Dinitrotoluene
Bis(chloromethyl)ether
N-nitrosodi-n-propylamine
Acifluorifen
Ametryn
Baygon
Bentazon
Broacilm
Butylate
Carbaryl
Carboxin
Carboxin sulfoxide
Chloramben
Chlorothalonil
Cyanazine
Cycloate
DCPA
DCPA acid metabolites
Diazanon
Dicamba
1,3-Dichloropropene
3,5-Dichlorobenzoic acid
Diphenamid
Disulfoton and sulfone
Diuron
ETU
Fenamiphos sulfone
Fenamiphos sulfoxide
Fluormeturon
Hexazinone
Hexachlorobenzene
Hydroxydicamba
Methomyl
Methyl paraoxon
Metolachlor
Metribuzin
Metribuzin DA, DADK, DK
Prometon
Prometryn
Pronamide
Pronamide metabolite
Propachlor
Propazine
Propham
Tebuthiuron
Terbacil
Trifluralin
2,4,5-T
Chloroform
Bromodichloromethane
Bromoform
1,1,1,2-Tetrachloroethane
Ethylbenzene
1,3-Dichloropropane
Bromobenzene
Chloromethane
Styrene
Bromome thane
1,2,3-Trichloropropane
1,1,2,2-Tetrachloroethane
Chloroethane
2,2-Dichloropropane
o-Chlorotoluene
p-Chlorotoluene
1,1 -Dichloropropene
1,1 -Dichloroethane
2-51
-------
Table n-16 Human Pathogens, Parasites, and
Indicator Organisms(l)
Table n-16 (Notes, Continued)
Analytes
I. Microbiological
A. Viruses
1. Non-pathogens (indicators of
pathogens)
Coliphage
2.Pathogens
Adenovirus (30 + types)
Cossackievirus A (24 types)
Coxsackievirus B (6 types)
Echovirus (34 types)
Gastroenteritis type Norwalk (2
types)
Hepatitis type A( 1 type)
Norwalk (Gastroenteritis type)
Agents (2 types)
Poliovirus (3 types)
Reovirus (3 types)
Rotavirus ( 4 types)
B. Bacteria
1. Non-pathogens (indicators of
pathogens)
Clostridium perfringers
Fecal coliforms
Fecal streptococci
Staphylococci (coagulase positive)
2. Pathogens
Aeromonas hydrophila
Clostridium botulinum
Enteropathogenic E. coli
Legionella
Leptospira
Mycobacteria
Pseudomonas aeruginosa
Salmonella
Shigella
Vibrio cholerae
Vibrio parahemolyticus
C. Protozoa
Balantinium coli
Cryptosporidium
Entamoeba histolytica
Giardia lamblia
D. Worms, worm larvae, and eggs
Nematodes
Ascaris ova
Taenia ova
Trichuris ova
Source
of
Methods
5
3,4
3,4
3
5
5
3
2
3
5
3
4
3
3
5
5
2
5
6
3
5
5
5
(1) Code for Sources of Methods
l.Berg, G., R. S. Safferman, D. R. Dahling, D. Berman, and
C. J. Hurst.l984.USEPA Manual of Methods for
Virology-Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency,
Cincinnati, Ohio.EPA 600/4-84-013.
2. Methods remaining to be developed
3. APHA.1985.Standard Methods for the Examination of
Water and.Wastewater, 16th ed. Amer. Publ. Hlth. Assoc.,
Washington, DC.
4. Bordner, R. H. and J. A. Winter. 1978. Microbiological
Methods for.Monitoring the Environment, Water and
Wastes. Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency,
Cincinnati, Ohio. EPA-600/8-78-017.
5. Methods are available in EPA reports and/or open
literature.
6. Methods currently being developed.
Table 11-17 Toxicity Tests
Analytes
Source of
Methods
1. Toxicity to algae, invertebrates, and fish 1,2,3
2. Microbial Mutagenicity (Ames Test) 4
3. Mammalian toxicity/mutagenicity (using 5
cell cultures)
4. Microbial toxicity (Toxicity to bacteria 5
providing assimilative capacity in surface
waters)
1. Peltier, W.H., and C.I. Weber. 1985. Methods for
Measuring the Acute Toxicity of Effluent to Freshwater
and Marine Organisms. Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection
Agency, Cincinnati, Ohio EPA-600/4-85-013.
2. Horning, W. B., and C. I. Weber. 1985. Short-Term
Methods for Estimating the Chronic Toxicity of Effluents
to Freshwater Organisms. Environmental Monitoring
and Support Laboratory, U.S. Environmental Protection
Agency, Cincinnati, Ohio. EPA-600/4-85-014.
3. Weber, C. I., W. B. Horning, D. J. Klemm, T. W.
Neiheisel, P. A. Lewis, E. L. Robinson, D. McMullen. 1987.
Short-Term Methods for Estimating the Chronic Toxicity
of Effluents to Marine and Estuarine Organisms.
Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati, Ohio.
EPA-600/4-87-028.
4. FR 50(165):34592; FR 51( 131 ):24897.
5. Williams, L. R., and J. E. Preston. 1982. Interim
Procedures for Conducting the Salmonella/Microsomal
Mutagenicity Assay (Ames Test). U.S. Environmental
Protection Agency, Environmental Monitoring Systems
Laboratory, Las Vegas, Nevada. EPA 600/4-82-068.
6. EPA methods remaining to be developed. Some methods
are available in the open literature.
2-52
-------
Table 11-18 Use of Captive Organisms in Bioaccumulation and Toxicity Tests (1)
Organism
Type of Test Phyto- Zoo- Peri- Macro- Macro-
plankton plankton phyton phyton invert
Fish
IN SITU TESTS
1. Bioaccumulation
Toxic Metals X
Pesticides (organics) X
Flesh Tainting
2. Toxicity Tests
Acute Toxicity
Histopathology
Histochemistry
Cholinesterase
IN-PLANT TESTS (EFFLUENTS)
1. Bioaccumulation
Toxic metals X
Pesticides (organics) X
Flesh tainting
2. Toxicity tests
Acute toxicity X
Low-level responses
(behavioral responses)
Histpathology
3. Biostimulatory tests
Algal growth response X
LABORATORY TESTS
1. Bioaccumulation
Toxic Metals X
Pesticides (organics). X
2. Toxicity tests
Acute toxicity X
Chronic toxicity X
Histopathology
Low-level responses (behavioral
responses)
3. Biostimulatory tests X
X X X X
X X X X
X
X
X
XXX
X
X X X X
X X X X
X
X X
X
X
X
X X X X
XX X X
X X
X X X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(1) From 2-5
2-53
-------
Table 11-19 Properties ofjndigenous Communities of Aquatic Organisms Used in Determining the
Biological Integrity of Surface Waters (1)
Biological Community
Parameters Phyto- Zoo- Peri- Macro- Macro-
plankton plankton phyton phyton invert
Fish
STANDING CROP
1. Count
2. Volume
3. Wet weight
4. Dry weight
5. Ashfree weight
6. DNA content
7. ATP content
8. Chlorophyll a content
TAXONOMIC COMPOSITION
1. Species identification
Indicator species
Numbers within species
Total number of species
Diversity index
2. Pigment composition
Biomass/Chlorophyll a
Chloro a/Chloro b
Chloro a/Chloro c
Pheophytin content
3. Nitrogen fixation
METABOLIC
ACTIVITY/CONDITION
1. Primary Productivity
Carbon-14 uptake
Oxygen evolution
2. Respiration rate
Plankton oxygen uptake
Electron Transport
Benthic oxygen uptake
3. Nitrogen fixation
4. Chemical composition
Macronutrient content
Enzyme content
Cholinesterase
Phosphatase
Nitrate reductase
Toxic chemical content
5. Flesh tainting
6. Histopathology
7. Condition factor
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
• X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(1) From 2-5
2-54
-------
Table 11-20 List of Required or Recommended
Microbiological Analytes Under FWPCA and SDWA
Test Test Time
Species or parameter
Temperature Period
Safe Drinking Water Act
(l)Totalcoliforms
(2)Fecal coliforms
(3)Fecal Streptococci
(4) Heterotrophic plate count
(5) Salmonella spp
(6) Enterovirus
(7) Cryptosporidium
(to be developed)
(8) Giardia lamblia
(9) Legionella (to be
developed)
35C
44.5
35
35
various
36.5.
28
-
-
24-48 hrs
24hrs
48 hrs
48-72 hrs
various
2 hrs
7 days
-
-
diminish the usefulness of biological analytes,
biological monitoring that is not focused on a
specific biological component of an ecosystem,
increases the chances of detecting unpredictable
but often significant consequences of man's
activities.
As evidenced by Table 11-23, a significant
part of the biomonitoring program under the
FWPCA is required by the NPDES permit
program. Other than FWPCA and SDWA
requirements for microbiological monitoring in
municipal, industrial effluents, and public water
supplies, this program requires the most
frequent monitoring across the broadest area.
Biomonitoring under the NPDES program has
been evolving, as previously described in this
chapter, due to an increased emphasis on the
control of toxics to protect human health and the
integrity of biological systems.
In an effort to obtain "ground truth" data,
the various regional offices of the EPA and the
appropriate State agencies were surveyed in
1986, (2-15). Regions and States were asked the
number of NPDES permits they administered,
Table 11-21 Water Quality Standards for Microbiological Parameters
Microbiological Standards
Water or Waste water Coliforms/100 ml Reference Source
Total Fecal
Potable Water
Chlorinated Effluents
2" Treatment Wastes
Selected Industrial Wastes
Leather and Tanning
Feed Lots
Meat Products
Beet Sugar
Canned Fruits and Vegetables
Textiles
Effluents from Marine Sanitation
Devices- Type I
Effluents from Marine .Sanitation
Devices- Type 1 1
<5
200-400
200-400
200-400
400
400
400
400
400
400
1000
200
PL 93-523
PL 92-500
40 CFR Part 133
PL 92-500
40 CFR Part 425
40 CFR Part 412
40 CFR Part 432
40 CFR Part 409
40 CFR Part 407
40 CFR Part 410
40 CFR Part 140 and
Amendments
40 CFR Part 140 and
Amendments
2-55
-------
Table 11-22 Water Quality Criteria for Microbiological Parameters
Microbiological Standards
Statistical Measure Coliforms/100 ml
Enterococci
Total Fecal
Water or
Wastewater
Reference
Source
Public Water Supply
Recreational Water:
Freshwater
Marine Waters
Shellfish-Raising
Waters
logX
geometric mean of
>5 samples/30 days
geometric mean of
>5 samples/30 days
Daily Median
Highest 10% of
Daily Values
20,000
33
35
2,000
126
14
43
A,B
A,B
A,C
Quality Criteria for Water, EPA 1986. Office of Water Regulations and Standards, Washington, DC 20460
EPA 440/5-86-001.
EPA, 1986. Ambient Water Quality Criteria for Bacteria -1986 Office of Water Regulations and Standards,
EPA, Washington, DC EPA 440/5-84-002.
National Shellfish Sanitation Program Manual of Operation. U.S. Dept of HEW, 1965. Public Health
Service Publ. No 33. Superintendent of Documents, U.S. Government Printing Office, Washington, DC
20402.
the number of permits with a biological toxicity
testing requirement, the number of permits with
expressed toxicity limits and with requirements
for toxicity reduction evaluations. Regional and
State programs were discussed, including the
use of biological testing such as acute and
chronic bioassay techniques, instream biotic
assessments, analysis of aquatic organisms for
bioaccumulation, as well as the use of biological
investigative techniques. The results of the
survey must be characterized as extremely
diverse due to the different stages each Region
or State had reached in the evolution of their
program. Responses ranged from "no current
program" through "an emerging program" to a
"developing program."
To date, few states have a formal written
policy or strategy on the use of biological testing
in their NPDES program. However, many states
have developed preliminary policies or were
developing a policy. Biological testing methods
were generally either effluent (end-of-pipe)
testing or determining the biological integrity of
receiving waters. Permits requiring effluent
testing were the most prevalent. Required
toxicity tests were typically static or flow-
through tests of undiluted or diluted wastewater
for 96 hours or less (acute testing) or up to 7 days
(chronic testing). These state or federal
programs required methods appropriate for
ambient or environmental damage assessment
from toxic pollutants, including:
• studies and assessments related to
macroinvertebrates, fish, algae, periphy-
ton, protozoa,
• primary productivity,
• sediment bioassays and analyses,
• fish flesh tainting,
• fish and mussel flesh analyses for
bioaccumulated compounds,
• toxicity to caged organism, and
2-56
-------
• fish avoidance reactions (behavioral
bioassays).
Table 11-24 summerizes the statistics for the
regions and states. Several figures, which are
noteworthy, resulted from this study:
• 1,802 NPDES permits or 24 percent of the
number of major permits required
biological toxicity testing.
• 1,417 industrial permits required effluent
biological toxicity testing; this is 79
percent of permits requiring testing and 38
percent of the number of major industrial
permits.
• 385 municipal permits required effluent
biological toxicity testing; this is 21
percent of permits requiring testing and 11
percent of the number of major municipal
permits.
• 37 States required industries to conduct
bioassays.
• 27 States required municipalities to
conduct bioassays.
A brief review of the responses found that
the following species or test methods were being
specifically required or used:
• Water flea (Daphnia spp.).
• Fathead minnow (Pimephales promelas).
• Silversides (Menidia sp).
• Mysid shrimp (Mysidopsis bahia).
• Ceriodaphnia sp.
• Ames test (screening only).
• Killifish.
• Threespine stickle back (Gasterosteus
aculeatus).
• Golden shiner.
• Rainbow trout.
• Lobster (American).
• Algae (Selenastrum sp.).
• Sheepshead minnow.
• Salmonid fish.
• Amphipods (Gammarus sp. Hyallela sp.).
• Mayfly (Hexagenia sp.).
• Oyster larvae (Crassostrea virginica,
C.gigas).
• Microtox test method (Photobacterium
phosphoreum).
Based on the information in Table 11-24, the
Regions with significant biomonitoring
requirements were Regions II, IV, V, VI, and IX.
The biomonitoring requirements of Regions II,
V, VI, IX were investigated further by
examining the specific analytes being required
for all current NPDES permits issued within the
region. As of July, 1987, due to the lag period
between the implementation of the toxic
monitoring policy by the Regional offices and the
States and the initial filing of data with the
Regional offices (DMR Reports), few Regional
offices were requiring toxicity data as reported
in the STORET files. The number of times that
biological toxicity testing requirements were
cited in permits is presented below:
Region II
Bioassay (not otherwise specified).
LC50, Fathead Minnow, flow
through
LC50, Fathead Minnow, static
LC50, Mysid shrimp, static
LC50, Sheepshead minnow, static
Toxicity, Concentration
Toxicity, Final concentration
Region IV
Bioassay
Toxicity Limits
Region V
Bioassay {not otherwise specified)
Toxicity, Concentration
Region VI
Bioassay (not otherwise specified)
Toxicity, concentration
Region IX
Bioassay
Toxicity, Final concentration
149
1
8
3
3
1
3
364
141
1
2
334
2
47
50
It is believed that the number of NPDES
permits requiring toxicity testing will
significantly increase when "round three"
permits begin to be cited in the STORET files.
For instance, Region VI reports that the number
of permits with bioassay requirements will
increase from 334 to 980. It should be recognized
that general permits (e.g., offshore oil and gas
operations) will significantly increase the
amount of bioassay data being generated but
will not increase the tabulated number of
permits requiring bioassay data proportionally
2-57
-------
because general permits are reported as one
permit.
The only other biological analyte required in
NPDES permits relates to microbiological
analytes. Again, for Regions II, V, VI, and IX,
the following number of NPDES permits
required microbiological monitoring:
Region II
Coliform, fecal
Coliform, total
Region V
Coliform, fecal
ColJform, fecal, MF, M-FC
Coliform, fecal, MPN + MF
Coliform, total
Region VI
Coliform, fecal
Coliform, total
Region IX
Coliform, fecal
Coliform, total
904
180
689
158
80
1
593
1
55
231
No listings were found within these four
regions for any other biological analytes for
effluent testing. It should be emphasized that
there are some apparent differences between the
Regional offices in coding NPDES permit
requirements for entry into the national Permit
Compliance System (PCS) Program. This will
cause the same confusion that was evident with
the chemical analytes where numerous names
were used for reporting the same analyte.
Clearly, compared to the extensive lists of
chemical analytes being specifically required,
biological analytes required for effluent testing
constitute a small percentage. However, the
total biological monitoring effort is significant
because numerous field studies of biological
integrity are conducted in support of the
issuance of permits (to determine wasteload
allocations), to determine ambient conditions,
and to determine compliance. Very few of these
data could be entered into the PCS because
biological data management software were not
available.
2-58
-------
Table 11-23 List of recommended or required species for acute or chronic toxicity testing under
NPDES permits program.
Species or parameter
Acute Toxicity
Freshwater
Vertebrates
Cold Water
Brook trout
Coho salmon
Rainbow trout
Warm Water
Bluegill
Channel catfish
Fathead minnow
Invertebrates
Cold Water
Stonefiles
Crayfish
Mayflies
Warm Water
Amphipods
Cladocera
Crayfish
Mayflies
Midges
Marine and Estuarine
Vertebrates
Cold Water
English sole
Sanddab
Winter flounder
Warm Water
Flounder
Longnose killfish
Mummiehog
Test
Temper
-ature
<°C)
Salvelinus fontinalis
Oncorhynchus kisutch
Salmo gairdneri
Lepomis macrochirus
Ictalurus punctatus
Pimephales promelas
Pteronarcys spp.
Pacifastacus leniusculus
Baetis spp. or Ephemerella spp.
Hyalella, spp.,
Gammarus lacustris, G. fasciatus or
G. pseudolimnaeus
Daphnia magna or D. pulex,
Ceriodaphnia spp.
Orconectes spp.,
Cambarus spp.,
Procambarus spp.,
Hexagenia limbata or H. bilineata
Chironomus spp.
Parophrys vetulus
Citkarichtkys stigmaeus
Pseudophleuronectes americanus
Paralichthys dentatus,
P. lefhostigma
Fundulus similis
Fundulus heteroclitus
12
12
12
20
20
20
12
12
12
20
20
20
20
20
20
20
20
20
20
12
12
12
20
20
20
Life Stage
30-90 days
30-90 days
30-90 days
1 -90 days
1 -90 days
1 -90 days
Larvae
Juveniles
Nymphs
Juveniles
Juveniles
Juveniles
l-24h
l-24h
Juveniles
Juveniles
Juveniles
Nymphs
Larvae
1-90 days
1-90 days
Postmetamorph
1-90 days
1-90 days
1-90 days
1-90 days
(Continued)
2-59
-------
Table 11-23 (Continued)
Species or parameter
Test Temperature
Life Stage
Pinfish
Sheepshead minnow
Silverside
Spot
Threespine
stickleback
Invertebrates
Cold Water
Dungeness crab
Oceanic shrimp
Green sea urchin
Purple sea urchin
San dollar
Warm Water
Blue crab
Mysid
Grass shrimp
Penaid shrimp
Sand shrimp
Pacific oyster
American oyster
Lagodon rhomboides
Cyprinodon variegatus
Menidia spp.
Leiostomus xanthurus
Gasterosteus aculeatus
Cancer magister
Pandalusjordani
Strongylocentrotus
droebachiensis
S.purpuratus
Dendraster excentricus
Callinectes sapidus
Mysidopsis spp.
Neomysis spp.
Palaemonetes spp.
Penaeus setiferus,
P. duorarum,
P. aztecus
Crangon spp.
Crassostrea gigas
Crassostrea virginica
20
20
20
20
20
12
12
12
12
12
20
20
20
20
20
20
20
1-90 days
1-90 days
1-90 days
1-90 days
1-90 days
Juvenile
Juvenile
Gametes/embryo
Gametes/embryo
Gametes/embryo
Juvenile
1-5 days
1-5 days
1-10 days
Post larval
Post larval
Post larval
Post larval
Post larval
Embryo/larval
Chronic Toxicity
Freshwater
Fathead minnow
Cladocera
Alga
(Pimephales promelas)
(Ceriodaphnia dubia)
(Selenastrum capricornutum)
25
25
24
Larvae/embryo
Neonate/adult
The following notes refer to the acute toxicity tests:
a. To avoid unnecessary logistical problems in trying to maintain different test temperatures for each test
organism, it would be sufficient to use one temperature (12°C) for cold water organisms and one
temperature (20°C) for warm water organisms.
b. The optimum life stage is not known for all test organisms.
c. Mayes et al., 1983, found no significant difference in the sensitivity of fish ranging in age from 10 to 100
days, in tests with nine toxicants.
d. Daphnia pulex is recommended over D. magna because it is more widely distributed in the United
States, test results are less sensitive to feeding during tests, and it is not as easily trapped on the surface
film.
2-60
-------
Table n-24. Summary of NPDES Permits Requiring Biological Toxicity Testing and States with Biological
Testing Programs. 2-18.
NPDES Permits
States
Alabama
Alaska
Arizona*
Arkansas
California
Colorado
Connecticut
Delaware
D.C.
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa*
Kansas*
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan*
Minnesota
Mississippi
Missouri*
Montana*
Nebraska*
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota*
Ohio*
Oklahoma
Oregon
Pennsylvania*
Major
Indus-
trial
82
308
23
56
98
70
130
21
0
122
60
19
42
104
88
34
14
205
145
56
52
57
122
28
39
70
6
26
3
57
200
16
166
94
7
150
36
23
171
Indus-
trial
with
Bio-
assays
1
25
2
0
.34
440
0
1
5
0
35
25
2
3
4
6
0
0
17
100
10
13
10
3
2
20
0
2
0
0
10
118
5
10
30
0
1
22
15
0
With
Toxic-
ity
Limits
25
0
0
0
440
0
1
0
0
35
0
0
0
0
0
0
0
1
0
8
0
8
0
0
4
0
0
0
0
8
118
0
0
30
0
0
0
2
0
Major
Mu-
nicipal
85
19
19
59
148
70
68
15
1
125
120
11
28
175
94
62
32
56
75
68
35
68
95
50
45
70
17
44
10
69
160
21
266
121
15
155
59
36
225
Mu-
nicipal
with
Bio-
assays
1
0
0
0
0
110
8
0
1
1
10
1
1
2
1
0
0
0
3
0
8
20
8
2
0
0
0
0
0
1
9
111
0
10
24
0
0
0
0
0
With
Toxic-
ity
Limits
0 .
0
0
0
110
0
0
0
0
10
0
0
0
1
0
0
0
2
0
5
0
5
0
0
0
0
0
0
1
5
111
0
0
24
0
0
0
0
0
Biotic
As-
sess-
ments
Re-
quired
0
0
0
0
0
0
0
0
0
0
0
3
0
0
0
0
0
0
6
0
0
0
0
0
0
2
0
0
1
0
0
0
0
0
0
0
0
1
0
State Program
Flow-
Static through/
Bio- Chronic
assays Bio-
assays
Few
0
0
12
Some
2
100
0
0
0
Many
0
0
25
15
0
Few
50
0
0
Few
0
30
75
15
0
10
0
0
0
5
0
0
150
0
75
0
4
0
10
0
0
0
Some
2
10
0
0
0
12
0
0
10
0
0
0
0
0
0
Few
0
5
2
0
16
2
0
0
0
5
0
10
12
0
10
0
30
0
Biotic
•As-
sess-
ment
Loca-
tions
7
0
0
40
0
3
6
2
0
0
20
0
0
30
5
2
4
12
0
0
0
0
50
0
1
200
8
6
0
0
Few
8
5
50
0
20
0
15
35
(Con-
tinued)
*States with a principally pollutant specific approach for toxics-
Numbers may represent major and minor permits.
2-61
-------
Table 11-24. (Continued)
NPDES Permits
States
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont*
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Totals
No. of States
Major
Indus-
trial
16
80
4
86
234
19
8
100
45
75
62
30
3759
-
Indus-
trial
with
Bioas-
saysl
12
55
0
12
133
0
0
120
40
39
36
0
1417
-
With
Toxic-
ity
Limits
0
5
0
5
0
0
0
0
30
39
0
0
759
-
Major
Mu-
nicipal
19
115
29
75
241
39
31
25
45
34
88
20
3652
-
Mu-
nicipal
with
Bioas-
saysl
12
5
1
2
0
14
0
25
3
0
0
2
385
-
With
Toxic-
ity
Limits
0
0
0
0
0
0
0
0
0
0
0
0
274
-
Biotic
As-
sess-
ments
Re-
quired
0
40
0
0
0
0
0
20
0
0
0
0
73
State Program
Static
Bio-
assays
0
100
0
Many
0
0
0
36
0
100
0
0
.
23
Flow-
through/
Chronic
Bio-
assays
0
10
0
12
0
0
0
2
6
0
0
0
.
20
Biotic
As-
sess-
ment
Loca-
tions
0
15
16
12
0
0
0
.Few
0
60
450
0
_
29
'States with a principally pollutant specific approach for toxics..
Numbers may represent major and minor permits.
2-62
-------
Chapter Two References
1. Rogers, W.H., 1977. Environmental Law.
West Publishing Company. St. Paul, MN.
956 pp.
2. EPA, 1984. Paragraph 4(c) Program
Summary Report. Effluent Guidelines
Division. EPA. Washington, D.C. 46 pp.
3. EPA. 1975. Model State Water
Monitoring Program. Monitoring and Data
Support Division, Office of Water and
Hazardous Materials, U.S. Environmental
Protection Aency, Washington, D.C.
4. EPA. 1977. Basic Water Monitoring
Program, Monitoring and Data Support
Division, Office of Water and Hazardous
Materials, U.S. Environmental Protection
Agency, Washington, D.C., EPA-440/9-76-
025.
5. Weber, C.I. 1980, Federal and state
biomonitoring programs. In: D. Worf (ed),
Biological Monitoring for Environmental
Effects. Lexington.Books, Lexington, MA.
pp. 25-52.
6. Natural Resources Defense Council V. Train
(8 ERC 2120, D.D.C., 1976).
7. Arbuekle, J.G. and T.A. Vanderver, 1980.
Water Pollution Control Laws and
Regulations. In: Proc., Environmental Law
Symposium. Government Institutes.
Washington, D.C. pp 3-1 to 3-35.
8. Wall, T.M. and R. Hanmer, 1987. Biological
testing to control toxic water pollutants. J.
Wat. Poll. Control. Fed. 59(1):7-12.
9. EPA, 1984. Development of water quality-
based permit limitations for toxic pollutants.
49 Federal Register:9016. March 9,1984.
10. EPA, 1987. Permit writer's guide to water
quality-based permitting for toxic
pollutants. Office of Water. July, 1987. 30 pp
+ app.
11. FWPCA §502(13), 42. U.S. C.A. §1362(13).
12. FWPCA §101(a)(3); 42. U.S.C.A. §1251(a)(3).
13. The 1987 Industrial Technology Division
List of Analytes
14. The 1987 Industrial Technology Division
List of Lists
15. List (Phase 1) of Hazardous Constituents for
Ground Water Monitoring (52 FR 25942)
16. Peltier, W.H.and C.I. Weber. 1985. Methods
for measuring the acute toxicity of Effluents
to Freshwater and Marine Organisms. Third
Edition. EPA, Environmental Monitoring
and Support Laboratory, Cincinnati.
EPA/600/4-85-013 Section 5. Test
organisms, pp. 13-16 -
17. Horning, W.C. and C.I. Weber, 1985, Short-
term methods for estimating the chronic
toxicity of effluents and receiving waters to
freshwater organisms. EPA, Environmental
Monitoring and Support Laboratory,
Cincinnati,.OH. EPA/600/4-85-014. 162 pp.
18. U.S. Environmental Protection Agency,
1986. Program survey - biological toxicity
testing in the NPDES permits program.
Office of Water, Permits Division. July 1986.
72pp.
19. EPA, 1984. Paragraph 4(c) Program,
Summary Report Effluent Guidelines
Division. January, 1984.
20. EPA, 1980. Definitions - National Summary
of State Water Quality.Standards. Nalesnik
Associates Incorporated, Washington, DC.
October, 1980.
21. EPA, 1986. Summary of Rulemaking
Activities Affecting Indirect Discharges,
Volume II. Industrial Technology Division,
May, 1986.
22. EPA, 1980. Pesticides, Water Quality
Standards Criteria Summaries, A
Compilation of State/Federal Criteria Office
of Water, October, 1980.
23. EPA, 1980. Cyanide - National Summary of
State Water Quality Standards, Nalesnik
Associates Incorporated, Washington, DC,
July 1980.
24. EPA, 1980. General Provisions/Freedoms -
National Summary of State Water.Quality
Standards, Nalesnik Associates
2-63
-------
Incorporated, Washington, DC, September,
1980.
25. EPA, 1979. Acidity-Alkalinity (pH) - Water
Quality Standards Criteria Digest, A
Compilation of State/Federal Criteria, Office
of Water, December, 1979.
26. EPA, 1980 Turbidity - National Summary of
State Water Quality Standards, Nalesnik
Associates Incorporated, Washington, DC,
September, 1980.
27. EPA, 1980. Other Elements - National
Summary of State Water Quality Standards,
Nalesnik Associates Incorporated,
Washington, DC, October, 1980.
28. EPA, 1979. Dissolved Solids - Water Quality
Standards Criteria Digest, A Compilation of
State/Federal Criteria, Office of Water.
December 1979.
29. EPA, 1980. Intermittent Streams,
Provisions/Policies - National Summary of
State Water Quality Standards. Nalesnik
Associates Incorporated, Washington, DC,
September, 1980.
30. EPA, 1980. Mixing Zones - Water Quality
Standards Criteria Summaries,
A.compilation of State/Federal Criteria.
Office of Water. July, 1980.
31. Gaskill, A.Jr., E.D. Estes and D.L. Hardison,
•Evaluation of Techniques for Determining
Chlorine in Used Oils. Research Triangle
Institute, NC, August, 1987.
32. Summary of the Regulated Toxic
Parameters (Indirect Dischargers). Effluent
Guidelines Division, April, 1984.
33. Gaskill, A.Jr., E.D. Estes and D.L. Hardison,
Evaluation of Techniques for Determining
Chlorine in Used Oils. Research Triangle
Institute, NC, August, 1987.
34. Summary of the Regulated Toxic
Parameters (Indirect Dischargers).
Effluent.Guidelines Division, April, 1984.
35. Code of Federal Regulations, Title 40, Parts
400-471, July 1986.
36. EPA, 1986. Quality Criteria for Water
1986.Office of Water, May 1,1986.
37. EPA, 1987. White Paper on EPA
Environmental Analytical Methods
Development. Office of Acid Deposition,
Environmental Monitoring and Quality
Assurance, Washington, DC, January, 1987.
38. EPA, 1986. Numeric Criteria for Toxic
Pollutants in State Water Quality
Standards, Office of Water Regulations and
Standards. April, 1986
39. Telliard, W.A., M.B. Rubin, and D.
Rushneck, 1987. Control of Pollutants in
Waste Water. J. Chromatogr. Sci. 25:322-
327.
40. Weber, C.I., 1973. Biological Field and
Laboratory Methods for Measuring the
Quality of Surface Waters and Effluents.
Methods Development and Quality
Assurance Laboratory, Environmental
Protection Agency, EPA-670/4-73-001.
2-64
-------
CHAPTER THREE
CRITERIA FOR DETERMINATION OF ADEQUACY
OF TESTING METHODS
The adequacy of a method is based on its
performance characteristics relative to the data
requirements. Obviously, a method that is
adequate in one situation could be inadequate in
another. For example, a method developed to
measure a pollutant at a concentration of 10
mg/L is adequate for measuring an industrial
discharge with an effluent limitation of 100
mg/L but is inadequate for measuring the same
pollutant in ambient water at a water quality
criteria concentration of 0.1 mg/L.
A thorough understanding of a method's
performance characteristics is therefore
essential in assessing its adequacy for a given
need; In addition, a method developed for
monitoring purposes should be based on sound
scientific principles and be practical for routine
use. The development and standardization of a
method to this level of use is a multistep process
termed validation. The validation process
verifies that the method is capable of reliably
producing results of a known quality.
Because of time restrictions and the need to
provide monitoring methods to the regulated
community, methods are often published
without performing the level of validation
required to identify and remedy any weaknesses
of the method. The performance characteristics
and the degree of standardization of a method
are therefore the controlling criteria for the
determination of adequacy relative to a specific
need.
For any given combination of analytes and
samples, an array of test methods may be
available. These methods typically have been
developed by different laboratories and achieved
very different levels of documentation and
standardization. The methods will not
necessarily provide equivalent results in terms
of detection limits, precision or bias. However,
based on the data quality objectives of the user,
each may be adequate. The determination of
adequacy of a specific method is therefore
dependent on the specific monitoring needs.
A method that has completed an initial
validation phase may be suitable for research or
limited monitoring applications. However, when
methods which have not been fully validated are
promulgated or required for routine monitoring
use, the Agency may expose itself to criticism
from the regulated community. Resources and
time are not available to fully validate all
methods nor is this required as a pre-condition of
program use under the FWPCA. There should be
an appropriate balance, depending on the data
quality objectives, between the level of effort
expended in standardizing a method and the
return gained in the confidence and respect of
the community of laboratories who must use
these methods.
This chapter defines criteria for judging the
adequacy of a method, first by defining
performance characteristics and then by
discussing the validation and standardization
process.
This chapter has been divided into two
sections. The first part discusses the criteria for
chemical procedures and the second part
3-1
-------
addresses the criteria for biological methods.
Where there is overlap between the two sections,
the overlapping discussion has been placed in
the first section.
Method Performance
Characteristics
There are many characteristics of a method
that can be used to evaluate its performance. In
most cases, no single method will contain all of
the desirable characteristics. The selection of a
method is therefore based on evaluating which
characteristics are important for a given need.
For the purposes of this report, certain
characteristics which are directly applicable to
establishing the adequacy of a method were
identified. This section provides a brief
description of these characteristics,
summarizing information presented elsewhere
(3-1 to 3-9).
Detection Limits
The definition and determination of
detection limits are a controversial subject of
debate in the scientific and regulatory
community. This controversy exists in two
areas. First, what is the most appropriate and
meaningful measure of the limit of detection?
Second, how should a protocol be designed to
collect the information that will result in
establishing realistic and useful detection
limits? A number of terms have been defined
relating to detection limits (3-9, 3-10). These
terms and their definitions are shown in Table
III-l. Within the EPA, Superfund focuses on
sample quantification limits, the Federal Water
Pollution Control Act (FWPCA), on method
detection limits, and the Safe Drinking Water
Act (SDWA) and the Resource Conservation and
Recovery Act (RCRA) on practical quantitation
limit. Limits of detection and limit of
quantitation have also been established by the
American Chemical Society with funding and
staff participation from the EPA. The PQL is an
interlaboratory concept while LOQ is specific to
an individual laboratory. The Agency developed
the PQL concept to define a measurement
concentration that is time and laboratory
independent for laboratory purposes. The
detection limit terms defined in Table III-l have
a quantifiable relationship. A method should
contain an experimentally determined, clearly
identified and defined detection limit for each
analyte and matrix for which the method is
applicable.
The detection limit should be related to
results obtained during routine analyses of
environmental samples, since many times
detection limits are used to establish regulatory
limits. The American Chemical Society states
that "quantitative interpretation, decision
making and regulatory actions should be limited
to data at or above the limit of quantification"
(3-9). The Agency's PQL concept is based not
only on quantitation but also on precision and
accuracy, normal operating conditions of a
laboratory, and the fundamental need (in
compliance monitoring) to have a sufficient
number of laboratories available to conduct the
analyses. The PQLs do not actually represent
the results of normal laboratory procedures but
are a model of what normal laboratory
procedures might achieve. The Agency should
establish one common definition of and means
for determining a quantitation limit for a
method and all applications of that method.
Precision
Precision is a measure of agreement among
individual measurements of the same property,
under prescribed similar conditions (3-11, 3-12).
For analytical methods, precision may be
specified as either "intralaboratory" (within
laboratory) or "interlaboratory" (between
laboratories) precision. Intralaboratory
precision estimates represent the agreement
expected when a single laboratory uses the
method to make repeated measurements of the
same sample. Interlaboratory precision refers to
the agreement expected when two or more
laboratories analyze the same sample with the
same method. Intralaboratory precision is more
commonly reported in methods because it is
easier to obtain, but interlaboratory precision
assessments may be more appropriate for
regulatory applications and should be included
in the methods.
3-2
-------
Table EQ-1 Examples of Detection Limit Definitions
Instrument Detection Limit
(IDL)
Method Detection Limit
(MDL)
Limit of Detection (LOD)
Limit of Quantitation (LOQ)
Practical Quantitation Limit
(PQL)
The smallest signal above
background noise that an
instrument can detect at a
99% confidence level.
The minimum concentration
of a substance that can be
identified, measured and
reported with 99%
confidence that the analyte
concentration is greater than
zero and is determined from
analysis of a sample in a
given matrix containing the
analyte.
The lowest concentration
level that can be determined
to be statistically different
from a blank, numerically '
defined as 3 times the
standard deviation of seven
replicate measurements.
The level' above which
quantitative results may be
obtained with a specified
degree of confidence,
numerically defined as 10
times the standard deviation
of seven replicate
measurements. It is specific
to an individual laboratory.
The PQL is analogous to the
LOQ It is an interlaboratory
concept and is numerically
estimated at 5 to 10 times
the MDL. PQLs are derived
from laboratory performance,
under ideal circumstances, of
the best laboratories and not
all laboratories. PQLs provide
routine performance goals
that many laboratories must
strive to achieve.
Precision estimates should ideally represent
the entire measurement process, including
sampling, preparation, analysis, calibration,
and any other components of the method. For
water programs however, precision estimates
contained in a method are usually used to
describe only the laboratory performance
component, rather than the entire measurement
process.
Accuracy
Accuracy is a measure of the closeness of an
individual measurement to the true
concentration. It includes both precision and
bias. It is determined by analyzing a sample
containing a known native or spiked
concentration of the target pollutant. Accuracy
is usually expressed either as a percent recovery
(R) or as a percent bias (R-100). As with
precision, the accuracy estimate in a method for
water-based matrices usually applies to the
laboratory performance portion of the
measurement system rather than to the entire
measurement process.
Interferences
Because of the complexity of environmental
samples, most analytical methods are subject to
interferences. Interferences that are not
accounted for can cause analytical results to be
biased. Interferences can be classified into three
categories: 1) interferences that can be
eliminated by exercising an qption within the
method; 2) interferences which are numerically
related to another analyte which can be
corrected for arithmetically; and 3) interferences
that cannot be eliminated. The best way to
eliminate an interference is to remove the
interfering substance. Techniques include: 1)
chemical techniques, such as the addition of
reagents that will precipitate, complex or
chemically alter the interfering substance; 2)
separation techniques such as liquid-liquid
partition or column partition to remove the
interfering substance; and 3) physical
techniques such as distillation, filtration, or
purging which can isolate either the analyte of
interest or the interfering substance.
However, despite these techniques, many
interferences cannot be eliminated. This
problem often limits the usefulness of methods
since the response from the interfering
substances may overwhelm any response due to
trace levels of the target analytes. For example,
large quantities of petroleum hydrocarbons may
prevent the determination of the trace
quantities of chlorinated volatile organic
chemicals in a sample analyzed by gas
chromatography/mass spectrometry. Alternate
methods may be used to minimize the effects of
the interference. In the example stated above,
the use of a chlorine specific gas chro-
3-3
-------
matography detector may resolve the
interference problem.
In any event, each method should contain a
discussion of known interferences and provide
procedures for handling each. Where
modifications beyond the scope of the method
have been required to address interferences, the
specific detection limits, accuracy and precision
data obtained using these modifications should
be reported with the sample results.
Applicability
A method developed for regulatory use
should represent state-of-the-art technology that
has been demonstrated to be practical for
routine use. Frequently, in the process of
developing technology to this level for a specific
need, (e.g., routine monitoring for benzene in
water at the ppb level) the major problems
associated with implementing the technology in
other areas (e.g., monitoring benzene in wastes)
have also been solved. Thus, small modifications
of a method can result in the application of a
method developed for a specific sample matrix to
an entirely different program and sample
matrix.
This aspect of analytical method
development presents two fundamental issues:
• The method development and performance
data collection process only defines the
quality of the data for the matrix and
analytes originally tested, and
• Changes in the method for a new matrix or
the inclusion of additional analytes will
require the performance testing of the
"new" method for the new analytes and
sample types.
Therefore, it is important that a method
contain information regarding its applicability.
If a method is stated to be applicable to a variety
of matrices (waters, soils, wastes, etc.) then the
method must provide the following:
• Operational details of how to modify
procedural steps to accommodate the
different matrices,
• Method performance data (detection limit,
precision and accuracy statements, holding
times, etc.) for each matrix for which the
method is stated to be applicable, and
• Performance criteria to meet if the method
is used for other applications.
Once the data quality objectives of a
particular need are defined, then it can be
determined if a method is adequate for its
intended use.
Dynamic Range
In general, methods can only be used to
measure analytes over a specified concentration
range, defined as the linear dynamic range. The
linear dynamic range is limited at the lower
level by the detection limit and above the
detection limit by the linearity of the
measurement process. This range is usually
defined by the performance characteristics of the
instrument detector, although other factors such
as integration software, mass loading on
column, etc., can sometimes limit this range.
In most cases, samples containing high
concentrations of the target analytes can be
diluted to extend the range. However, a broad
dynamic range is desirable to minimize
reanalyses of samples containing target
analytes in concentrations exceeding the linear
range. A method should provide information
pertaining to the linear dynamic range. This
information must be verified by each laboratory
using working calibration standards over the
range of interest. A method should also describe
what operational steps should be performed
when target analytes are present at
concentrations exceeding this range.
Analytes
Many methods, especially methods for
organic compounds and metals can be used to
simultaneously measure many analytes of
similar chemical properties. The increasing
emphasis on an ever expanding list of toxic
pollutants combined with the need for analytical
methods to meet program demands has resulted
in a tendency to add analytes to existing
methods. It is often technically feasible, and
3-4
-------
from a practical viewpoint desirable, to add
analytes to existing methods.
Even though the underlying principle of a
method may be appropriate for the inclusion of
additional analytes, the method must be tested
to demonstrate that the method reliably
measures the additional analytes. Test methods
should list all analytes for which the method can
be used. Performance data should be contained
in the method for each analyte listed.
Unfortunately, many analytes are listed in
proposed or final regulations without any
supporting performance data. In addition,
uniform criteria to define adequate performance
have not been defined by the Agency. If known,
the classes of chemicals for which each
multianalyte method is technically applicable
should be stated. This would aid in the selection
of test methodology for special applications.
Reporting
In order to ensure that all appropriate
quality control procedures were followed in the
analysis process, specific documentation of QC
results should be required to be provided with
the analytical results. Results should be
expressed so that their meaning is not distorted
by the reporting process. Therefore, uniform
units should be used throughout the report for
chemically related analytes. The reports should
also make clear which results, if any, have been
corrected for blank and recovery measurements.
Detection limits should carefully be adjusted if
necessary as a result of the need to dilute
samples.
Analysis Time/Capacity/Cost
The often overriding method characteristics
which constrain the final selection of a method
are the analysis time and cost. In addition,
factors such as the availability of laboratories
and/or instrumentation to perform the method
can constrain the selection process. Clearly,
these factors should not be used as a rationale
for the collection of data inappropriate for the
intended use.
However, the advantages of methods which
can be performed by more laboratories, in
shorter times at lower costs can outweigh the
need for more expensive techniques which
provided data of only slightly better quality. The
key factor in this decision is to recognize the
limitations of data acquired by alternate, less
expensive techniques and ensure that these
limitations do not conflict with the program
needs. There currently are many methods in 40
CFR 136 which have different cost/quality
tradeoffs. However, no criteria have been
established to allow a laboratory to make an
intelligent choice of the appropriate methods.
Method Validation and
Standardization
The previous section described how the
performance characteristics of a method were
important criteria for defining adequacy. This
section describes how the degree of validation
and standardization of a method is also an
important criteria. A fully validated and
standardized method is a method that has been
ruggedized by a systematic process and is
applicable for its intended use. Ideally, only
those methods that have been fully validated
and standardized should be used for Agency
needs. However, due to resource and time
constraints, it is not always possible to fully
validate and standardize every method for every
application required by the Agency. The degree
of validation and standardization required for a
given method depends to some extent on the
intended use of the data. For example, methods
which will be used extensively for regulatory
purposes or where significant decisions must be
based on the quality of the analytical data
normally require more extensive validation and
standardization than methods developed to
collect preliminary baseline data.
The validation process includes: 1) the
selection of a method that is capable of
producing measurements of the type and quality
needed for a particular application and is a cost-
effective approach to the analytical
requirement; and 2) the verification that the
method selected is based on sound technical
principals and that it has been reduced to
practice for practical purposes (3-13). This level
of validation ensures that the method has been
generally validated. General validation consists
of testing, evaluating and characterizing the
method to the extent necessary to demonstrate
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that the method achieves a specified
performance. This process establishes
quantitative measures of performance under
typical conditions of use. A method that is
generally validated cannot unequivocally be
assumed to be valid for every specific use (3-6).
As shown in Figure III-l, there are three levels
of validation and standardization. The first level
represents the initial documentation and
development of a method that must be
performed for any method that is to be used for
Agency purposes. A method validated to this
level can be considered to be minimally
validated.
Methods that have been minimally
validated may be adequate for some program
needs. For example, the extensive validation
process may not be justified for a method with
limited application, such as a method
appropriate only for a single discharger, (e.g., for
a specific pesticide produced by only one
manufacturer). The costs and time required to
fully validate and standardize a method beyond
this minimal level must therefore be balanced
against factors such as the degree of use of the
method and the importance of the data for
decision making. The use of a method that is
only minimally validated should be carefully
evaluated based on the circumstances. The user
of the method should understand the potential
limitations of the usefulness of the data. Where
possible, and in all cases for methods that will
have extensive regulatory use, a method should
be fully validated and standardized. This
increased level of validation verifies that the
method is suitable for its intended use.
A method that is fully developed and
standardized can be used as the basic framework
for specific needs. Depending on the program
needs, the method may require additional
validation specific for each intended use of the
data. For example, a procedure that has been
generally validated for water may require
additional validation to document its
performance at regulatory levels. A method that
has been generally validated can also be used as
the basis for expansion of the method into new
areas, such as additional matrices or analytes.
These three levels of validation and
standardization, and the components of each
level, are shown in Figure 3-1, and are discussed
in more detail in the subsequent sections.
Initial Demonstration of Method
Performance (Minimal Validation)
As described previously, a user's particular
need may sometimes outweigh the advantages of
using a fully validated and standardized
method. There is, however, a minimum level of
validation that should be expected of any
method used to generate environmental
measurement data. This level of validation is
associated with the initial testing of the method.
This initial phase is required to:
• Document the operational details of the
method,
• Provide single laboratory performance
data, and
• Ensure that the method can be used by at
least one other laboratory.
The process used to achieve this minimal
level of validation includes the following
activities:
• Definition of the requirements,
• Selection and basic method development,
• Collection of basic performance data,
• Confirmation testing, and
• Interim method description.
The initial method selection process should
be based on the measurement need. This process
should identify the analytes of interest, define
the matrices to be measured and specify the
required performance of the method. Existing
methods are then reviewed to identify candidate
methods which are potentially adequate to meet
the requirements. If no existing method can be
adapted, a new method must be developed.
The next step in this initial development
process is to test the method in the laboratory to
collect basic operational information. The
analysis of reference materials, blanks and
typical sample matrices are performed to
generate the appropriate data. These laboratory
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Validation for Specific Use
1. Specific Matrices
2. Specific Analytes
3. Innovation
-Reduce Cost
-Improve Performance
Generally Validated and Standardized
1.Formal Validation Study
2.Peer Review and Comment
3.Method Modifications
4.Acceptance Criteria
S.Promulgation/Standardization
Minimally Validated
1.Definition of the Requirements
2.Selection and Basic Development
S.Collection of Preliminary Performance Data
4.Confirmatory Testing
5.Interim Method Description
Figure III-l. Hierarchy of analytical methods.
tests should, at a minimum, provide other users
of the method information related to:
• Operative variables, (e.g., GC retention
times, key mass spectral ion fragment),
• Routinely achievable detection limits,
• Useful dynamic range, and
• Typical spike recoveries in sample types of
interest.
Although not required, it is prudent at this
point to disseminate information about the
method to the technical community, either by
presentations at scientific conferences or
through an informal distribution of the method.
By allowing the technical community the
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opportunity to experiment with the method,
improvements can be incorporated.
Once a method has been developed by the
researcher, limited confirmatory testing to
verify the previous work should be performed.
The primary purpose of confirmatory testing is
to provide independent confirmation of the
method performance, i.e., whether or not at least
one other competent laboratory can follow the
method and obtain similar detection limits,
precision and bias.
Following completion of the confirmatory
testing, an interim method description can be
written. The method should be sufficiently
characterized by this time that any changes to
the method resulting from further development
work would be minor in nature. A method that
has been developed to this level can be
considered to be adequate for at least some
needs. For example, a method at this level may
be adequate as an interim method for collecting
baseline data for a program with urgent needs.
The adequacy of methods which have not
been developed to this minimum level cannot be
defined. It is highly likely that methods used for
a specific program which do not have this level of
development and standardization will be
subjected to close scrutiny and challenge by the
regulated community. In addition, changes to
the method which will occur as a method
becomes better developed may later render the
initial data unusable.
General Validation and Standardization
A method which has been minimally
validated as described above is capable of
generating adequate data for many needs.
However, some program needs require methods
which have tighter controls and have been more
thoroughly tested and developed. Examples of
this type of need are methods which will be used
by thousands in response to National Pollutant
Discharge Elimination System (NPDES)
monitoring requirements.
Methods that have been minimally
validated have been used in discharge
regulations promulgated by EPA's Industrial
Technology Division (ITD). In order to fulfill its
mandate under the FWPCA and CWA to
regulate substances that may be a threat to
human health or the environment, ITD had
applied specialized methods to site and
industrial subcategory specific discharges. Some
examples are:
(1) A method for determination of diesel oil in
drilling muds and drill cuttings. This
method was initially validated in a single
commercial laboratory under contract to
EPA, then further validated and applied by
the Offshore Oil and Gas industry in a study
of the use of diesel oil to free stuck drill bits
in drilling operations.
(2) Methods determination of chlorinated
dioxins and furans for the National Dioxin
Study. These methods were developed by,
and validated in, EPA's individual research
laboratories. In order to meet Congressional
deadlines, time constraints precluded full
validation.
Fully validated and standardized methods
incorporate the following features which may
not be found in minimally developed methods:
• Formal performance testing
• Peer review and comment
• Method modifications
• Development of acceptance criteria
• QA/QC Requirements
• Promulgation
• Ongoing assessment
Formal Testing
' Formal testing is a process which uses
established well designed methods to collect
performance data. A formal well-designed
performance study generally results in a
substantially better characterization of method
performance as compared to the initial
development work described previously. This
testing can occur as a collaborative study or
alternatively as an ongoing process whereby
performance data are collected during routine
use of the method.
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Many of the 40 CFR 136 methods have
undergone formal collaborative interlaboratory
studies. (See Chapter 6). These studies involved
the testing of the method over a wide
concentration range and on a variety of sample
matrices using many laboratories. Where
monitoring activities have been initiated before
completion of a collaborative study, data to
support method performance have been obtained
by collecting ongoing quality control data from
laboratories using the method on a routine basis.
For example, information has been collected for
representative analytes from contract
laboratories using specified analytical protocols
under the Superfund Contract Laboratory
Program. In both cases, data collected from
formal testing programs are statistically
evaluated to establish acceptance criteria for
routine use. In addition, minor changes which
are deemed appropriate based on either the
results from the study or input from study
participants are incorporated.
Peer Review and Comment
As required in Section 101(e) of the FWPCA,
the EPA "is required to invite and consider
written comments on proposed and interim
regulations from any interested or affected
persons or organizations" (40 CFR 25.10). This
policy is based on a number of objectives
involving public participation. Nowhere is this
policy more important than in the development
of analytical methods. By presenting the
information at an early stage and encouraging
the involvement of the technical community,
many potential problems are resolved, thus
minimizing wasted analytical efforts.
It should be noted that once a validated
method has been proposed for use it gains a
much higher degree of acceptability. This factor
is due to the fact that the method is generally
available and many users confuse proposal by
the Agency with promulgation. For this reason,
it is important to only propose test methods
which have been minimally validated and
standardized. A proposed method should be
capable of being used routinely.
For example, the "600 Series" methods
proposed in 1979 were sound methods that had
not been fully validated at the time of proposal.
Before finalization, thousands of samples were
analyzed using these methods. The methods
gained wide acceptance and were generally
recognized to provide adequate data. The actual
performance data collected during this period as
well as the practical experience gained in the
use of the methods led to improvements in the
methods when they were finally promulgated.
Revisions were made in the methods to give
analysts more flexibility to practice professional
judgment as long as specified performance
criteria were achieved.
Promulgation/General Acceptance
The use of fully validated and standardized
methods offer advantages over methods which
are minimally validated. These advantages
include factors such as:
• Improved comparability of data,
• Increased availability of a standard
reference,
• Higher degree of legal acceptability, and
• Increased assurance of data quality.
Methods which have not been fully
developed and documented are subject to change
or interpretation by the analysts using the
methods. In addition, modifications to the
method may be operational changes. These
changes may result in data which are not
directly comparable either over a long period of
time or between different laboratories. A fully
developed validated and standardized method
helps to resolve these issues.
The wide distribution of a validated method
enables all users to ensure that the same method
was followed. Thus, to the extent defined by the
method, data generated by all laboratories using
the method can theoretically be comparable. A
method that has been fully validated contains
data pertaining to the critical method
performance characteristics. Thus, the user has
assurance that data generated by the method
will be of a known, defined quality.
As a method gains widespread use, it may
evolve to where the users may decide that it
should be formally standardized by consensus by
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a standards organization. A method used by the
Agency for regulatory purposes may require
formal promulgation. In both cases, methods
which are developed to this level generally gain
widespread acceptance. Guidelines for the
format of standardized methods have been
established by EPA, ASTM, AOAC, ACS, USGS
and other organizations.
The prototype format developed by EMSL-
Cincinnati is regarded as an acceptable model
for the format of a method. In this system, each
method should be referenced by a unique
number and should contain the following
elements:
• Title
Legal or regulatory criteria, if
appropriate
Originating organization
• Scope and Application
Matrices
Analytes
• Summary of Method
• Definitions
• Interferences
• Safety Precautions
• Apparatus and Equipment
• Sample Collection, Preservation and
Storage
• Reagents
• Calibration
• Method
• Quality Control
• Calculations
• Performance Data
Precision
Bias
Detection Limits
Dynamic Range
• Reporting Requirements
Ongoing Assessment
It is essential to continuously assess the
performance of the method on an ongoing basis.
For example, data collected over a long period of
time on performance evaluation samples has
been used to assess the relative detection limits,
precision and accuracy of methods. Such
information can be used to determine if a
method can provide adequate data for a specific
use and can also be used to assess whether the
method requires additional modification.
Validation for a Specific Use
In developing a method for a specific need,
the best starting point is a method that has been
generally validated. A generally validated
method will have the important operational
details documented. For example, the only
change required to make an instrumental
method developed for a water matrix applicable
to a solid matrix may be changing the sample
preparation step. Similarly, a method developed
to measure one compound can be demonstrated
to measure a related compound.
A generally validated method thus provides
a reference base for the development of new
methods. The performance characteristics
(detection limit, precision, etc.) of the developed
method can be used to assess the performance of
the new method.
A generally validated method has an
additional advantage. It serves as the yardstick
by which alternative methods can be measured.
As technology improves, modifications to the
existing method may be warranted. The impact
of these modifications can be evaluated with
respect to the performance of the existing
method to determine if the modifications are
really an improvement. For example, the
methods in 40 CFR 136 have formed the basis of
methods developed for other needs.
Criteria for Determination of
Adequacy of Biological Methods
The generation of scientifically accurate and
valid biological measurements for
environmental pollutants requires
approximately the same criteria for assessing
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the adequacy of a method as previously
described for chemical analyses. The same
performance characteristics and development
states of the method must be known in order to
make an assessment of adequacy, and those
sections will not be repeated.
However, there are several differences
which are important. Instrument specific
characteristics such as detection limits and
dynamic range are good examples. These
characteristics, which measure the capacity,
ability, or efficiency of the analytical instrument
being used to make the chemical measurement,
are not usually appropriate concepts for all
biological measurements unless instrument-
ation is required. Biological methods may or
may not be dependent on instrumental efficiency
depending on the amount of instrumentation
required to perform the test method. For
instance, a field survey of the number and types
of aquatic weeds along a stream bank can be
accomplished without any instrumentation. In
this case, the detection limit of the method is
based on the visual acuity and knowledge of the
observer, not a limit imposed by instrument-
ation. In the case of chlorophyll measurements,
involving the use of an ultraviolet/visible
spectrophotometer or flowmeter, instrument
characteristics would be important.
Biological Detection Limits
The "health" of the test organism or
biological system being monitored is a unique
attribute without a complimentary attribute for
analytical methods. The health of a toxicity test
organism has a profound effect on the quality of
the data, and must therefore be considered a key
criterion for assessing adequacy. Biological
system health is primarily relevant to biological
field assessments.
The health of test organisms and biological
systems cannot be "calibrated" before the
experiment in the same way as analytical
instrumentation. A single living organism is far
more complex than the most sophisticated
analytical instrumentation ever conceived.
Organisms can adapt to their environment,
hybridize, mutate, or go dormant during the
measurement time period. There are no knobs to
turn to adjust for these factors to achieve
consistent performance during a test method.
For these reasons, the biological procedure must
include biological standards (e.g., standard
reference toxicants) in order to ensure data
integrity.
Precision
The precision of toxicity measurements is
similar to that of finely tuned instruments
operating at detection limits. The users of
biological methods must account for the
inherent variability in response. Typically for
toxicity test methods, this means using replicate
exposures at each concentration and running
parallel tests with each sample or batch of test
organisms using a standardized toxicant so that
the "health" or sensitivity of the test organisms
can be independently measured. It also means
that the natural variability in sensitivity will
have to be accounted for. More importantly, this
variability must also be accounted for when
permit limits, criteria, or standards are set.
In aquatic toxicity tests, most EPA methods
require that a control or series of controls be run
concurrently with the test series and that the
survivorship in the controls must be 80-90% or
greater in order for the test results to be
acceptable. Chronic tests have minimal
performance requirements also. As an
additional check, the results from the standard
toxicant test with the same batch of test
organisms should be similar to previously
generated data (cusum graph). In a sense, using
requirements such as these two examples are
means of calibrating the method. As with
chemical methods, variability is an essential
criterion for assessing the adequacy of a test
method. The mechanism within each method for
making this assessment is the quality
assurance/quality control (QA/QC) section.
Precision statements, detection limits,
dynamic range, and the inherent biological
variability are intricately related. For instance,
single laboratory precision for an acute toxicity
test can be determined by performing multiple
standard toxicant tests with the same batch of
test organisms. Precision can be described by a
mean, standard deviation, and relative standard
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deviation (percent coefficient of variation, or
C V) of the point estimates from replicated tests.
However, with chronic tests, the results are
reported in terms of the No-Observed-Effect-
Concentration (NOEC) or the Lowest-Observed-
Effect-Concentration (LOEC). These concen-
tration levels, essentially the detection limits of
the test organisms or population, would clearly
be a function of the concentration series and the
health of the test organism or test population
including such factors as age, physiological
condition, and quality of diet. For these
situations, precision can only be described by
listing the NOEC-LOEC interval for each test
rather than calculating a statistic. When all
tests of the toxicant yield the same NOEC-LOEC
intervals, maximum precision has been
attained, yet the "true" NOEC could fall
anywhere within the interval, NOEC± (NOEC-
LOEC). This means that the dynamic range
could be changing both within and between
replicate runs with the test method.
Applicability
As with the chemical method
characteristics, applicability of the biological
method is a key criterion for assessing the
method's adequacy. For biological methods, a
key component of applicability is whether
special conditions in the lab or a unique lab
location (e.g., coastal area) are required to
perform the test. For instance, those organisms
that require large amounts of high quality,
flowing natural seawater, natural freshwater, or
tidal fluctuations obviously cannot be used
because they would require a highly specialized
lab or location that may be difficult or
impossible to recreate at all labs across the
country. For the test method to be applicable,
particularly for widespread NPDES
biomonitoring, biological test methods must be
adaptable to a wide variety of labs. The
availability of labs that can realistically perform
the test methods with reproducible results
should be a key criterion in determining
applicability of a method. Similarly, the choice
of a test species must also be based on available
culturing techniques or widespread, constant
sources of test organisms to ensure timely
testing. The test organism should not be overly
susceptible to disease or stress, require unique
water quality requirements, or exhibit
unpredictable population characteristics (e.g.,
sudden mortalities). The key criterion for
determining applicability is the ease with which
the test can be performed on a routine basis.
For field assessment methods, the necessary
element for determining applicability is the
degree of flexibility allowed in the method for
each unique field assessment. Field assessment
methods must be specific enough to ensure
consistency between replicate measurements of
the same ecosystem, but flexible enough to allow
for tailoring of the method to each unique
ecosystem.
Chapter Three References
1. Riggin, R.M., 1983. Technical Assistance
Document for Sampling and Analysis of
Toxic Organic Compounds in Ambient Air.
Battelle-Columbus Laboratories, Columbus,
OH. EPA-600/4-83-027.
2. EPA, 1986. Interim Report on
Institutionalizing the Data Quality
Objective Process in Integrated
Federal/Region/State Surface Water
Monitoring Programs. November, 1986.
3. EPA, 1984. Calculation of Precision, Bias,
and Method Detection Limit for Chemical
and Physical Measurements. Quality
Assurance Management and Special Studies
Staff, Office of Monitoring Systems and
Quality Assurance, Washington, DC. March,
1984.
4. Kopp, J.F. Guidelines and Format
forEMSL-Cincinnati Methods. Physical and
Chemical Methods Branch, Environmental
Monitoring and Support Laboratory,
Cincinnati, OH 45268. EPA-600/8-83-020.
August, 1983.
5. Taylor, J.K. Principles of Quality Assurance
of Chemical Measurements. U.S.
Department of Commerce, National Bureau
of Standards, Gaithersburg, MD. February,
1985.
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6. Taylor, J.K. Validation of Analytical
Methods. Analytical Chemistry, Vol. 55, No.
6, May 1983.
7. Improving analytical chemical data used for
public purposes. C & EN, June 7,1982.
8. Hertz, H.S., W.E. May, S.A. Wise, and S.N.
Chesler. Trace Organics Analysis.
Analytical Chemistry, Vol. 50, No. 4, April,
1978.
9. Principles of Environmental Analysis. The
American Chemical Society. Revision to the
"Guidelines for Data Acquisition and Data
Quality Evaluation in Environmental
Chemistry:, which appeared in Anal. Chem.
1980, 52,2242-2249.
10. Glaser, J.A., D.L. Foerst, G.D. McKee, S.A.
Quave, W.L. Budde. Trace analyses for
wastewaters. Environmental Science &
Technology, Vol. 15, No. 12, December,
1981.
11. Quality Assurance for Environmental
Measurements. ASTM Special Technical
Publication - J.K. Taylor and T.W. Stanley,
Editors. American Society for Testing and
Materials, 1985.
12. Kateman, G. and F.W. Pijpers. Quality
Control in Analytical Chemistry. John
Wiley & Sons, Inc., 1981.
13. EPA, 1987. Guidelines for Selection and
Validation of USEPA's Measurement
Methods. Office of Acid Deposition. April,
1987.
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CHAPTER FOUR
AVAILABILITY AND ADEQUACY OF METHODS TO
SUPPORT TESTING REQUIRED UNDER THE FEDERAL
WATER POLLUTION CONTROL ACT (FWPCA)
While methods are promulgated in 40 CFR
136 under the authority of §304(h) to support the
National Pollution Discharge Elimination
System (NPDES) and industrial pretreatment
programs, the broader potential applicability of
these methods to all FWPCA programs is
addressed in this chapter. First, the history and
status of the §304(h) and method equivalency
programs are reviewed. Subsequently, the
availability and adequacy of methodology to
support all FWPCA programs are reviewed.
Test methods for FWPCA monitoring needs
are promulgated in 40 CFR 136. Over 500
specific test methods have been approved for the
determination of 252 biological, inorganic
chemical, non-pesticide organic chemical,
pesticide organic chemical and radiological
analytes. For most analytes, an array of methods
are available to meet the specific capability and
needs of the user. Some methods require
extensive and/or expensive instrumentation
(e.g., GC/MS) and can only be performed by well-
equipped laboratories. Other methods are within
the capability of smaller laboratories and may
be appropriate for a specific monitoring need.
The philosophy behind the promulgation of
the §304(h) methods is to provide standardized
methods that are as near to state-of-the-art as
possible that are also practical for routine use.
Overview of §304(h) Program
Authority
Standardized analytical test methods are
promulgated under the authority of §§301,
304(h), 307 and 501(a) of the FWPCA
Amendments of 1972 as amended by the Clean
Water Act (CWA) of 1977. Section 304(h)
requires the Administrator to promulgate
"guidelines establishing test methods for the
analysis of pollutants that shall include the
factors which must be provided in any
certification pursuant to §401 of the FWPCA or
permit application pursuant to §402 of the
FWPCA." Section 501(a) authorizes the
Administrator "to prescribe such regulations as
are necessary to carry out his function under the
Act."
The Administrator has also made these test
methods applicable to monitoring and reporting
of NPDES permits (40 CFR 122, 122.21, 122.41,
122.44 and 123.25), and implementation of the
pretreatment standards issued pursuant to 307
of the FWPCA (40 CFR 403,403.10 and 403.12).
History and Background
On October 16,1973, the Agency established
test methods for 71 analytes in 40 CFR 136 (38
FR 28758). The analytes were grouped as
follows:
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• General analytical methods, 15 analytes
• Metals, 28 analytes
• Nutrients, anions and organics, 17
analytes
• Physical and biological analytes, 6
analytes
• Radiological analytes, 5 analytes
The methods which were approved were for the
most part cited in three compilations of methods.
• Annual Book of Standards, Part 23, Water,
1972, American Society for Testing and
Materials (ASTM),
• Methods for Chemical Analysis of Water
and Wastes, 1971, EPA, and
• Standard Methods for the Examination of
Water and Wastewater, American Public
Health Association, 13th Edition.
Since 1973, 40 CFR 136 has been amended 13
times. Most of these amendments have
pertained to approval of equivalent alternate
test methods. Two significant amendments, one
in 1976 and one in 1984, that greatly expanded
the scope of 40 CFR 136 are discussed below.
On December 1, 1976, forty-four additional
analytes were added (40 FR 52780). The
analytes were still listed in one table, grouped
into categories which were little changed from
the 1973 rule. However, this amendment
increased significantly the number of approved
methods and added, among other things,
methods developed by the U.S. Geological
Survey. In addition, criteria for sample
preservation and sample holding times were
established.
Probably the most significant amendment was
finalized on October 26, 1984. This amendment
established:
• New test methods (including quality
control requirements) for the analysis of
toxic organic pollutants;
• A new test based upon inductively coupled
plasma optical emission spectroscopy for
the analysis of metals;
• Mandatory container materials,
preservatives, and holding times; and
• Definition of the method performance
characteristic "method detection limit".
The list of analytes and approved methods
(Table I of 40 CFR 136) was restructured into
five tables and additional analytes were added
as summarized below:
• Table 1A - Biological Test Methods, 5
analytes
• Table IB - Inorganic Test Methods, 75
analytes
• Table 1C - Non-Pesticide Organic
Compound Methods, 97 analytes
• Table ID - Pesticide Methods, 70 analytes
• Table IE - Radiological Analytes, 5
analytes
The mandatory container-s, preservation
techniques and holding times were summarized
in a separate table.
This amendment resulted in the addition of 12
GC or HPLC methods and five GC/MS methods.
The full texts of these methods were printed as
Appendix A to Part 136. The full text of the ICP
method was printed in Appendix C. The
definition of and procedure for the
determination of the method detection limit
(MDL) was set forth in Appendix B.
As a result of a settlement agreement between
EPA and Virginia Electric Power Company,
EPA proposed on September 3, 1987, to
incorporate results of method standardization
studies for the inductively coupled plasma and
flame and furnace atomic absorption test
methods into 40 CFR 136. Among other things,
the Agency also proposed that the public be
given the opportunity to comment on nationwide
approval of alternate test methods.
Future Actions
Below are brief descriptions of activities
currently being addressed by the §304(h)
workgroup. On October 26, 1984, the Agency
proposed to add 32 additional organic analytes to
4-2
-------
Table 1C. A draft Federal Register notice is in
review to finalize this proposed amendment.
A Federal Register notice has been drafted to
amend Table 1A, "List of Approved Biological
Test Methods," to propose methods for
measuring the toxicity of pollutants in effluents,
drilling muds, and receiving waters, including
short-term methods for estimating the acute and
chronic toxicity to freshwater and marine
organisms. Methods will also be proposed for
measuring mutagenicity, and monitoring for
viruses in wastewaters and sludges. Citations to
microbiological methods are also scheduled to be
updated.
A Federal Register notice has been prepared to
conclude the rulemaking published October 26,
1984. This final rule under the FWPCA will
promulgate control limits for analytical
methods, delete several outmoded analytical
methods, approve the use of certain analytical
methods, e.g., 1624 and 1625 for 32 pollutants,
and update references.
The 304(h) EPA workgroup also intends to
propose an array of pesticide methods, as well as
update method citations for current pesticide
analytes in 40 CFR 136 to withdraw out-dated
methods (e.g. thin layer chromatography) as
proposed in October, and to add approximately
61 more pesticide analytes to Table ID of Part
136.
The Process of Incorporating Standard
Analytical Test Procedures into 40 CFR
136
Briefly presented are the various steps that a
new test procedure goes through prior to
promulgation in 40 CFR 136 under the authority
of 304(h) of the FWPCA.
A standing group of the Agency, called the
Steering Committee, has been established with
representation from each EPA Assistant
Administrator and the General Counsel. This
committee is the primary mechanism for
coordinating and integrating the Agency's
regulatory development activities. Its key
functions are to approve Start Action Requests
(SAR) (A SAR initiates work on a rule or related
action) and charter workgroups, .monitor the
progress of staff-level workgroups, especially
regarding cross-media or inter-office problem-
solving, and ensure, when appropriate, that
significant issues are resolved or elevated to top
management.
The primary purpose of a workgroup is to
develop regulatory actions and supporting
materials. The workgroup's first task is to
prepare a SAR. For major and significant rules,
the workgroup takes the responsibility of
preparing a Development Plan (DP) to present to
the Steering Committee for review. The DP sets
forth the framework for developing proposed
major or significant Agency rules. Its purpose is
to explain the need for the action, identify
regulatory goals and objectives; present the
major regulatory issues and alternatives; and
identify any policies, decision criteria or other
factors that will influence regulatory choices;
and present the work plan for developing the
regulation. The workgroup's chairperson also
prepares periodic workgroup reports for the
Steering Committee.
Prior to presenting a FR notice to the
Administrator or other approving official for
sign-off, the notice undergoes a formal review by
senior management (usually Assistant and
Regional Administrators and the General
Counsel). This is called Red Border Review.
Concurrent with the Red Border Review process,
since information requirements are generally
included in a §304(h) rule, e.g., reporting,
monitoring or record-keeping, an Information
Collection Request (ICR) must be prepared and
submitted to the Office of Management and
Budget (OMB) for their clearance. This is
required under the Paperwork Reduction Act.
Information requirements in final rules are not
valid and enforceable until OMB clears the
corresponding ICR.
Upon final sign-off by the Administrator or
other approving official, the proposed notice is
published in the Federal Register.
Methods Equivalency Program
Once test methods are promulgated, a flexible
control system in §304(h) allows improved
methods to be adopted by the laboratory
community. As part of this program, data
4-3
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comparability must be assured. Section 136.4 of
the amended regulations published December 1,
1976, established the Methods Equivalency
Program (4-1). The regulations allow for two
levels of approval of alternate test methods.
Limited use may be granted to an individual
National Pollution Discharge Elimination
System (NPDES) permit holder, or commercial,
state or U. S. Environmental Protection Agency
(USEPA) Regional Laboratory. Nationwide
approvals may be initiated by any person or
organization, but are primarily intended for
instrument or analytical system manufacturers.
On September 3, 1987, EPA proposed that the
public be given the opportunity to comment on
test methods before they are given nationwide
approval.
The Environmental Monitoring and Support
Laboratory - Cincinnati (EMSL-Cincinnati) has
the responsibility for nationwide coordination of
a methods equivalency program to determine
the technical acceptability of proposed alternate
test methods under the provisions of the
FWPCA, and to make recommendations to the
appropriate regional director for final approval
or denial of the proposed method.
Objectives
The provision for approval of alternate
analytical techniques is based on two principles.
First, it was realized that for some dischargers,
effluent characteristics or other circumstances
would preclude the use of approved test methods.
For these dischargers, it was the Agency's dual
objective to allow some flexibility for analytical
methods while maintaining control over method
modifications. These goals are realized through
the mechanism of the limited-use approval of
alternate test methods. Secondly, the Agency
recognized that it must be continuously
informed of advances in analytical technology as
they relate to present and future compliance
monitoring requirements. Toward that end, a
mechanism was established by which
manufacturers of innovative analytical
equipment or instrumentation would gain
nationwide approval that would enable any
entity regulated by the FWPCA to routinely use
the method for reportable measurements.
Description of Program
Applications for limited-use approval of
alternate test methods are evaluated on a case-
by-case basis for methods which, in the opinion
of the applicant are required because of unique
waste characteristics which would preclude the
use of approved test methods. Many requests for
limited-use approval are initiated because the
proposed is more accurate or precise than
approved methods. In states which have been
approved by EPA to administer the NPDES
program, such applications are submitted to the
state permitting authority. Each application
includes a detailed method description,
appropriate literature, performance
comparability data, quality control data, and
precision and accuracy data. Minimum
comparability data requirements for limited
approvals includes data from analyses of three
grab samples from each permitted discharge.
Each sample must be analyzed eight times; four
each by the approved and proposed methods.
This results in 24 data points for each
contaminant for which approval is sought. All
requirements for sampling, preservation and
storage must be carefully followed.
In non-primacy states, the applications are
directed to the EPA Regional Administrator or
designee, usually the Regional Quality
Assurance Officer (QAO). The QAO provides a
copy of the application to the Director, EMSL-
Cincinnati, who, through the Equivalency
Program coordinates internal and external
technical reviews of the application. For these
reviews, technical experts at EMSL-Cincinnati
or, in the case of methods for radioactivity, the
Environmental Monitoring Systems Laboratory
- Las Vegas provide supporting technical
expertise. Statistical support is obtained
through the Computer Services and Systems
Division at the Andrew W. Breidenbach
Environmental Research Center, Cincinnati.
One intent of the nationwide approval process is
to provide a mechanism for instrument
manufacturers to seek approval of their
instruments. However, any applicant may
request nationwide approval of an alternate test
method. Requests are submitted to the Director,
EMSL-Cincinnati, and must contain the same
4-4
-------
type of information required for limited-use
approvals, except that more data is collected to
establish comparability. Nationwide NPDES
approval of alternate test methods is based on
comparability data from analyses of five
representative wastewater types. For each
industry or discharge type specified by EMSL-
Cincinnati, the applicant must collect six
samples and analyze each eight times; four each
by the approved and proposed methods.
Completed applications including comparability
data are subjected to rigorous internal and
external review by the same staff as used for
limited NPDES approvals described above.
Statistical evaluation is performed by contractor
personnel using a package of proven statistical
tests known as the Equivalency Data Analysis
and Storage System (EDASS). Based on review
comments and the results of statistical testing of
the data, the Director, EMSL- Cincinnati
recommends approval or denial of the request. If
approval is indicated, the entire application
package, including supporting information, and
technical and statistical reviews are submitted
to the Chairman of the §304(h) workgroup with
a request that the proposed method be
considered for incorporation into 40 CFR 136 as
an approved test method.
Summary of Equivalency Applications
Since its beginning in 1977, the Methods
Equivalency Program has been highly visible
and widely utilized. To date, over 600 requests
for approval of alternate test methods have been
processed for the NPDES compliance monitoring
program. Approximately 500 of those
applications were requests for limited-use
approval; the remaining were for nationwide
approval. Method variances have been requested
for all of the approved methods, both biological
and chemical (organic and inorganic). For
inorganic analytes, the most common inquiries
have been for approval of rapid methods such as
test kits and automated techniques and for
elimination of labor-intensive steps such as
digestions or distillations when, in the opinion of
the applicant, those steps are not necessary to
achieve acceptable analytical results.
Applications for approval to modify methods for
organic analytes, the 600-series methods,
comprise approximately 10% of the total number
of applications. Variances most often sought for
the organic methods involve substitution of
capillary chromatographic columns for the
prescribed packed columns and for modifications
in extraction and concentration methods. These
variances are frequently justified on the basis of
decreased sample processing time and the
resultant savings in resources.
The desire by the regulated community and the
Agency for sensitive, rapid, reliable, and
inexpensive test methods is evident when
examining the types of analytical techniques for
which EMSL-Cincinnati has recommended
nationwide approval. Most recent among them
are the inductively-coupled argon plasma (ICP)
and direct current plasma (DCP) optical
emission spectrometric methods. ICP is widely
used and represents state-of-the-art analysis for
up to 30 metals simultaneously. The DCP
method has similar capabilities and is also
expected to be well accepted and result in
considerable savings, especially for larger
laboratories. Electrode methods for chloride and
fluoride and test kit methods for numerous
inorganics are now approved for general use, as
are flow injection versions of the currently
approved continuous flow (Technicon and
others) methods. Other refinements of
previously approved methods have also been
approved. Examples of these include automatic
hydride generation accessories to replace the
manual method for selenium and arsenic and a
scaled-down test procedure for chemical oxygen
demand, the micro-COD.
Innovative methodology that shows great
potential for compliance monitoring programs is
currently being studied and is expected to be
submitted for nationwide approval. One
technique involves digestion of effluent samples
using closed vessel microwave heating. This
method would decrease digestion time by up to
80% of that currently required by hotplate
digestion methods. Applications are also
expected from manufacturers of ion
chromatographic instruments capable of
simplified analyses of multiple inorganic ariions
in the same sample. When these new principles
4-5
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can be used with the Agency's compliance
programs, they can result in improved data
quality and impressive savings of resources and
time. Thus it is to the advantage of the entire
regulated community to expeditiously approve
methods based on these concepts. These new
techniques are discussed in more detail in
Chapter Seven.
Availability and Adequacy of §304(h)
Methods for Measuring Chemical
Analytes
Over 500 test methods covering 247 chemical
analytes have been promulgated in 40 CFR 136.
Approximately one third of these methods have
been developed or standardized by EMSL-
Cincinnati. The remaining methods, developed
by other organizations, are primarily cited for
inorganic analytes. In fact, only three non-EPA
methods, ASTM D3086 and "Standard Methods"
methods 509A and 509B have been promulgated
for the determination of specific organic
chemicals.
In addition to the methods promulgated under
§304(h), EMSL-Cincinnati has developed and
standardized many other methods to support
water program needs. Examples of these
methods include:
• the extended 600 series methods for
pesticides, some of which were
promulgated in 40 CFR 455 before this
part was remanded
• the 500 series methods, for measuring
organics under SDWA
Many of these methods are used routinely by the
regulated community. For example, method 614,
developed for the measurement of
organophosphorus pesticides is frequently used
in studies associated with determining these
analytes, although it has not been promulgated
in 40 CFR 136. This test procedure formed the
basis for method 8140, contained in the methods
manual of the Office of Solid Waste, SW-846.
Thus, some methods which are commonly used
for environmental measurements have not been
promulgated in 40 CFR 136, due to the
boundaries currently imposed on the §304(h)
process, i.e., if a method is not required for the
NPDES or industrial pretreatment programs,
the method has not been promulgated under
§304(h).
This section assesses the availability and
adequacy of the §304(h) methods to meet
FWPCA monitoring requirements. This
assessment has grouped the §304(h) methods
into four major groups.
• EPA methods promulgated in 40 CFR 136
• Other methods promulgated in 40 CFR 136
• EMSL-Cincinnati methods that have been
developed and standardized, but not
promulgated in 40 CFR 136
• EMSL-Cincinnati methods that are under
development
Methods for the Measurement of
Analytes Listed in Table II-l
Table II-l listed 323 chemical analytes that
must be mentioned under various Agency
programs. Of these, 91 are contained in
monitoring requirements and analytical
methods associated only with the Resource
Conservation and Recovery Act (RCRA),
Comprehensive Environmental Response
Compensation and Liability Act (CERCLA) of
1980 or Safe Drinking Water Act regulations.
These analytes are listed in Table IV-1. Due to
consolidation in the Agency programs, these
analytes may be required to be measured to
support some FWPCA programs in the future.
No 40 CFR 136 methods specifically address
these analytes. However, many of these analytes
could be measured in water samples using
approved §304(h) methods, if the need
developed. For example, many volatile organic
chemicals contained in Appendix IX to 40 CFR
264 can be measured using the technology
promulgated in 40 CFR 136 for volatile organics..
Of the 91 analytes listed in Table IV-1, 32 are
clearly measurable using either the EPA 500
series methods or the methods in the Superfund
Contract Laboratory Program. With the
exception of oxirane (ethylene oxide), the
remaining analytes are all contained in the
RCRA Appendix IX list. Ongoing efforts within
the Agency are directed towards generating
method performance data for these compounds
4-6
-------
in water samples. Based on the preliminary
results from these evaluations, it is reasonable
to expect that existing 304(h) methods could be
extended to the measurement of these analytes.
Furthermore, standardized methods are
available for the measurement of SDWA and
CERCLA analytes in water samples. For
example, standardized methods have been
established for all of the SDWA volatile organic
contaminants shown in Table IV-1. These
methods (502.1, 502.2, 503.1, 504, 524.1 and
524.2) have been standardized to the degree that
they could be promulgated in 40 CFR 136 if
required.
Of the remaining 232 analytes which are
directly associated with the FWPCA needs
stated in Chapter 2, 173 have test methods
promulgated in 40 CFR 136 and 59 do not.
However, as shown in Table IV-2, of these 59
analytes, 32 have methods that have been
proposed for promulgation in 40 CFR 136 and
methods have been validated by EMSL-
Cincinnati for another 7 analytes. In addition to
the analytes in Table IV-2, Table II-5 listed 30
analytes that were shown as examples of the
analytes contained in NPDES permits with no
methods available in 40 CFR 136. Methods for
some of these analytes have been developed by
EMSL- Cincinnati. Finally, Table II-12 listed 61
pesticides that were remanded in 40 CFR 455.
As shown in the table, methods are available for
these analytes although these methods
currently are not promulgated in 40 CFR 136.
In summary, methods are available in some
degree of standardization and validation for the
232 analytes identified in Chapter 2. Methods
for many of these compounds have been
promulgated in 40 CFR 136 or proposed for
promulgation. Methods for the remaining
analytes need to be proposed by USEPA.
In order to assess the adequacy of the §304(h)
methods, three aspects were reviewed:
• The development status of both §304(h)
methods and non-304(h) methods
developed by EMSL-Cincinnati;
• Method performance characteristics
contained in each method, as defined in
Chapter Three;
• Actual method performance data.
These three aspects of the methods are
summarized below.
Development Status and Performance
Characteristics
Over the past 10 years, the definition of an
adequate method has changed. Methods
promulgated in the 1970's were adequate for the
needs at that time, and in many cases are still
suitable for specific needs. However, the
increased concern over toxics and the increased
scrutiny that analytical data routinely undergo
has required a reexamination of the adequacy of
some methods.
For example, methods that were developed in
the 1970's for pesticides reflected the state-of-
the-art at that time. Furthermore, these
methods did not contain all of the elements (e.g.,
quality control requirements) that are now
recognized as essential elements for any method.
Since then, technology has improved and the
Agency has recognized the need to incorporate
additional requirements into methods. One
result of this ongoing and evolving process is
that those methods that have not been
incorporated into 40 CFR 136 (e.g., method
524.2) contain method elements (e.g., capillary
column technology and demonstration of method
detection limits) that would be desirable to
incorporate into the existing promulgated
methods.
A second result of this process is that some
promulgated methods are probably now
obsolete. For example, in October, 1984, the
Agency proposed (49 FR 43437) to withdraw
approval for "Standard Methods" 509A and
ASTM D-3086 promulgated for the
measurement of pesticides. Compared to the
EPA method, Method 608, these methods do not
contain adequate QC requirements and do not
stipulate control limits for analytical
performance. A review of the development
status of the §304(h) methods developed by EPA
indicates that with the exception of certain older
4-7
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Table IV-1. Chemical Parameters Listed in Table H-l with no CWA Monitoring
Requirements
PARAMETER
SDWA LISTS
RCRA LISTS
CERCLA
LISTS
ACETOPHENONE APPENDIX IX
ACETONITRILE APPENDIX IX
2-ACETYLAMINO- APPENDIX IX
FLUORENE
ALLYL CHLORIDE APPENDIX IX
4-AMINOBIPHENYL APPENDIX IX
ARAMITE APPENDIX IX
BENZYL ALCOHOL APPENDIX IX CLP
BROMOBENZENE ALL
BROMOCHLORO- ALL
METHANE
n-BUTYLBENZENE DISC
sec-BUTYLBENZENE DISC
tert-BUTYLBENZENE DISC
p-CHLOROANILINE APPENDIX IX CLP
CHLOROBENZILATE APPENDIX IX
CHLOROPRENE APPENDIX IX
o-CHLOROTOLUENE ALL
p-CHLOROTOLUENE ALL
m-CRESOL* APPENDIX IX CLP
o-CRESOL* APPENDIX IX CLP/HSL
p-CRESOL* APPENDIX IX CLP
DIALLATE APPENDIX IX
1.2-DIBROMO-3- VUL APPENDIX IX
CHLOROPROPANE
trans-l,4-DICHLORO-2- APPENDIX IX
BUTENE
1,3-DICHLOROPROPANE ALL
2,2-DICHLOROPROPANE ALL
1,1-DICHLOROPROPENE ALL
p-(DIMETHYLAMINO)
AZOBENZENE
7,12-DIMETHYLBENZ(A)
ANTHRACENE
3,3'-DIMETHYL-
BENZIDINE
alpha,alpha-DIMETHYL-
PHENETHYLAMINE
m-DINITROBENZENE
DINOSEB
DISULFOTON
ETHYL METHACRYLATE
ETHYL METHANE-
SULFONATE
FAMPHUR
HEXACHLORODIBENZO-
P-DIOXINS
HEXACHLORODIBENZO-
FURANS
HEXACHLOROPHENE
HEXACHLOROPROPENE
IODOMETHANE
ISOBUTYL ALCOHOL
ISODRIN
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
(Continued)
4-8
-------
TableIV-1. (Continued)
PARAMETER SDWA LISTS
ISOPROPYLBENZENE DISC
p-ISOPROPYLTOLUENE DISC
ISOSAFROLE
KEPONE
METHACRYLONITRILE
METHAPYRILENE
3-METHYL-
CHOLANTHRENE
METHYLENE BROMIDE
METHYL
METHACRYLATE
METHYL
METHANESULFONATE
2-METHYL-
NAPHTHALENE
METHYL PARATHION
METHYL ISOBUTYL
KETONE*
1 ,4-NAPHTHOQUINONE
1-NAPHTHYLAMINE
o-NITROANILINE
m-NITROANILINE
p-NITROANILINE
4-NITROQUINOLINE 1-
OXIDE
N-NITROSOMETHYL-
ETHYLAMINE
N-NITROSO-
MORPHOLINE
N-NITROSOPIPERIDINE
5-NIITRO-O-TOLUIDINE
OXIRANE
PENTACHLORO-
DIBENZO-P-DIOXINS
PENTACHLORO-
DIBENZOFURANS
PHENACETIN
p-PHENYLENEDIAMINE
PHORATE
PRONAMIDE
PROPIONITRILE
RCRA LISTS
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
CERCLA
LISTS
CLP
CLP
CLP/HSL
CLP
CLP
CLP
CLP/HSL
HSL
(Continued)
4-9
-------
Table IV-1. (Continued)
PARAMETER
n-PROPYLBENZENE
SAFROLE
SULFOTEPP
TETRACHLORO-
DIBENZO-P-DIOXINS
TETRACHLORODI-
BENZOFURANS
1,1,1,2-TETRACHLORO-
ETHANE
THIONAZIN
o-TOLUIDINE
1,2,3-TRICHLORO-
PROPANE
0,0,0-TRIETHYL PHOS-
PHOROTHIOATE
1,2,4-TRIMETHYL-
BENZENE
1,3,5-TRIMETHYL-
BENZENE
sym-TRINITROBENZENE
p-XYLENE
o-XYLENE
m-XYLENE
SDWA LISTS
DISC
ALL
ALL
DISC
DISC
ALL
ALL
ALL
RCRA LISTS
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
APPENDIX IX
CERCLA
LISTS
GLP/HSL
CLP/HSL
CLP/HSL
methods, the methods are highly developed and
standardized. The methods typically contain the
method performance data discussed in Chapter
Three and have been thoroughly tested. The two
exceptions to this general assessment are 1)
many of the methods for inorganic analytes
published in "Methods for Chemical Analysis of
Water and Wastes (MCAWW), 1983"; and 2)
methods for organic analytes published in
"Methods for Benzidine, Chlorinated Organic
Compounds, Pentachlorophenol and Pesticides
in Water and Wastewater, 1978."
Most of the inorganics methods in MCAWW are
consensus methods. The methods have been
subjected to extensive use over several decades
and as shown later in this chapter, their method
performance is known and adequate. By
comparison, the methods provided in the 1978
manual for organics have for the most part been
superseded by the 600 Series methods.
The Agency has proposed to withdraw the
obsolete methods for the pesticides listed in
Table ID of 40 CFR 136, that have a
corresponding 600 series method. The Agency
has not proposed to delete the obsolete pesticides
methods in Table ID for the analytes that do not
have a 600 series counterpart. These obsolete
methods, for the remaining 49 pesticides, do not
meet the minimum requirements specified in
Chapter Three and should also be withdrawn. It
will be necessary to replace these methods in 40
CFR 136.
As stated previously, with the exception of
obsolete organic methods that have been
proposed for withdrawal, non-EPA methods are
approved only for biological, inorganic and
radiological analytes. Three hundred thirty-five
non-EPA methods for inorganic analytes are
approved in 40 CFR 136,Table IB. As described
in more detail in Chapter Five, these methods
are not as fully developed and standardized as
the EPA methods. Essential method elements
such as detection limits, performance criteria
and QC requirements are typically not included
4-10
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TableIV-2 Chemical Parameters Required for CWA Monitoring
with No 304(h) Methods
OTHER PROCEDURES
PARAMETER
CLP
EMSL
ACETONE*
ANILINE
ASBESTOS
BENZOIC ACID*
BIPHENYL*
BIS(2-CHLOROMETHYL)ETHER
CARBAZOLE*
CARBON DISULFIDE
CHLORPYRIFOS
p-CYMENE*
DACONIL
DACTHAL
n-DECANE*
DEMETON
DIBENZOFURAN*
DIBENZOTHIOPHENE*
1,2-DIBROMOETHANE
cis-l,2-DICHLOROETHYLENE
2,6-DICHLOROPHENOL
DIETHYL ETHER*
DIMETHOATE
1,4-DIOXANE*
DIPHENYLAMINE*
DIPHENYL ETHER*
1,2-DIPHENYLH YDRAZINE*
n-DOCOSANE*
n-DODECANE*
n-EICOSANE*
GUTHION
GLYPHOSATE
n-HEXACOSANE*
n-HEXADECANE*
HEXANOIC ACID*
2-HEXANONE
INDIUM
METHYL ETHYL KETONE*
MIREX
2-NAPTHYLAMINE*
N-NITROSODIETHYLAMINE
N-NITROSODIBUTYLAMINE
N-NITROSOPYROLIDINE
n-OCTACOSANE*
n-OCTADECANE*
PARAQUAT
PENTACHLOROBENZENE
2-PICOLINE*
PYRIDINE
STYRENE*
TANTALUM
X
X
X
1624
1625
1625
1625
622
1624
1625
614
1625
1625
504
1624
1624
1624
1625
1625
1625
1625
1625
140 A
1625
1625
1625
1624
617
1625
1625
1625
1625
1624
4-11
-------
TableIV-2: (Continued)
PARAMETER
OTHER PROCEDURES
CLP
EMSL
alpha-TERPINEOL*
1,2,4,5-TETRACHLOROBENZENE
2,3,4,6-TETRACHLOROPHENOL
n-TETRACOSANE*
n-TETRADECANE*
n-TRIACONTANE*
1,2,3-TRICHLOROBENZENE*
2,3,6-TRICHLOROPHENOL*
2,4,5-TRICHLOROPHENOL*
TUNGSTEN
1624
1625
1625
1625
1625
1625
1625
in these methods. EPA methods have been
approved for all analytes in 40 CFR136.
Based on results of the Water Supply (WS),
Water Pollution (WP) and Discharge Monitoring
Report-Quality Assurance (DMR-QA) perform-
ance evaluation studies, many of the inorganic
methods are used by less than one percent of the
participating laboratories and should be
proposed for deletion from 40 CFR 136. For
example, over 4500 results for cadmium are
contained in the SDWA Performance Evaluation
Study for Water Supplies (WS) data base. Over
90% of these results are from laboratories using
EPA methods 213.1 and 213.2. Most of the
remaining results are from laboratories using
"Standard Methods" AA methods. Four results
are from laboratories using ASTM methods. No
results are contained in the data base from the
"Standard Methods" colorimetric method, or
from any United States Geological Survey
(USGS), American National Standards Institute
(ANSI) or Association of Official Analytical
Chemists (AOAC) method. The cost of
maintaining these methods may not be justified
as long as there are other acceptable methods
available.
Many other EMSL-Cincinnati methods have
been standardized to the extent that they can be
considered to be appropriate for various FWPCA
needs. These methods have been through the
steps defined as the initial demonstration of
method performance in Figure 3-1, but have not
been promulgated in 40 CFR 136. These
methods are listed in Table IV-3.
Table IV-3 Test Procedures Developed by EMSL-
Cincinnati not Promulgated in 40 CFR 136
A. INORGANIC PROCEDURES
Method 200.1 Determination of Acid Soluble Metals
Method200.11 Determination of Metals in Fish
Tissue by Inductively Coupled Plasma
- Atomic Emission Spectrometry
Method300.0* The Determination of Inorganic
Anions in Water by Ion
Chromatography
B. NON-PESTICIDE ORGANIC PROCEDURES
Method502.1* Volatile Halogenated Organic
Compounds in Water by Purge and
Trap Gas Chromatography
Method502.2* Volatile Organic Compounds In
Water By Purge and Trap Capillary
Column Gas Chromatography With
Photo-ionization and Electrolytic
Conductivity Detectors in Series
Method 503.1* Volatile Aromatic and Unsaturated
Organic Compounds in Water by
Purge and Trap Gas Chromatography
Method504* 1,2-Dibromoethane (EDB) and 1,2-
Dibromo-3-chloropropane (DBGP) in
Water by Microextraction and Gas
Chromatography
Method524.1* Volatile Organic Compounds in
Water by Purge and Trap Gas
Chromatography/Mass Spectrometry
Method524.2* Volatile Organic Compounds in
Water by Purge and Trap Capillary
4-12
-------
Column Gas Chromatography/Mass
Spectrometry
C. PESTICIDE PROCEDURES
Method 505 Analysis of Organohalide Pesticides
and Aroclors in Drinking Water by
Microextraction and Gas
Chromatography
Method515 Determination of Chlorinated
Herbicides in Drinking Water
Method 608.1 The Determination of Organochlorine
Pesticides in Industrial and
Municipal Wastewater
Method 608.2 Analysis of Certain Organochlorine
Pesticides in Wastewater by Gas
Chromatography
Method614 The Determination of
Organophosphorous Pesticides in
Industrial and Municipal Wastewater
Method614.1 Analysis of Organo-phosphorous
Pesticides in Wastewater by Gas
Chromatography
Method 615 Determination of Phenoxy Acid
Herbicides in Industrial & Municipal
Wastewater
Method 617 The Determination of Organohalide
Pesticides and PCBs in Industrial and
Municipal Wastewater
Method 618 Determination of Volatile Pesticides
in Municipal and Industrial
Wastewaters by Gas Chromatography
Method 619 The Determination of Triazine
Pesticides in Industrial and
Municipal Wastewater
Method 622 The Determination of
Organophosphorus Pesticides in
Industrial and Municipal Wastewater
Method 622.1 Thiophosphate Pesticides
Method 627 The Determination of Dinitroaniline
Pesticides in Industrial and
Municipal Wastewater
Method 630 The Determination of
Dithiocarbamate Pesticides in
Industrial and Municipal Wastewater
Method 630.1 The Determination of
Dithiocarbamates Pesticides in
Wastewater as Carbon bisulfide by
Gas Chromatography
Method 632 The Determination of Carbamate and
Urea Pesticides in Industrial and
Municipal Wastewater
Method 632.1
Method 633
Method 633.1
Method 634
Method 645
Method 646
Method 680
Method 1**
Method 2**
Methods**
Method 4**
Methods**
Method 6*
Analysis of Carbamate and Amide
Pesticides in Wastewater by Liquid
Chromatography
The Determination of Organonitro
Pesticides in Industrial and
Municipal Wastewater
Neutral Nitrogen-Containing
Pesticides
Determination of Thiocarbamate
Pesticides in Industrial and
Municipal Wastewaters by Gas
Chromatography
Analysis of Certain Amine Pesticides
and Lethane in Wastewater by Gas
Chromatography
Analysis of Dinitro Aromatic
Pesticides in Wastewater by Gas
Chromatography
Determination of Pesticides and PCBs
in Water and Soil/Sediment by Gas
Chromatography/Mass Spectrometry
Determination of Nitrogen- and
Phosphorus- Containing Pesticides in
Groundwater by Gas
Chromatography with a Nitrogen-
Phosphorus Detector
Determination of Chlorinated
Pesticides in Ground water by Gas
Chromatography with an Electron
Capture Detector
Determination of Chlorinated Acids
in Groundwater by Gas
Chromatography with an Electron
Capture Detector
Determination of Pesticides in
Ground Water by High Performance
Liquid Chromatography with an
Ultraviolet Detector
Measurement of N-
Methylcarbamoyloximes and N-
Methylcarbamates in Ground water
by Direct Aqueous Injection High
Performance Liquid Chromatograph
(HPLC) with Post Column Derivation
Determination of Ethylene Thiourea
(ETU) in Ground water by Gas
Chromatography with a Nitrogen-
Phosphorus Detector
* Procedure has been approved for SDWA use
** National Pesticide Survey Methods
4-13
-------
Method Performance Data
The data obtained through EMSL-Cincinnati's
WS, WP and DMR-QA performance evaluation
sample studies, although limited to a purge
water matrix, can be used to establish certain
performance characteristics of methods used by
environmental monitoring laboratories. In
addition, the performance of alternate methods
for a specific analyte can be compared with one
another, and can be used to compare method
performance for a specific pollutant with the
regulatory levels which have been established
for that pollutant. Since the ultimate objective of
the Agency's analytical methods review is to
support the Agency's regulatory or enforcement
activities, the precision, mean recovery, and
detection limits of the methods for each
regulated pollutant should be sufficient to
ensure that the resulting data will be of
adequate, known quality and legally defensible.
The PWPCA WP performance evaluation
studies and SDWA WS performance evaluation
studies are described in Chapter Six. The two
programs consist of sending prepared sample
concentrates with specified analytes at unknown
concentrations, to governmental, industrial and
commercial laboratories. These laboratories
analyze the samples and report the results back
to EMSL- Cincinnati. The data from the WP and
WS studies have been used by EPA to establish
the precision, mean recovery, and to a limited
degree practical quantitation limits for a
number of the 40 CFR 136 methods and SDWA
methods, by typical users.
Precision and mean recovery are expressed in
the form of linear regression equations which
represent overall, interlaboratory values for
standard deviation of a single measurement of
each analyte (precision) and the expected
recovery of that analyte using a specified
analytical method. This is the same form of
regression analysis used to construct the control
limits promulgated in the methods for organic
chemicals in Appendix A of 40 CFR 136. Since
participants can select any methods approved for
an analyte when multiple methods are available
for the analyte, analysis of the WS and WP data
bases result in regression equations which in
some instances can be used to compare the
performance of two analytical methods.
The total number of analytes and corresponding
methods found in the WS and WP data bases are
shown in Tables IV-4 through IV-6, grouped
following 40 CFR 136 as inorganics, non-
pesticide organics, and pesticides. These lists
exclude any analyte or method that had
insufficient data (statistical elements for at least
two true values and seven or more reported
values for at least one of those true values) to
develop regression equations for mean recovery
and precision.
In this report, the regression equations for
precision and mean recovery of specific methods
developed from the WS and WP studies are
compared with the equations used to specify the
QA/QC control limits for the promulgated
methods, where such equations are available.
This comparison of the control limits equations
to the actual performance gives a good
indication of how closely the QA/QC methods are
being followed and how realistically achievable
they are. Where the WS and WP studies had
data for the same analyte and the same
analytical method, the regression equations
used in this and subsequent comparisons were
based on the combined WS and WP data.
The regression equations for precision and mean
recovery can be used effectively to evaluate how
well the analytical methods support regulatory
goals. This is done by using the equations for a
specific method and constituent to calculate the
expected precision and mean recovery of
measurements at the applicable regulatory
limit. This has been done in tabular form as
shown by the examples in Table IV-7 through
IV-10. These four tables present method
performance data for arsenic (Table IV-7),
barium (Table IV-8), 1,1,1-trichloroethane
(Table IV-9), and aldrin (Table IV-10). The
tables for all chemicals and analytical methods
which were compared in this way are included in
the Appendix to this report. Only those methods
for which there were sufficient performance
evaluation data in the WS and WP data bases to
develop precision and mean recovery regression
equations were compared. For some methods
4-14
-------
and chemicals, there are insufficient data to
develop reliable regression equations.
In Tables IV-7 through IV-10, method
performance is shown for each analytical
method which is applicable. The range of
analyte concentrations under the term
"database range" shown in the table represents
the extremes of the true values for the test
solutions sent to the participating laboratories.
Extrapolation of the regression equations for
precision and mean recovery outside these
ranges results in precision and mean recovery
estimates which are inherently more uncertain
than estimates within the range. In this
evaluation, however, extrapolation was done if
the concentration of interest was within one
order of magnitude of the low or high ends of this
concentration range.
Three regression equations derived from the WS
and WP data are shown: mean recovery in units
of mass per unit of sample volume (for example,
micrograms per liter, milligrams per liter);
mean recovery expressed as a percentage of the
true concentration in the check sample; and
precision, expressed as mass per unit of sample
volume. The precision equation calculates the
standard deviation of the analytical
measurements about the true value of the
sample concentration. It can be used directly to
calculate the range of expected measurements at
any desired concentration level by simply
multiplying by the number of standard
deviations from the true concentration for a
desired probability level. For example, the 95
percent probability level is 1.96 standard
deviations from the mean recovery. Thus, the
range of measurements which could be expected
to occur 95 percent of the time for a specified
true concentration (or regulatory limit) may be
estimated by multiplying the precision
estimated from the applicable regression
equation by 1.96 and adding or subtracting the
resulting value from the mean recovery of the
true concentration.
For evaluation of the performance of the
analytical methods in relation to regulatory
requirements, four water-based regulatory
levels are used as shown in the example in Table
IV-7 through IV-10. These regulatory levels are
as follows:
• SDWA maximum contaminant levels
(MCLs)
• FWPCA industrial effluent limitations
guidelines (ELG)
• FWPCA industrial categorical
pretreatment standards (PS)
• FWPCA 303 water quality criteria (Gold
Book).
The SDWA MCLs as used in these comparisons
are promulgated or proposed primary and
secondary MCLs wherever possible. For some
water quality constituents, there are no current
promulgated drinking water standards, so
criteria which were previously developed by
EPA (Quality Criteria for Water, July 1976,
EPA) were used for drinking water. For certain
organic chemicals, EPA has proposed
recommended maximum contaminant levels
(RMCLs, now called maximum contaminant
level goals-MCLG) and these have been used as
the basis of comparison with the analytical
methods performance. If the RMCLs or MCLGs
are zero, which is the case for chemicals
suspected or known to be carcinogenic, and there
is no proposed MCL, then adjusted acceptable
daily intakes (AADI) were used if available. The
categorical industrial effluent limitations
guidelines (ELG) and pretreatment standards
(PS) establish maximum allowable discharges of
conventional, nonconventional, and toxic
pollutants to receiving waters and publicly
owned treatment works (POTWs), respectively.
These ELG and PS serve as the basis for permit
limits for specific plants unless water quality-
based standards, which are more stringent, are
used to derive the permit limits. The permittee
must self-monitor its discharge, using approved
analytical methods, to document to the
regulatory agencies that the permit limits are
being achieved. The regulatory agencies may
also collect samples of a discharger's effluent
and analyze them to determine compliance with
the permit.
Most of these guidelines and standards are
promulgated as mass discharges of a pollutant
per unit of manufacturing production or raw
4-15
-------
Table IV-4 List of Analytes and Methods with Regression Equations in Combined WS and WP Studies
5-DAY BOD
METHOD 11 R24 - 405.1
METHOD 22 R53 - 507.1
METHOD 52 R34 - 33.019
INORGANICS
WINKLER (AZIDE MODIFICATION)
WINKLER (AZIDE MODIFICATION)
ELECTRODE
ALUMINUM
METHOD 13 R19 - 200.7
METHOD 14
METHOD 15
METHOD 23
METHOD 24
R24 -
R24 -
R53 -
R53 -
202.1
202.2
303C
304
AMMONIA-NITROGEN
METHOD 14
METHOD 15
METHOD 16
METHOD 17
METHOD 24
METHOD 25
METHOD 26
METHOD 27
ANTIMONY
METHOD 13
METHOD 14
METHOD 15
METHOD 21
METHOD 22
ARSENIC
METHOD 14
METHOD 15
METHOD 16
METHOD 17
METHOD 24
METHOD 25
METHOD 26
METHOD 27
METHOD 32
BARIUM
METHOD 14
METHOD 15
METHOD 22
BERYLLIUM
METHOD 13
METHOD 14
METHOD 15
METHOD 23
R24 -
R24 -
R24 -
R24 -
R53 -
R53 -
R53 -
R53 -
R24 -
R24 -
R19 -
R53 -
R53 -
R19 -
R24 -
R24 -
R24 -
R3 -
R3 -
R53 -
R53 -
R25 -
R24 -
R24 -
R3 -
R19 -
R24 -
R24 -
R53 -
350.2
350.3
350.1
350.2
417B
417D
417G
417E
204.1
204.2
200.7
303A
304
200.7
206.2
206.3
206.4
404A AFTER B(4)
301A-VII
303E
304
D2 972-7 8B
208.1
208.2
301A-IV
200.7
210.1
210.2
303C
INDUCTIVELY COUPLED PLASMA (ICP>
ATOMIC ABSORPTION(AA)
AA; FURNACE
AA
AA; FURNACE
TITRATION
ELECTRODE
AUTOMATED PHENATE
NESSLERIZATION
NESSLERIZATION
TITRATION
AUTOMATED PHENATE
ELECTRODE
AA
AA; FURNACE
ICP
AA
AA; FURNACE
ICP
AA; FURNACE
AA; GASEOUS HYDRIDE
SILVER DIETHYLDITHIOCARBAMATE
SILVER DIETHYLDITHIOCARBAMATE
AA; GASEOUS HYDRIDE
AA; GASEOUS HYDRIDE
AA; FURNACE
AA; GASEOUS HYDRIDE
AA
AA; FURNACE
AA
ICP
AA
AA; FURNACE
AA
4-16
-------
Table IV-4 (Continued)
INORGANICS
CADMIUM
METHOD 13 R19 - 200.7
METHOD 14 R24 - 213.1
METHOD 15 R24 - 213.2
METHOD 23 R3 - 301A-II
METHOD 25 R3 - 301A-III
METHOD 26 R53 - 303A
METHOD 28 R53 - 304
ICP
AA
AA; FURNACE
AA
AA
AA
AA; FURNACE
CALCIUM
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
12
13
14
21
22
23
24
R19
R24
R24
R3
R3
R53
R53
- 200.7
- 215.1
- 215.2
- 301A
- 306C
- 303A
- 311C
CHLORIDE
METHOD
METHOD
METHOD
METHOD
METHOD
13
14
15
24
25
R24
R24
R24
R53
R53
- 325.3
- 325.1
- 325.2
- 407A
- 407B
CHROMIUM
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
COBALT
METHOD
METHOD
METHOD
METHOD
METHOD
COD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
13
14
15
24
26
27
29
13
14
15
22
24
12
13
14
15
22
54
55
R19
R24
R24
R3
R3
R53
R53
R19
R24
R24
R53
R53
R24
R24
R24
R24
R53
R41
R42
- 200.7
- 218.1
- 218.2
- 301A-II
- 301A-III
- 303A
- 304
- 200.7
- 219.1
- 219.2
- 303A
- 304
- 410.1
- 410.2
- 410.3
- 410.4
- 508A
- 8000
- P. 1
ICP
AA
EDTA
AA
EDTA
AA
EDTA
MERCURIC NITRATE
AUTOMATED FERRICYANIDE
AUTOMATED FERRICYANIDE
SILVER NITRATE
MERCURIC NITRATE
ICP
AA
AA; FURNACE
AA
AA
AA
AA; FURNACE
ICP
AA
AA; FURNACE
AA
AA; FURNACE
DICHROMATE REFLUX
DICHROMATE REFLUX
DICHROMATE REFLUX
SPECTROPHOTOMETRIC
DICHROMATE REFLUX
SPECTROPHOTOMETRIC
SPECTROPHOTOMETRIC
4-17
-------
Table IV-4 (Continued)
COPPER
METHOD 13 R19 - 200.7
METHOD 14 R24 - 220.1
METHOD 15 R24 - 220.2
METHOD 23 R53 - 303A
METHOD 25 R53 - 304
METHOD 54 R41 - 8506
INORGANICS
ICP
AA
AA; FURNACE
AA
AA; FURNACE
BICINCHONINATE
CORROSIVITY
METHOD 21 R3 - 203
LANGELIER INDEX
FLUORIDE
METHOD 14 R24 - 340.1
METHOD 15 R24 - 340.2
METHOD 16 R24 - 340.3
METHOD 24 R3 - 414B
METHOD 25 R3 - 414A AND C
METHOD 27 R53 - 413B
METHOD 28 R53 - 413C
METHOD 44 R52 - 1-4327-84
METHOD 52 R28 - 380-75WE
SPADNS
MANUAL ELECTRODE
AUTOMATED COMPLEXONE
ELECTRODE
SPADNS
MANUAL ELECTRODE
SPANDS
AUTOMATED ELECTRODE
ELECTRODE
IRON
METHOD 13 R19 - 200.7
METHOD 14 R24 - 236.1
METHOD 15 R24 - 236.2
METHOD 23 R53 - 303A
METHOD 26 R53 - 315B
METHOD 53 R44 - 8008
ICP
AA
AA; FURNACE
AA
PHENANTHROLINE
PHENANTHROLINE
KJELDAHL-NITROGEN
METHOD 14 R24 -
METHOD 15 R24 -
METHOD 16 R24 -
METHOD 17 R24 -
METHOD 18 R24 -
METHOD 19 R24 -
METHOD 23 R53 -
METHOD 24 R53 -
METHOD 25 R53 -
METHOD 27 R53 -
351.3
351.4
351.2
351.3
351.3
351.1
420A +
420A +
420A +
420B +
417D
417E
417E
417B
NESSLERIZATION
POTENTIOMETRIC
SEMI-AUTOMATED BLOCK DIGESTION
TITRATION
ELECTRODE
AUTOMATED PHENATE
TITRATION
NESSLERIZATION
ELECTRODE
NESSLERIZATION
LEAD
METHOD 13 R19 - 200.7
METHOD 14 R24 - 239.1
METHOD 15 R24 - 239.2
METHOD 23 R3 - 301A-II
METHOD 25 R3 - 301A-III
METHOD 26 R53 - 303A
METHOD 28 R53 - 304
ICP
AA
AA; FURNACE
AA
AA
AA
AA; FURNACE
4-18
-------
Table IV-4 (Continued)
MAGNESIUM
METHOD 12 R19 - 200.7
METHOD 13 R24 - 242.1
METHOD 23 R53 - 303A
METHOD 24 R53 - 318B
INORGANICS
ICP
AA
AA
GRAVIMETRIC
MANGANESE
METHOD 13 R19 - 200.7
METHOD 14 R24 - 243.1
METHOD 15 R24 - 243.2
METHOD 24 R53 - 303A
METHOD 27 R53 - 319B
METHOD 54 R41 - 8034
MERCURY
METHOD 13 R24 - 245.1
METHOD 14 R24 - 245.2
METHOD 21 R3 - 3Q1A-VI
METHOD 22 R53 - 303F
ICP
AA
AA; FURNACE
AA
PERSULFATE
PERIODATA (PP. 2-113 AND 2-117)
MANUAL COLD VAPOR
AUTOMATED COLD VAPOR
MANUAL COLD VAPOR
MANUAL COLD VAPOR
MOLYBDENUM
METHOD 13 R19 - 200.7
METHOD 14 R24 - 246.1
METHOD 15 R24 - 246.2
METHOD 21 R53 - 303C
ICP
AA
AA; FURNACE
AA
NICKEL
METHOD 13 R19 - 200.7
METHOD 14 R24 - 249.1
METHOD 15 R53 - 249.2
METHOD 23 R53 - 303A
METHOD 25 R53 - 304
ICP
AA
AA; FURNACE
AA
AA; FURNACE
NITRATE-NITROGEN
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
METHOD
15
16
17
18
19
26
27
27
28
29
54
70
R24 -
R24 -
R24 -
R24 -
R24 -
R3 -
R3 -
R3 -
R3 -
R53 -
R37 -
R53 -
352.1
353.1 '
353.2
353.3
300.0
419C
419D
419D
605
418C
93MM-79
418F
BRUCINE SULFATE
AUTOMATED HYDRAZINE REDUCTION
AUTOMATED CADMIUM REDUCTION
CADMIUM REDUCTION
ION CHROMATOGRAPHIC (SUPPRESSED)
CADMIUM REDUCTION
BRUCINE SULFATE
BRUCINE SULFATE
AUTOMATED CADMIUM REDUCTION
CADMIUM REDUCTION
ELECTRODE
AUTOMATED CADMIUM REDUCTION
NON-FILTERABLE RESIDUE
METHOD 12 R24 - 160.2
METHOD 23 R53 - 209C
4-19
GLASS FIBER 103 TO 105 C
GALSS FIBER 103 TO 105 C
-------
TabIeIV-4 (Continued)
INORGANICS
OIL AND GREASE
METHOD 12 R24 - 413.1
METHOD 22 R53 - 503A
ORTHOPHOSPHATE
METHOD 13 R24 - 365.1
METHOD 14 R24 - 365.2
METHOD 15 R24 - 365.3
METHOD 24 R53 - 424F
PH-UNITS
METHOD 12 R24 - 150.1
METHOD 21 R3 - 424
METHOD 22 R53 - 423
TRICLOOROTRIFLUOROETHANE GRIMTRC
TRICLOOROTRIFLUOROETHANE GRIMTRC
AUTOMATED ASCORBIC ACID REDUCTION
MANUAL ASCORBIC ACID REDUCTION
MANUAL TWO REAGENT
MANUAL ASCORBIC ACID REDUCTION
ELECTRODE
ELECTRODE
ELECTRODE
POTASSIUM
METHOD 12 R19 - 200.7
METHOD 13 R24 - 258.1
METHOD 23 R53 - 303A
METHOD 24 R53 - 322B
ICP
AA
AA
FLAME PHOTOMETRIC
RESIDUAL FREE CHLORINE
METHOD 24 R3 - 409F
METHOD 25 R3 - 409E
SELENIUM
METHOD 12 R19
METHOD 13 R24
METHOD 14 R24
METHOD 22 R3
METHOD 23 R53
METHOD 24 R53
METHOD 31 R25
SILVER
METHOD 13 R19
METHOD 14 R24
METHOD 15 R24
METHOD 24 R3
METHOD 26 R53
METHOD 28 R53
200.7
270.2
270.3
301A-VII
304
303E
D3859-79
200.7
272.1
272.2
301A-II
303A
304
SODIUM
METHOD 12 R19 - 200.7
METHOD 13 R24 - 273.1
METHOD 21 R3 - 320A
METHOD 22 R53 - 303A
METHOD 23 R53 - 325B
DPD COLORIMETRIC
DPD TITRAMETRIC
ICP
AA; FURNACE
AA; GASEOUS HYDRIDE
AA
AA; FURNACE
AA; GASEOUS HYDRIDE
AA; GASEOUS HYDRIDE
ICP
AA
AA; FURNACE
AA
AA
AA; FURNACE
ICP ,
AA
FLAME PHOTOMETRIC
AA
FLAME PHOTOMETRIC
4-20
-------
Table IV-4 (Continued)
INORGANICS
SPECIFIC CONDUCTIVITY
METHOD 12 R24 - 120.1
METHOD 22 R53 - 205
SULFATE
METHOD 14 R24 - 375.3
METHOD 15 R24 - 375.4
METHOD 16 R24 - 375.1
METHOD 23 R53 - 426A
METHOD 24 R53 - 426B
METHOD 25 R33 - 246C
THALLIUM
METHOD 13 R19 - 200.7
METHOD 14 R24 - 279.1
METHOD 15 R24 - 279.2
METHOD 21 R53 - 303A
TITANIUM
METHOD 13 R24 - 283,1
METHOD 14 R24 - 283.2
METHOD 21 R53 - 303C
TOC
METHOD 12 R24 - 415.1
METHOD 22 R53 - 505
METHOD 41 R9 - P. 41
TOTAL ALKALINITY
METHOD 13 R24 - 310.1
METHOD 14 R24 - 310.2
METHOD 21 R3 - 403
METHOD 22 R53 - 403
TOTAL CYANIDE
METHOD 13 R24 - 335.2
METHOD 14 R24 - 335.3
METHOD 23 R53 - 412C
METHOD 24 R53 - 412D
TOTAL FILTERABLE RESIDUE
METHOD 12 R24 - 160.1
METHOD 21 R3 - 208B
METHOD 22 R53 - 209B
WHEATSTONE BRIDGE
WHEATSTONE BRIDGE
GRAVIMETRIC
TURBIDIMETRIC
AUTOMATED COLORIMETER (BAR. CHLORANILATE)
GRAVIMETRIC
GRAVIMETRIC
TURBIDIMETRIC
ICP
AA
AA; FURNACE
AA
AA
AA; FURNACE
AA
COMBUSTION OR OXIDATION
COMBUSTION OR OXIDATION
COMBUSTION/INFRARED
MANUAL TITRATION
AUTOMATED TITRATION
MANUAL TITRATION
MANUAL TITRATION
MANUAL SPECTROPHOTOMETRIC
AUTOMATED SPECTROPHOTOMETRIC
TITRIMETRIC
MANUAL SPECTROPHOTOMETRIC
GLASS FIBER FILTRATION, 180 C
GLASS FIBER FILTRATION, 180 C
GLASS FIBER FILTRATION, 180 C
4-21
-------
Table IV-4 (Continued)
INORGANICS
TOTAL HARDNESS
METHOD 14 R24 - 130.1
METHOD 15 R24 - 130.2
METHOD 16 R24 - 215.1 + 242.1
METHOD 22 R53 - 314B
METHOD 23 R53 - 303A
AUTOMATED COLORIMETRIC
EDTA
AA (SUM OF CA AND MG AS GORBONATE)
EDTA
AA. (SUM OF CA AMD MG AS CARBONATE)
TOTAL PHENOLICS
METHOD 11
METHOD 12
METHOD 21
METHOD 22
METHOD 31
R24 - 420.1
R24 - 420.2
R3 - 510A + 510B
R3 - 510A + 510C
R25 - D1783-80A
MANUAL 4-AAP WITH DISTILLATION
AUTOMATED 4-AAP WITH DISTILLATION
MANUAL 4-AAP WITH DIST.+CHLOROFORM EXTR.
MANUAL 4-AAP WITH DISTILLATION
MANUAL 4-AAP WITH DIST.+CHLOROFORM EXTR
TOTAL PHOSPHORUS
METHOD 13 R24 - 365.2
METHOD 14 R24 - 365.3
METHOD 15 R24 - 365.1
METHOD 16 R24 - 365.4
METHOD 24 R53 - 424F
MANUAL ASCORBIC ACID REDUCTION
MAN. ASC. ACID RED. (2 REAGENTS)
AUTOMATED ASCORBIC ACID RED.
SEMI-AUTO. BLOCK DIGESTION
MANUAL ASCORBIC ACID REDUCTION
TOTAL RESIDUAL
METHOD 11 R24
METHOD 12 R24
METHOD 13 R24
METHOD 14 R24
METHOD 15 R24
METHOD 21 R53
METHOD 22 R53
METHOD 23 R53
METHOD 24 R53
METHOD 25 R53
CHLORINE
- 330.1
- 330.2
- 330.3
- 330.4
- 330.5
- 40 8A
- 408B
- 408C
- 408D
- 408E
TITRIMETRIC - AMPEROMETRIC
STARCH AND PRINT
IODOMETRIC
DPD-FAS
SPECTROPHOTOMETRIC, DPD
IODOMETRIC '.
STARCH AND POINT
TITRIMETRIC - AMPEROMETRIC
DPD - FAS
SPECTROPHOTOMETRIC, DPD
TURBIDITY
METHOD 12 R24 - 180.1
METHOD 22 R3 - 214A
NEPHELOMETRIC
NEPHELOMETRIC
VANADIUM
METHOD 13 R19 - 200.7
METHOD 14 R24 - 286.1
METHOD 15 R24 - 286.2
METHOD 23 R53 - 303C
METHOD 24 R53 - 304
ICP
AA
AA; FURNACE
AA
AA; FURNACE
ZINC
METHOD 13 R19 - 200.7
METHOD 14 R24 - 289.1
METHOD 15 R24 - 289.2
METHOD 23 R53 - 303A
ICP
AA
AA; FURNACE
AA
4-22
-------
Table IV-5 List of Analytes and Methods with Regression Equations in Combined WS and WP Studies
ORGANICS
1,1,1-TRICHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 15 R55 - 524.1
METHOD 16 R55 - 524.2
METHOD 17 R56- 502.2
1,1,1,2-TETRACHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
1,1,2,2-TETRACHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524ll
1,1,2-TRICHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
1,1-DICHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
1,1-DICHLOROETHENE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
METHOD 16 R55 - 524.2
METHOD 17 R56 - 502.2
I,1-DICHLOROPROPANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
1,2-DICHLOROETHANE
METHOD 11 R55 - 502.1
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 15 R55 - 524.1
METHOD 16 R55 - 524.2
METHOD 17 R56 - 502.2
1,2,3-TRICHLOROPROPANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
PURGE AND TRAP, HALIDE GC
GC/MS
GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, CAP. COLUMN GC/MS
PURGE AND TRAP, CAP. COLUMN GC
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, CAP. COLUMN GC/MS
PURGE AND TRAP, CAP. COLUMN GC
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
GC/MS
GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, CAP. COLUMN GC/MS
PURGE AND TRAP, CAP. COLUMN GC
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
4-23
-------
Table IV-5 (Continued)
ORGANICS
1,2-DICHLOROBENZENE
METHOD 11 R54 - 601
METHOD 12 R54 - 602
METHOD 14 R54 - 624
METHOD 15 R54 - 625
1,3-DICHLOROBENZENE
METHOD 11 R54 - 601
METHOD 12 R54 - 602
METHOD 14 R54 - 624
METHOD 15 R54 - 625
1,3-DICHLOROPROPANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
1,4-DICHLOROBENZENE
METHOD 11 R54 - 601
METHOD 12 R54 - 602
METHOD 15 R54 - 625
GC
GC
GC/MS
GC/MS
GC
GC
GC/MS
GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
GC
GC
GC/MS
2,2-DICHLOROPROPANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
BENZENE
METHOD 11 R54 - 602
METHOD 12 R54 - 624
GC
GC/MS
BROMODICHLOROMETHANE
METHOD 11 R30 - 501.1
METHOD 12 R31 - 501.2
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 18 R39 - 501.3
METHOD 19 R48 - 524
PURGE AND TRAP, HALIDE GC
LIQUID/LIQUID, ECGC
GC/MS
GC
PURGE AND TRAP, SELECTED ION GC/MS
PURGE AND TRAP, GC/MS
BROMOFORM
METHOD 11
METHOD 11
METHOD 12
METHOD 13
METHOD 14
METHOD 15
METHOD 18
METHOD 19
R30
R55
R31
R54
R54
R55
R39
R48
501.1
502.1
501.2
624
601
524.1
501.3
524
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, HALIDE GC
LIQUID/LIQUID, ECGC
GC/MS
GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, SELECTED ION GC/MS
PURGE AND TRAP, GC/MS
4-24
-------
Table IV-5 (Continued)
CARBONTETRACHLORIDE
METHOD 13 R54 - 624
METHOD 14 R54 - 601
ORGftNICS
GC/MS
GC
CHLOROBENZENE
METHOD 11 R54 - 601
METHOD 12 R54 - 602
METHOD 13 R54 - 624
GC
GC
GC/MS
CHLOROFORM
METHOD 11 R30 - 501.1
METHOD 12 R31 - 501.2
METHOD 18 R39 - 501.3
METHOD 19 R48 - 524
DIBROMOCHLOROMETHANE
METHOD 11 R30 - 501.1
METHOD 12 R31 - 501.2
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 18 R39 - 501.3
METHOD 19 R48 - 524
DIBROMOMETHANE
METHOD 11 R55 - 502.1
METHOD 15 R55 - 524.1
ETHYLBENZENE
METHOD 11 R54 - 602
METHOD 12 R54 - 624
METHYLENE CHLORIDE
METHOD 11 R55 - 502.1
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 15 R55 - 524.1
METHOD 16 R55 - 524.2
METHOD 17 R56 - 502.2
PCB-AROCLOR 1016/1242
METHOD 16 R54 - 608
METHOD 18 R46 - P. 43
PCB-AROCLOR 1232
METHOD 16 R54 - 608
METHOD 18 R46 - P. 43
PURGE AND TRAP, HALIDE GC
LIQUID/LIQUID, ECGC
PURGE AND TRAP, SELECTED ION GC/MS
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
LIQUID/LIQUID, ECGC
GC/MS
GC
PURGE AND TRAP, SELECTED ION GC/MS
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
PURGE AND TRAP, GC/MS
GC
GC/MS
PURGE AND TRAP, HALIDE GC
GC/MS
GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, CAP.
PURGE AND TRAP, CAP.
COLUMN GC/MS
COLUMN GC
GC
GC
GC
GC
4-25
-------
Table IV-5 (Continued)
PCB-AROCLOR 1248
METHOD 16 R54 - 608
METHOD 18 R46 - P. 43
PCB-AROCLOR 1254
METHOD 16 R54 - 608
METHOD 18 R46 - P. 43
PCB-AROCLOR 1260
METHOD 16 R54 - 608
METHOD 18 R46 - P. 43
TETRACHLOROETHENE
METHOD 13 R54 - 624
METHOD 14 R54 - 601
TOLUENE
METHOD 11 R54 - 602
METHOD 12 R54 - 624
TOTAL TRIHALOMETHAME
METHOD 11 R30 - 501.1
METHOD 12 R31 - 501.2
METHOD 18 R39 - 501.3
METHOD 19 R48 - 524
TRICHLOROETHENE
METHOD 11 R55 - 502.1
METHOD 13 R54 - 624
METHOD 14 R54 - 601
METHOD 15 R55 - 524.1
METHOD 16 R55 - 524.2
METHOD 17 R56 - 502.2
ORGANICS
GC
GC
GC
GC
GC
GC
GC/MS
GC
GC
GC/MS
PURGE AND TRAP,-HALIDE GC
LIQUID/LIQUID, ECGC
PURGE AND TRAP, SELECTED ION GC/MS
PURGE AND TRAP, GC/MS
PURGE AND TRAP, HALIDE GC
GC/MS
GC
PURGE AND TRAP, GC/MS
PURGE AND TRAP, CAP. COLUMN GC/MS
PURGE AND TRAP, CAP. COLUMN GC
4-26
-------
Table IV-6 List of Analytes and Methods with Regression Equations in Combined WS and WP Studies
PESTICIDES
2,4,5-TP (SILVEX)
METHOD 12 R29 - P. 20 DERIVATIZATION-GC
METHOD 21 R3 - 509B DERIVATIZATION-GC
METHOD 32 R25 - D3.478-79 DERIVATIZATION-GC
2,4-D .
METHOD 12 R29 -P. 20
METHOD 21 R3 -509B
METHOD 32 R25 - D3478-79
DERIVATIZATION-GC
DERIVATIZATION-GC
DERIVATIZATION-GC
ALDRIN
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 50 9A
GC
GC
GC
CHLORDANE
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 509A
GC
GC
GC
ODD
METHOD 16 R54 - 608
METHOD 18 R46 - P..7
METHOD 23 R33 - 509A
GC
GC
GC
DDE
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 509A
GC
GC
GC
DDT
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 509A
GC
GC
GC
DIELDRIN
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 509A
GC
GC
GC
ENDRIN
METHOD 14 R29 - P. 1
METHOD 22 R3 - 509A
GC
GC
HEPTACHLOR
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 -r 509A
GC
GC
GC
4-27
-------
Table IV-6 (Continued)
HEPTACHLOR EPOXIDE
METHOD 16 R54 - 608
METHOD 18 R46 - P. 7
METHOD 23 R33 - 509A
LINDANE
METHOD 14 R29 - P. 1
METHOD 22 R3 - 509A1
METHOXYCHLOR
METHOD 14 R29 - P. 1
METHOD 22 R3 - 509A
METHOD 32 R25 - D3086-79
TOXAPHENE
METHOD 14 R29 - P. 1
METHOD 22 R3 - 509A
METHOD 41 R9 - P.24
PESTICIDES
GC
GC
GC
GC
GC
GC
GC
GC
GC
GC
4-28
-------
Table IV-7 Method. Performance and Comparison with Drinking Water Standards, Discharge Limitations, and
Water Quality Criteria
• , " • ARSENIC
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION
EQUATIONS*
Standard/Criterion, T** (ug/L)
SDWA
MCLs(a)
50.0
CWA
ELG(b) PTRT (c)
30.0
50.0
GOLD
BOOK(d)
0.0022
METHOD 14 R19 - 200.7
ICP
Published performance data
Database range (ug/L)
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Intralab MDL*** (ug/L)
[ 69.00 - 1887.00]
X=1.044T-12.200
P=104.4-1220.0/T
S=0.124X+ 2.400
53.0
WS and WP studies (Number of analyses
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 13.00 -
X=1.030T+ 2.455
P=103.0+ 245.5/T
Overall precision(ug/L) Ss
Interlab MDL+ (ug/L)
:00 40.0
0/T 180.0%
100 7.36
= 185)
468.00]
155 54.0
5/T 107.9%
'09 7.86
19.1
63.7%
4.77
33.4
111.2%
6.20
40.0
80.0%
7.36
54.0
107.9%
7.86
0.083T+ 3.709
5.13 (MDL meets all criteria.)
OTR
OTR
OTR
OTR
OTR
OTR
METHOD 15 R24 - 206.2
AA; FURNACE
Published performance data
Database range (ug/L)
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Intralab MDL*** (ug/L)
[ 9.78 - 237.00]
X=0.965T+ 2.112 50.4
P= 96.5+ 211.2/T 100.7%
S=0.141X+ 1.873 8.98
1.00
WS and WP studies (Number of analyses - 4458)
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
(ug/L) [ 13.00 - 468.00]
X=0.975T+ 0.433 49.2
P= 97.5+ 43.3/T 98.4%
S=0.108T+ 0.423 5.82
31.1
103.6%
6.26
29.7
98.9%
3.66
50.4
100.7%
8.98
49.2
98.4%
5.82
OTR
OTR
OTR
OTR
OTR
OTR
4.85 (Does not meet criterion 1.)
METHOD 16 R24 - 206.3
AA; GASEOUS HYDRIDE
Published performance data
Intralab MDL*** (ug/L)
2.00
WS and WP studies (Number of analyses - 1120)
Database range (ug/L) [ 13.00 - 468.00]
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L) S=0.195T+ 1.034
X=0.937T+ 0.420
P= 93.7+ 42.0/T
47.3
94.5%
10.8
28.5
95.1%
6.88
Interlab MDL+
(ug/L) 6.93 (MDL -meets all criteria.)
4-29
47.3
94.5%
10.8
OTR
OTR
OTR
-------
Table IV-7 (Continued)
ARSENIC •
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION SDWA
EQUATIONS* MCLs(a)
CWA
ELG(b) PTRT(c)
Standard/Criterion, T** (ug/L)
METHOD 17 R24 - 206.4
SILVER DIETHYLDITHIOCARBAMATE
Published performance data
Database range (ug/L) [ 20.00 -
Accuracy (ug/L)
Accuracy (%)
50.0
30.0
50.0
292
X=0.850T- 0.250
P= 85.0- 25.0/T
Overall precision(ug/L) S=0.198X+ 5.930
Intralab MDL*** (ug/L) 10.0
WS and WP studies (Number of analyses
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 15.00 -
X=1.011T- 2.555
P=101.1- 255.5/T
Overall precision(ug/L) S=
Interlab MDL+ (ug/L)
=0.091T+ 3.993
17.4 (Doe:
!.00]
42.3
? 84.5%
14.3
107)
!.00]
48.0
? 96.0%
8.54
i not meet
25.3
84.2%
10.9
27.8
92.6%
6.72
criteria 2
42.3
84.5%
14.3
48.0
96.0%
8,54
and 3.
METHOD 24 R3 - 404A AFTER B(4)
SILVER DIETHYLDITHIOCARBAMATE
Published performance data
Intralab MDL*** (ug/L) (Not available.)
WS and WP studies (Number of analyses = 106)
(ug/L) [ 15.00 - 112.00]
X-0.955T+ 0.613 48.4
P= 95.5+ 61.3/T 96.7%
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L) S=0.169T+ 2.189
10.6
29.3
97.5%
7.26
Interlab MDL+
(ug/L)
14.6 (Does not meet criteria 1
48.4
96.7%
10.6
and 3.
METHOD 25 R3 - 301A-VII
AA;GASEOUS HYDRIDE
Published performance data
Intralab MDL*** (ug/L) (Not available.)
WS and WP studies (Number of analyses = 301)
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 15.00 - 112.00]
X=0.985T+ 0.150
P- 98.5+ 15.0/T
Overall precision(ug/L) S=0.211T- 0.381
49.4
98.8%
10.2
29.7
99.0%
5.95
49.4
98.8%
10.2
Interlab MDL+
(ug/L)
8.74 (Does not meet criterion 1.)
GOLD
BOOK(d)
0.0022
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
4-30
-------
Table IV-7 (Continued)
ARSENIC
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION
EQUATIONS*
Standard/Criterion, T** (ug/L)
METHOD 26 R53 - 303E
AA; GASEOUS HYDRIDE
Published performance data
Intralab MDL*** (ug/L)
WS and WP studies
Database range
Accuracy (ug/L)
Accuracy (%)
SDWA
MCLs(a)
50.0
CWA
ELG(b) PTRT(c)
30.0
50.0
2.00
(Number of analyses = 203)
(ug/L) [ 13.00 - 468.00]
X=0.929T+ 0.312 ' 46.8
P= 92.9+ 31.2/T 93.5%
Overall precision(ug/L) S=0.307T- 0.259
15.1
28.2
93.9%
8.95
46.8
93.5%
15.1
Interlab MDL+ (ug/L)
R53 - 304
10.1 (Does not meet criterion 3.)
METHOD 27
AA; FURNACE
Published performance data
Intralab MDL*** (ug/L)
WS and WP studies
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
1.00
(Number of analyses = 162)
(ug/L)
[ 13.00 - 468.00]
X=0.965T+ 1.148 49.4
P= 96.5+ 114.8/T 98.8%
S=0.101T+ 2.487 7.54
30.1
100.3%
5.52
49.4
98.8%
7.54
10.8 (Does not meet criteria 1 and 3.)
METHOD 32 R25 - D2972-78B
AA; GASEOUS HYDRIDE
Published performance data
Intralab MDL*** (ug/L)
1.00
WS and WP studies (Number of analyses =
Database range (ug/L) [ 15.00 - 112
Accuracy (ug/L) X=0.998T- 1.118
Accuracy (%)
Overall precision (ug/L) S;
Interlab MDL+ (ug/L)
P= 99.8- 111.8/T
0.188T- 0.512
68)
,00]
48.8
97.6%
8.89
28.8
96.1%
5.13
48.8
97.6%
8.89
8.07 (Does not meet criterion 1.)
GOLD
BOOK(d)
0.0022
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
OTR
4-31
-------
Table IV-7 (Continued)
ARSENIC .
(CONCENTRATIONS are in ug/L)
NSC - No standard or criterion
OTR - Outside the range for extrapolating the regression equations. Range is
one-half the lower database range value to 2 times the upper database
range value.
(a)Final regulations, 40CFR141.il
(b)Proposed BAT, Option 1, 50FR29082
(c)Proposed PSES, Option I, 50FR29086
(d) Human health, drinking and fish ingestion . . . ,
* See note 1 (regression,equations), at beginning of Appendix.
** See note 2 (limit concentrations), at beginning of Appendix.
***See note 3 (published intralab MDL), at beginning of Appendix.
+ See note 4 (calculated.interlab MDL), at beginning of Appendix.
Criteria for calculated MDL:
(1) The lowest true concentration of the analyte is less than or equal to iO
times the published MDL in reagent water.
(2) The lowest true concentration of the analyte is greater than the calculated
MDL.
(3) Eighty percent (80%) of the laboratories (i.e., analytical results) are
within plus or minus 40 percent of the lowest true concentration.
4-32
-------
Table IV-8 Method Performance and Comparison with Drinking Water Standards, Discharge Limitations, and
Water Quality Criteria
BARIUM
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION
EQUATIONS*
Standard/Criterion, T** (ug/L)
METHOD 14 R24 - 208.1
AA
Published performance data
'Intralab MDL*** (ug/L) 100.0
WS and WP studies (Number of analyses
(ug/L) [ 63.00 -
SDWA
MCLs(a)
1000.
Database range
Accuracy (ug/L) X=0.968T+ 5.004
Accuracy (%) P= 96.8+ 500.4/T
Overall precision(ug/L) S=0.075T+ 7,134
Interlab MDL+ (ug/L)
= 2223)
882.00]
973.0
97.3%
82.1
CWA
ELG(b) PTRT(c)
GOLD
BOOK(d)
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
33.1 (MDL meets all criteria.)
METHOD 15 R24 - 208.2
AA; FURNACE
Published performance data
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 56.50 - 437.00]
X=?0.827T+59.460 OTR
P- 82.7+5946.0/T OTR
Overall precision(ug/L) S=0.247X+ 6.436 OTR
Intralab MDL*** (ug/L) 2.00
WS and WP studies (Number of analyses = 1545)
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 63.00 - 882.00]
X=0.974T+ 3.701
P= 97.4+ 370.1/T
Overall precision(ug/L) S=
Interlab MDL+ (ug/L)
METHOD 22 R3 - 301A-IV
AA
Published performance data
Intralab MDL*** (ug/L)
'0.105T+ 4.166
977.7
97.8%
109.2
NSC
NSC
NSC
NSC
NSC
NS,C
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
27.1 (Does not meet criterion 1.)
30.0
WS and WP studies (Number of analyses = 397)
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 63.00 - 882.00]
X=0.943T+10.458 953.5
P= 94.3+1045.8/T 95.3%
NSC NSC
NSC NSC
Overall precision(ug/L) S=0.112T+13.0i8 125.0 NSC NSC
Interlab MDL+ (ug/L) 60,3 (Does no£ meet criterion 3.)
NSC
NSC
NSC
4-33
-------
Table IV-8 (Continued)
BARIUM
(CONCENTRATIONS are in ug/L)
NSC — No standard or criterion
OTR - Outside the range for extrapolating the regression equations. Range is
one-half the lower database range value to 2 times the upper database
range value.
(a)Final regulations, 40CFR141.il
(b)No guideline
(c)No guideline
(d)No criterion
* See note 1 (regression equations), at beginning of Appendix.
** See note 2 (limit concentrations), at beginning of Appendix.
***See note 3 (published intralab MDL), at beginning of Appendix.
+ See note 4 (calculated interlab MDL), at beginning of Appendix.
Criteria for calculated MDL:
(1) The lowest true concentration of the analyte is less than or equal to 10
times the published MDL in reagent water.
(2) The lowest true concentration of the analyte is greater than the calculated
MDL.
(3) Eighty percent (80%) of the laboratories (i.e., analytical results) are
within plus or minus 40 percent of the lowest true concentration.
4-34
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Table IV-9 Method Performance and Comparison with Drinking Water Standards, Discharge Limitations, and
Water Quality Criteria
. .ALDRIN
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION
EQUATIONS*
SDWA
MCLs(a)
CWA
ELG(b) PTRT(c)
Standard/Criterion, T** (ug/L)
METHOD 16 R54 - 608
GC
Published performance data
Intralab MDL*** (ug/L) 0.0040
WS and WP studies (Number of analyses = 1446)
GOLD
BOOK(d)
0.000074
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 0.07 - 0.82]
X=0.797T+ 0.004 NSC
P= 79.7+ . 0.4/T NSC
NSC NSC
NSC NSC
Overall precision(ug/L) S=0.220T+ 0.005 NSC NSC NSC
Interlab MDL+ (ug/L) 0.051 (Does not meet criteria 1 and 3.
OTR
OTR
OTR
METHOD 18 R46 - P. 7
GC , , • ...
Published performance data
Intralab MDL*** (ug/L) (Not available.)
WS and WP studies (Number of analyses =
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ 0.07 - 0
X=0.788T+ 0.000
P= 78.8+ 0.0/T
Overall precision(ug/L) S=0.159T+ 0.004
64)
,82]
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
NSC
OTR
OTR
OTR
Interlab MDL+ (ug/L)
0.087 (Does not meet criteria 1,2, or 3.)
METHOD 23 R33 - 509A
GC
Published performance data
Intralab MDL*** (ug/L) (Not available.)
WS and WP studies (Number of analyses =
Database range (ug/L) [ 0.07 - 0,
Accuracy (ug/L) X=0.768T+ 0.012
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
P= 76.8+ 1.-2/T
S=0.197T+ 0.013
89)
82]
NSC
NSC
NSC
NSC
NSC
NSC
0.054 (Does not meet criteria
NSC
NSC
NSC
1 and 3.)
OTR
OTR
OTR
4-35
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Table IV-9 (Continued) ,
ALDRIN
(CONCENTRATIONS are in ug/L)
NSC - No standard or criterion
OTR - Outside the range for extrapolating the regression equations. Range is
one-half the lower database range value to 2 times the upper database
range value.
(a)No standard
(b)No guideline
(c)No guideline
(d)Human health,
drinking and fish ingestion
* See note 1 (regression equations), at beginning of Appendix.
** See note 2 (limit concentrations), at beginning of Appendix.
***See note 3 (published intralab MDL), at beginning of Appendix.
4- See note 4 (calculated interlab MDL), at beginning of Appendix.
Criteria for calculated MDL:
(1) The lowest true concentration of the analyte is less than or equal to 10
times the published MDL in reagent water.
(2) The lowest true concentration of the analyte is greater than the calculated
MDL. ,
(3) Eighty percent (80%) of the laboratories (i.e., analytical results) are
within plus or minus 40 percent of the lowest true concentration.
4-36
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Table IV-10 Method Performance and Comparison with Drinking Water Standards, Discharge Limitations, and
Water Quality Criteria
1,1,1-TRICHLOROETHANE
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION SDWA
EQUATIONS* MCLs(a)
CWA
ELG(b) PTRT(c)
Standard/Criterion, T** (ug/L)
METHOD 13 R54 - 624
GC/MS
Published performance data
(ug/L)
200.0
10.0
10.0
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L) S
Intralab MDL*** (ug/L)
WS and WP studies
Database range
Accuracy (ug/L)
Accuracy (%)
[ 5.00 - 600.00]
X=1.060T+ 0.730 212.7
P=106.0+ 73.0/T 106.4%
0.210X- 0.390 44.3
3.80
(Number of analyses = 679)
(ug/L) [ 4.08 - 73.80]
X=1.024T+ 0.187 OTR
P=102.4+ 18.7/T OTR
Overall precision(ug/L) S=0.148T+ 0.331 OTR
11.3
113.3%
1.99
10.4
104.3%
1.81
11.3
113.3%
1.99
10.4
104.3%
1.81
Interlab MDL+ (ug/L)
METHOD 14 R54 - 601
GC
Published performance data
2.21 (MDL meets all criteria.)
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) I 8.00 - 500.00]
X=0.900T- 0.160
P= 90.0- 16.0/T
Overall precision(ug/L) S=
Intralab MDL*** (ug/L)
'0.200X+ 0.370
0.030
179.8
89.9%
36.3
WS and WP studies (Number of analyses
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
764)
(ug/L) [ 4.08 - 73.80]
X=1.021T+ 0.139 OTR
P=102.1+ 13.9/T OTR
S=0.162T+ 0.671 OTR
GOLD
BOOK(d)
18400.
OTR
OTR
OTR
OTR
OTR
OTR
3.63
8.84
88.4%
2.14
10.3
103.5%
2.29
criteria
8.84
88.4%
2.14
10.3
103.5%
2.29
1 and 3.)
OTR
OTR
OTR
OTR
OTR
OTR
4-37
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Table IV-10 (Continued)
1,1,1-TRICHLOROETHANE
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION SDWA
EQUATIONS* . MCLs(a)
CWA
ELG(b) PTRT(c)
Standard/Criterion, T** (ug/L)
METHOD 11 R55 - 502.1
PURGE AND TRAP, HALIDE GC
Published performance data
200.0
10.0
10.0
GOLD
BOOK(d)
18400.
Database range
Accuracy (ug/L)
Accuracy (%)
(ug/L) [ Not available. ]
X=0.920T+ 0.020 (Not calculated, no database range.)
P= 92.0+ 2.0/T (Not calculated, no database range.)
Overall precision(ug/L) S=0.270X- 0.760 (Not calculated, no database range.)
Intralab MDL*** (ug/L)
0.0030
WS and WP studies (Number of analyses = 237)
Database range (ug/L) [ 10.50 - 182.50]
X=1.001T+ 0.289 200.5
P=100.1+ 28.9/T 100.2%
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L) S=0.223T+ 0.086
44.7
10.3
103.0%
2.32
10.3
103.0%
2.32
Interlab MDL+ (ug/L)
METHOD 15 R55 - 524.1
PURGE AND TRAP, GC/MS
Published performance data
Intralab MDL*** (ug/L)
WS and WP studies
Database range
Accuracy (ug/L)
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
5.73 (Does not meet criterion 1.)
0.26
(Number of analyses = 138)
(ug/L) [ 10.50 - 182.50]
X-1.015T+ 0.402 ' 203.4
P=101.5+ 40.2/T 101.7%
S=0.251T- 0.780 49.4
10.6
105.5%
1.73
10'. 6
105.5%
1.73
4.41 (Does not meet criterion 1.)
METHOD 16 R55 - 524.2
PURGE AND TRAP, CAP.. COLUMN GC/MS
Published performance data
Intralab MDL*** (ug/L) 0.080
WS and WP studies (Number of analyses
Database range
Accuracy (ug/L)
Accuracy (%)
74)
(ug/L) [ 10.50 - 182.50]
X=1.003T+ 0.860
P=100.3+ 86.0/T
Overall precision(ug/L) S=0.273T- 0.257
201.5
100.7%
54.3
10.9
108.9%
2.47
10.9
108 .,9%
2.47
Interlab MDL+
(ug/L)
6.35 (Does not meet criteria 1 and 3.)
OTR
OTR
OTR
OTR
OTR
OTR
OTR
,OTR
OTR
4-38
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Table IV-10 (Continued)
1,I,l-TRICHLOROETHANE
(CONCENTRATIONS are in ug/L)
METHOD
REGRESSION
EQUATIONS*
SDWA
MCLs(a)
Standard/Criterion, T** (ug/L)
200.0
METHOD 17 R56 - 502.2
PURGE AND TRAP, CAP. COLUMN GC
Published performance data
Intralab MDL*** (ug/L) 0.030
WS and WP studies (Number of analyses =
Database range (ug/L) [ 10.50 - 182
Accuracy (ug/L) X=0.751T+ 1.259
Accuracy (%)
Overall precision(ug/L)
Interlab MDL+ (ug/L)
CWA
ELG(b) PTRT(c)
P= 75.1+ 125.9/T
S=0.554T- 2.372
10.0
10.0
31)
50]
151.5
75.7%
108.4
8.77
87.7%
3.17
8.77
87.7%
3.17
8.96 (Doe's not meet criteria 1 and 3.)
GOLD
BOOK(d)
18400.
OTR
OTR
OTR
NSC - No standard "or criterion
OTR - Outside the range for extrapolating the regression equations. Range is
one-half the lower database range value to 2 times the upper database
range value.
(a)Final regulations,40CFR141.61
(b)Final regulations,40CFR433, Stds are sum of specified TTO's above 10 ug/L
(c)Final regulations,40CFR433, Stds are sum of specified TTO's above 10 ug/L
(d)Human health, drinking and fish ingestion
* See note 1 (regression equations), at beginning of Appendix.
** See note 2 (limit concentrations), at beginning of Appendix.
***See note 3 (published intralab MDL), at beginning of Appendix.
+ See note 4 (calculated interlab MDL), at beginning of Appendix.
Criteria for calculated MDL:
(!) The lowest true concentration of the analyte is less than or equal to 10
times the published MDL in reagent water.
(2) The lowest true concentration of the analyte is greater than the•calculated
MDL.
(3) Eighty percent (80%) of the laboratories (i.e., analytical results) are
within plus or minus 40 percent of the lowest true concentration.
4-39
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Table IV-11 List of Approved Biological Test Procedures in 40 CFR 136.3
Parameter and units
Method1
EPA2
Page*
Standard
Methods ASTM
15th Ed.
USGS
Bacteria:
1.
2.
3.
4.
5.
Coliform (fecal number
per 100 mL)
Coliform (fecal) in
presence of chlorine
number per 100 mL
Coliform (total), number
per 100 mL)
Coliform (total) in
presence of chlorine,
number per 100 mL
Fecal streptococci,
number per 100 mL
MPN, 5 tube, 3 dilution; or,
membrane filter (MF)4,
single step
MPN, 5 tube, 3 dilution; or,
MF4, single step
MPN, 5 tube, 3 dilution; or,
MF4 single step or two step
MPN, 5 tube, 3 dilution; or
MF4with enrichment
MPN, 5 tube, 3 dilution;
MF4or,
plate count
132
124
132
124
114
108
114
111
139
136
143
908C
9,09C
908C
909C
908A
909A
908A
909(A + A.5c)
910A
910B
910C
B-0050-77
B-0050-77
B-0025-77
B-0025-77
B-0055-77
1The method used must be specified when results are reported.
2"Mferobiological Methods for Monitoring the Environment, Water and Waste, 1978", EPA-600/8-78-017, U.S.
Environmental Protection Agency.
3Greeson, P.E., et al., "Methods for Collection and Analysis of Aquatic Biological and Microbiological Samples",
U.S. Geological Survey, Techniques of Water-Resources Investigations, Book 5, Chapter A4, Laboratory Analysis, 1977.
40.45 um membrane filter or other pore size certified by the manufacturer to fully retain organisms to be
cultivated, and free of extractables which could interfere with their growth and development.
4ASince the membrane filter technique usually yields low and variable recovery from chlorinated wastewaters, the MPN
method will be required to resolve any controversies.
5Approved only if dissolution of the KF Streptococcus Agar (Section 5.1, USGS Method B-0055-77) is made in a boiling
water bath to avoid scorching of the medium.
material use. In this form, these are not useful
for assessing the adequacy of analytical methods
for documenting compliance or noncompliance.
EPA's Development Documents for Effluent
Limitations Guidelines and Standards, however,
present the basis for the guidelines and
standards, and identify the concentration basis
for the limits which are expressed as mass per
unit of production. However, by reviewing all
available promulgated and recently proposed
guidelines and standards, concentration ELG
and PS which are representative of the
minimum pollutant concentrations the Agency
has used for all of its categorical guidelines and
4-40
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standards were determined. Therefore, these
ELG and PS minimum concentrations represent
the most stringent test of the performance of the
analytical methods for precision, mean recovery,
and detection limits.
For certain of the organic chemical pollutants,
the EPA has promulgated ELG and PS based on
total toxic organics (TTO). TTO is defined as the
sum of the concentrations of all of a specified list
of organic priority pollutants which are present
in a sample at a minimum concentration of 10
ug/L. Thus, 10 ug/L is used as the required limit
on all such pollutants listed, since determination
of compliance with the TTO standard requires
quantitation of each specified chemical at or
above 10 ug/L. Each table for each pollutant
references the specific source of the
concentrations used as ELG and PS limits.
The last column in the table presents the
currently most restrictive water quality
criterion. These criteria are taken from the EPA
Gold Book (Quality Criteria for Water, 1986,
EPA 440/5-86-001, May, 1986). The specific
criterion used for the method performance
evaluation is either an aquatic life or human
health criterion, whichever is most restrictive
for the particular chemical.
In addition to information relating to precision
and mean recovery, Tables IV-7 through IV-10
present data relating to the published method
detection limit (MDL) and an MDL calculated
from the WP and WS data. The published MDL's
are found in the EPA analytical method
manuals and in 40 CFR 136. The published
MDL's are usually generated by a single EPA
laboratory, and are matrix-specific (usually they
represent contaminant-free reagent water). A
detection limit based on a non-replicative
interlaboratory study would be expected to be
significantly higher than an MDL.
The published MDL's are considered by EPA to
be the maximum achievable sensitivity of a
method for a specific water quality constituent
and are not necessarily routinely attainable (see
50 FR 46907,52 FR 25699). Because of this, EPA
has defined a practical quantitation limit (PQL)
for many analytical methods which must
measure analytes at low concentration levels
(see 50 FR 46907, 52 FR 25699). The PQL for
certain volatile SDWA analytes was defined as
the lowest concentration at which 80 percent of
the laboratories in the WS studies could obtain
results within plus or minus 40 percent of the
true concentration standard. It was stated to be
about 5 to 10 times the published MDL.
In this analysis the WS and WP data bases were
used to calculate what might be called an
interlaboratory detection limits (IDL). This is
what is identified as the "calculated MDL" in
Table IV-7 through IV-10 and was conceived as a
possible procedure for establishing PQL directly
from a WS or WP data base. The IDL was
estimated as follows:
• Use only those method data bases with
enough data to calculate regression
equations. Although the regression
equations are not used in the IDL
calculation, this step assures that
sufficient data are available to provide
some statistical confidence in the
calculation.
• Calculate the IDL as the interlaboratory
standard deviation times the Student's t
value for the 99 percent confidence level
and appropriate degrees of freedom
(number of analyses used to calculate the
standard deviation minus 1).
• Establish criteria for evaluating the
detection limit. If these criteria are not
met, the calculated detection limit is
flagged.
The criteria used to evaluate the interlaboratory
detection limit were as follows:
l)As stated in Appendix B to 40 CFR 136, MDL
calculations should be based on replicate
analyses of spike samples containing the
analyte at one to ten times the expected
detection limit. Although no replication was
involved in WS or WP, if the lowest "true
value" from the WS and WP studies
exceeded the interlaboratory detection limit
by a factor greater than 10, the "calculated
MDL" was flagged.
4-41
-------
2)The method for determining a method
detection limit specifies that the MDL
should be below the spike level. If the IDL
was not below the lowest "true value" in the
WS and WP studies, the "calculated MDL"
was flagged.
3)The IDL were evaluated against the PQL
criteria developed by EPA, to ensure that 80
percent of the laboratories must obtain
results within 40 percent of the true value. If
these PQL criteria were not achieved, the
"calculated MDL" was flagged.
As shown in Table IV-7 through IV-10, several
of the "calculated MDL's" did not meet criteria 1
(indicating WS/WP concentrations were too
high) and 3 (indicating that the data quality
objective stated for PQL were not always met by
IDL).
This approach uses elements from the MDL
estimation methodology given by the Agency at
40 CFR 136, Appendix B and the PQL
methodology. Comparison of the IDL to the
published MDL for a given method and chemical
provides a semi-quantitative basis for assessing
the interlaboratory effects on MDL's.
Evaluation of Method Performance Data
The data presented in these tables can be used to
assess the adequacy of the test methods where
specific data quality objectives (DQO's) are
identified. For example, Table IV-7 indicates
that arsenic could be measured using method
200.7. At a concentration (true value) of 50 ug/L,
the method would indicate arsenic at a
concentration of 54 ± 15 ug/L at a 95%
confidence level.
In a similar manner, at the MCL of 200 ug/L for
1,1,1-trichloroethane, method 502.1 would
measure 200.5 ± 87.6 ug/L. Thus, the
assessment of adequacy must answer the
question of how good a measurement must be.
The assessment in this report was limited to a
comparison of MDL's with water quality criteria
and standards or NPDES effluent limitations.
The adequacy of the 304(h) methods cannot be
further evaluated for precision and mean
recovery in the absence of detailed DQO's.
Availability of Biological Testing
Methods
The discussion on availability and adequacy has
been separated into two sections due to the
proposed significant additions to the available
304(h) methods in early 1988. The EPA proposes
to amend 40 CFR 136 by adding new
measurements and new test methods to Table
IA, "List of Approved Biological Test methods."
These methods include (1) methods for
measuring the toxicity of pollutants in effluents,
drilling muds, and receiving, waters, including
short-term methods for acute and chronic
toxicity to freshwater and marine organisms; (2)
methods for measuring mutagenicity; (3)
methods for monitoring viruses in wastewaters
and sludges; and (4) updated .citations to
microbiological methods. Under the 1984
national policy for development of water quality-
based permit limits, EPA expected toxicity tests
to play an important role in the issuance of
NPDES permits. EPA recognized the need for
uniformity in the test methods, drafted a
proposed amendment, and sought public
comments. Since the proposed changes to the list
of available methods is still in the comment
period, the two parts were separated to facilitate
possible revisions. Methods are listed as four
separate categories for discussion.
Standardized Methods Currently
Approved
There are currently five biological parameters
that are approved and included in 40 CFR 136.
All five parameters are microbiological
measurements (Table, IV-11) for indicating fecal
pollution or for measuring the overall
microbiological quality of ambient waters and
wastewaters. The methods are described in
detail in the EPA manual, "Microbiological
Methods for Monitoring the Environment" (4-2).
These same analytes have also been described by
the United States Geological Survey (USGS) (4-
3) as well as the American Public Health
Association (4-4). The Fifteenth Edition of the
APHA "Standard Methods" cited in Table IA has
been updated. Only microbiological methods
have been approved. The list does not include
any methods for aquatic toxicity test, viruses, or
pathogens. As previously discussed, EPA has
4-42
-------
proposed to amend the list in order to provide
standardized methods for monitoring programs.
Standardized Methods Proposed for
Approval
The proposed amendments to the list of
approved biological methods in 40 CFR 136 are
listed in Table IV-12. In the proposed
amendments, the citations to the existing
microbiological methods are updated to coincide
with the Sixteenth Edition of the APHA
Standard Methods (4-4). In addition, methods
are proposed for detecting enteroviruses in
water and sludge; mutagenicity (Ames Test);
acute toxicity methods for freshwater and
marine organisms; and chronic toxicity methods
for freshwater organisms. A brief description of
each method and the rationale supporting the
proposed amendments follows.
Enteroviruses in Water and Sludge
Pathogenic viruses are assumed to be included
in the definition of "toxic pollutants" to be
controlled under the FWPCA. In the past several
years, an increased awareness of the risks of
waterborne human pathogenic viruses has
developed with the agencies responsible for
surface waters, effluent, and sludge monitoring.
As a result of these concerns and at the
recommendation of the World Health
Organization (WHO), virus standards have been
included in the water quality standards of two
states. It is expected that additional states will
soon introduce virus standards and
requirements for monitoring viruses. Arizona
has set a limit of one enteric virus unit per 40
liters of sample for effluent-dominated
recreational waters in which there is full body
contact. For incidental contact, 125 enteric virus
units per 40 liters is allowed. Montgomery
County, Maryland has also adopted a virus
standard for discharges limiting the number of
detectable infectious virus units to 1 per 40
liters.
The methods for detecting enteroviruses in
water or sludge are described in the EPA
manual of Methods for Virology (4-5). The
method consists of instructions for sampling,
concentration, detection, and identification.
Because of the high infectivity of viruses, it may
be necessary to concentrate them from large
volumes of sample if they are present only in
small numbers. The concentration technique is
based on virus adsorption, followed by elution.
Viruses are detected and quantified by
innoculating an aliquot of the sample
concentrate into mammalian cell cultures.
Viruses are identified by neutralization tests
using specific antisera.
Mutagenic Test Methods
Mutagenic substances are also defined in the
FWPCA as toxic substances and are subject to
control. Mutagenic activity has been reported in
both domestic and industrial waste discharged
to surface waters, and has been included in the
Agency's toxics control strategy. Mutagenicity
tests are performed routinely on effluents in
some municipal and EPA field monitoring
laboratories, and are included in state toxics
control programs. Substances which test positive
in the Ames Test for mutagenicity have a high
potential for being mammalian mutagens and
carcinogens. Chemicals which damage DNA in
reproductive cells may cause birth defects and
genetic disorders. DNA damage in body or
somatic cells may result in the initiation of
cancer.
The proposed test method is based on the Ames
Test (4-6) and has been described in detail for
routine use (4-7). Mutagens in water and
wastewater samples are usually concentrated by
organic extraction techniques before being used
in the test. The test involves the use of mutant
bacterial cultures (Salmonella) to detect
mutagenic activity. The Salmonella strains
developed specifically for this test revert to the
"wild" type when acted upon by mutagenic
substances. The results of the test are expressed
in terms of the number of "revertants" (number
of bacteria that mutated) per unit volume of
sample or as the number of revertants per gram
of organic matter (extract) per liter.
Acute Toxicity Tests for Freshwater and
Marine Organisms
The 1984 EPA National Policy for establishing
water quality-based permit limitations for toxic
pollutants (4-8) proposed the use of toxicity tests
to assess and control the discharge of toxic
4-43
-------
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substances to the nation's waters through the
NPDES permits program. The policy states that
"biological testing of effluent is an important
aspect of the water quality-based approach for
controlling toxic pollutants." All states have
water quality standards which include narrative
statements prohibiting the discharge of "toxic
materials in toxic amounts." In the technical
support document issued after the national
policy was published, (4-9) the application of
biological methods for regulating effluents was
specifically discussed. It stated that "EPA will
use an integrated strategy consisting of both
biological and chemical methods to address toxic
and non-conventional pollutants from industrial
and municipal sources." In addition to enforcing
specific numerical criteria, EPA and the States
"will use biological techniques and available
data on chemical effects to assess toxicity
impacts and human health hazards."
Since the early 1970's there has been a
steady increase in the use of effluent toxicity
tests within the Agency and state NPDES
programs to identify and control toxic
discharges. To meet the program needs, EPA
prepared standardized methods for effluent
toxicity tests. The first acute toxicity test
methods developed specifically for effluents were
published in 1978 (4- 10) and revised and
expanded in 1985 (4-11).
The manual includes a preliminary range-
finding test, a screening test, and multi-
concentration (definitive) static and flow-
through toxicity tests. Also included are
guidelines on laboratory safety, quality
assurance, facilities and equipment, effluent
sampling and holding, dilution water, test
species selection and handling, data
interpretation and utilization, report
preparation, organism culturing, and dilutor
and mobile bioassay laboratory design. The 1985
(4-11) acute toxicity test methods manual
includes a list of 50 recommended freshwater
and marine test organisms. The tests are used to
determine the effluent concentration, expressed
as a percent volume, that causes the death of 50
percent of the organisms (LC50) or a measured
effect in 50 percent of the test population (ECso).
The manual also includes a brief discussion
of an effluent fractionation technique that is
useful in Toxicity Reduction Evaluation (TRE).
Should toxicity be demonstrated in the effluent,
the NPDES permit writer's guidelines (4-12)
state that the Regional office or the State agency
with responsibility for that permit should
require the permittee to reduce toxicity by
determining the causative toxicants or an
appropriate treatment method. Using the
fractionation technique, the source of toxicity
can be possibly discovered. The effluent is
subjected to a series of ion exchange resins to
separate out particulates from the effluent and
split the remaining liquid into an organic and
inorganic fractions. If either fraction exhibits
toxicity, subfractionation under basic and acidic
conditions is completed and each tested for
toxicity. The fractionation procedure is now
being updated and field tested.
Chronic Toxicity Tests for Freshwater,
Marine, andEstuarine Organisms
The use of short-term, partial chronic
toxicity tests in the NPDES permits program
was recommended in the 1984 National Policy
on water quality-based permit limits. The
methods were designed to provide a more direct
measurement of the "safe" concentration of
effluent in receiving waters (NOEC) than was
provided in acute toxicity tests at only a slight
increase in the time required to produce data.
Compared to the traditional full life-cycle
chronic tests for fish (months to years) and the
cladoceran tests (21-28 days), these short- term
chronic tests for freshwater and marine
organisms are relatively quick (4- 9 days) and
several can be run within nearly the same time
period as acute tests. The endpoints used in the
proposed chronic tests are survival, growth, and
reproduction. The effects include the synergistic,
antagonistic, and additive effects of all the
chemical, physical, and biological components
which adversely affect the physiological and
biochemical functions of the test organisms.
At this time, EPA proposes to approve
chronic methods for freshwater, marine and
estuarine organisms (4-13,4-14). The short-term
chronic toxicity tests are proposed to estimate
one or more of the following: (1) the chronic
toxicity of effluents collected at the end of the
discharge pipe and tested with a standard
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dilution water, (2) the chronic toxicity of
effluents collected at the end of the pipe and
tested with nontoxic receiving water collected
upstream from the outfall or with
uncontaminated surface water having the same
characteristics (salinity, hardness) as the
receiving water, (3) toxicity of the receiving
water downstream or within the zone of
influence of the outfall, and (4) the effects of
multiple discharges on the quality of the
receiving water. These tests may also be useful
to conduct Toxicity Reduction Evaluations
(TRE) and to develop site-specific water quality
criteria.
The four methods described for freshwater
organisms include a freshwater fish, an
invertebrate, and an alga. Each is described
briefly:
(1) EPA Test Method 1000.0. Fathead Minnow
(Pimephales promelas) Larval Survival and
Growth Test is a seven-day, static renewal,
larval survival and growth test. Less-than-
24-hour-old larvae are exposed to control
water, receiving water, and at least five
concentrations of the effluent/Test results
are based on survival and growth (weight
increase) of the larvae.
(2) EPA Test Method 1001.0. Fathead Minnow
(Pimephales promelas) Embryo Survival and
Teratogenicity Test is an eight-day, static
renewal, embryo-larval survival and
teratogenicity test. Embryos and larvae are
exposed to a series of effluent concentrations
or to receiving water from shortly after
fertilization of the eggs through four days
posthatehing (total of eight days). Test
results are based on the combined frequency
of mortality and gross morphological
deformities (terata).
(3) EPA Test Method 1002.0. Ceriodaphnia
Survival and Reproduction Test is a test
with the cladoceran, Ceriodaphnia dubia
during seven days (three broods) in a static
renewal test. Test results are based on
survival and reproduction. If the test is
conducted as described, the control
organisms should produce three broods of
young (20-30) during the seven days.
(4) EPA Test Method 1003.0. Algal
(Selenastrum capricornutum) Growth Test is
a four-day static growth test. A Selenastrum
population is exposed to a series of
concentrations of effluent or to receiving
water. The response of the population is
measured in terms of changes in cell density
(pell counts per milliliter), biomass,
chlorophyll content, or absorbance,
compared to the control.
Six short-term chronic methods for
estimating toxicity to marine and estuarine
organisms were published in May, 1988 (4-14).
The chronic marine methods are briefly
reviewed as follows:
(l)EPA Test Method 1004.0. Sheepshead
Minnow (Cyprinodon uariegatus) Larval
Survival and Growth Test is a seven-day,
subchronic, static renewal, larval survival
and growth test.
(2) EPA Test Method 1005.0. Sheepshead
Minnow (Cyprinodon uariegatus) Embryo-
Larval Survival and Teratogenicity Test is a
nine day, subchronic, static renewal embryo-
larval survival and teratogenicity test.
(3) EPA Test Method 1006.0. Inland Silversides
(Menidia beryllina) Larval Survival and
Growth Test is a seven day, subchronic,
static renewal test.
(4) EPA Test Method 1007.0. Mysid (Mysidopsis
bahia) Survival, Growth, and Reproduction
Test is a seven day, subchronic, static
renewal test.
(5) EPA Test Method 1008.0. Sea urchin
(Arbacia punctulata) Fertilization Test is a
one and one-half hour sperm cell toxicity test
to determine the concentration of a test
substance that reduces fertilization of
exposed eggs.
(6) EPA Test Method 1009.0. Red algae
(Champia paruula) Sexual Reproduction
Test is a two day exposure and 5-7 day
recovery period test in which the formation
of reproductive structures called cystocarps
(indicating fertilization) resulting from
sexual reproduction is monitored. The
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number of cystocarps per female are counted
and compared to the controls.
The results of these tests with effluents are
expressed as the "safe" concentration (percent
effluent volume), which is the highest
concentration in the dilution water at which no
adverse effect is observed (No-Observed-Effect-
Concentration or NOEC). To ensure quality
data, three reference toxicants are available
from the EPA Environmental Monitoring and
Support Laboratory in Cincinnati (sodium
dodecylsulfate, copper sulfate, and cadmium
chloride). Instructions for the use and the
expected toxicity values for the reference
toxicants are provided with the samples.
Additional Available EPA Methods
Methods for performing field surveys and
damage assessments due to toxic substances
discharged or inadvertently released are
available but are not being considered for
approval by EPA at this time. These methods
were developed by EPA to provide guidance for
Agency and state biological monitoring
programs (4-15). Biological monitoring methods
for field assessments of phytoplankton,
zooplankton, periphyton, macroplyton,
macroinvertebrates, and fish were described in
1973 (4-16). Although this manual requires
some updating, it is still widely used by EPA and
other monitoring programs.
Methods for quantitative ecological
assessments have also been developed by other
EPA research labs for specific needs. Under the
direction of the EPA Environmental Research
Lab at Corvallis, Oregon, a series of methods
specifically designed for the marine
environment were developed and published for
intertidal macrofauna, macrophyta, benthos,
zooplankton, and phytoplankton (4-17,18).
Methods were also developed for ecological
surveys of water bodies in semi-arid regions by
the Environmental Monitoring and Systems Lab
at Las Vegas (4-19). Included in these methods
Were methods for sampling macroinvertebrates
in streams in arid and semi-arid regions with
intermittent flow patterns.
A significant amount of additional methods
have been developed by EPA for specific needs
that have been published but not included in any
of the primary methods manuals. For instance,
the EPA Environmental Research Laboratory at
Gulf Breeze, FL has developed extensive
methods for culturing specific test organisms (4-
20), including brine shrimp (Artemia sp), a
mixohaline rotifer (Brachionus plicatilis), green
alga (Chlorella sp), and four atherinid fish
(Menidia beryllina, M. menidia, M. peninsulas,
and Lauresthes tennis). Included with the
culturing methods were also methods for toxicity
testing.
Lastly, FWPCA program-specific methods
have been developed by EPA that were tailored
to a specific monitoring need and sample matrix.
For instance, in order to satisfy the
requirements of the Ocean Dumping Program,
EPA developed bioassay methods for a wide
variety of marine species (4-21). In conjunction
with the U.S. Army Corps of Engineers, EPA
also developed bioassay methods for dredged and
fill material being discharged into marine and
estuarine environments (4-22). Bioassay
methods were also developed for evaluating the
toxicity to marine organisms of oil and oil
dispersants (4-23). These methods are outdated
and are not being proposed for approval as a
§304(h) method. Dredged material bioassays are
conducted extensively using these methods
within each Corps of Engineers District in
support of maintenance dredging.
Various other methods and guidelines are
available for biomonitoring under other federal
statutes. For instance, extensive guidelines were
developed by EPA to support pesticide
registrations under the Federal Insecticide,
Fungicide, and Rodenticide Act (FIFRA) (4-24).
These guidelines for developing an acceptable
protocol border on being a complete method
since a great deal of procedural information is
incorporated by reference. Many additional
methods have been developed by associations
outside of the federal government. Voluminous
methods, including methods for microbiology,
bioassay testing and field assessments, have
been published by the American Society for
Testing and Materials (ASTM). In many cases,
4-48
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these methods were developed in parallel with
equivalent EPA methods.
Adequacy of Biological Testing
Methods
In this section, adequacy will be evaluated
by comparing the inventory of environmental
analytes required under the FWPCA against the
available test methods identified in the
preceding section. Those methods that monitor a
required analyte will then be reviewed as to
development status (approved, standardized,
available, or in development). Approved or
standardized methods will then be compared to
the criteria for determining adequacy already
discussed. The minimum requirements for a
demonstration of adequacy is that the methods
have been subjected to ruggedness testing, and
that single and multilaboratory precision of the
methods have been established. Lastly, the
section will discuss the need for determining
whether laboratory methods are predictive of
impacts of effluents on the biological integrity of
receiving waters.
Prior to a detailed discussion of the adequacy
of'each test method it should be recognized that
overall, the number and types of approved
biological test methods are inadequate to
support the FWPCA monitoring program. Only
five microbiological parameters are on the
approved list. Clearly, these five parameters
cannot be used to totally satisfy the
Congressional mandated goals of "fishable and
swimmable waters." Methods are needed for
determining the health of ecosystems and their
components, for detecting human pathogens in
water, for preventing possible impacts on fish
and other aquatic biota and man from toxic
chemicals and effluents, for developing water
quality criteria that the states will use in
developing numerous water quality standards,
and for satisfying numerous other requirements
of the FWPCA, the Safe Drinking Water Act and
related statutes. In anticipation of these
programmatic needs, EPA has developed
numerous methods over the last few years.
These methods represent state-of-the-art
knowledge at the time of their development in
each area. Often, EPA has been the motivating
force behind significant scientific advances in
microbiology, virology, aquatic toxicology and
ecology. Since the development of these
methods, there has continued to be additional
scientific advances, additional new
environmental problems have been discovered,
and Congress has established more stringent
clean-up goals. For these reasons, EPA needs to
improve outdated methods, continue to develop
new methods, and continue to assess the
adequacy of its methods for monitoring the
environment.
Adequacy of Approved Methods
The microbiological test procedures that are
approved in 40 CFR 136 have been extensively
used across the nation and internationally for
decades. Fecal coliforms are routinely used to
monitor municipal effluents, certain industrial
effluents, and receiving waters. The ratio of fecal
coliform to fecal streptococci methods is used to
differentiate between non-human and human
sources of fecal pollution. Nonfecal members of
the coliform group occur naturally in water, soil,
and vegetation, and usually survive longer in
water than fecal coliforms; therefore, the
recency of pollution or proximity to the pollution
source can be determined by the fecal coliform
test. As discussed in the inventory section, a
survey of NPDES permits in four regions found
that fecal coliforms were a frequently required
analyte.
Adequacy of Proposed Methods
As previously discussed in the availability
section of this chapter, the Agency recognized
that the list of approved methods in 40 CFR 136
are inadequate to support the biological
monitoring programs under the FWPCA. There
are no EPA-approved methods for viruses,
mutagens, acute or chronic toxicity test
methods. In early 1988, EPA proposed that the
list of approved biological methods will be
amended to rectify this inadequacy. Each
4-49
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proposed addition is discussed below as to
adequacy.
Enteroviruses in Water
The enterovirus in water method being
proposed by the EPA has been evaluated for
ruggedness (4-25), single laboratory precision (4-
25), and multilaboratory precision (4-26). A
coefficient of variation (CV) for single lab
precision of 10-18% was calculated. The
multilaboratory precision of the method was in
the 60-70% range. Based on the available data,
these methods would appear to be adequate. The
EPA methods manual for virology (4-4) is quite
complete and well documented but should be
revised to incorporate recently available data on
test precision and replication of results.
Enteroviruses in Sludge
Ruggedness and multilaboratory precision
studies are available for the method.
Ruggedness (4-25) was determined to be
adequate and multilaboratory precision was
estimated to be within the range of 60-70% (4-
27). These data'are considered by EPA to be
adequate to support the proposed rulemaking.
Ames Test for Mutagenicity
Ruggedness data, and single and
multilaboratory precision studies are all
available on the Ames Test. Overall single
laboratory precision was reported to average +
12% (4-28) and was < 10% CV for 72% of the
groups of three replicate plates. Several studies
of the interlaboratory precision of the test have
been conducted (4-29).
Acute Toxicity Methods for Freshwater
and Marine Organisms
While some 50 species are recommended for
acute toxicity testing, depending on the nature
of the discharge or study site, all of the results
with these various species have been pooled for
comparison. Designed experiments to evaluate
ruggedness are limited to temperature, pH, and
age of test organisms for fathead minnows.
Particularly, few studies appear to be available
that examine the sources of problems in
culturing the organisms, the necessary first step
in toxicity testing.
Precision of acute toxicity tests depends
upon a number of factors, such as the species
used, the age, condition, or health of the
organisms, and test conditions such as
temperature, dissolved oxygen, food, water
quality, and the number of test organisms used
at each toxicant concentration. Single
laboratory test precision has been estimated by
using the same species of organisms under the
same test conditions, and employing a reference
toxicant. Most of the precision data available
were obtained with four standard test organisms
(i.e., Daphnia spp., fathead minnows,
sheepshead minnows and mysids). Limited data
exist for the remaining species. Data on single
laboratory precision (CV) from 92 reference
toxicant tests with three species ranged from
10% to 86% with a weighted mean of 38% (4-30).
The values for multilaboratory precision from
153 reference toxicant tests with six species
ranged from 22-167% and had a weighted mean
of 50%. For the 48 effluents for which single
laboratory data were available, 89.6% of the
effluents had coefficients of variation of less
than 40% and 89.6% of the effluents had
coefficients of variation of less than 30%. For the
141 effluents used in multilaboratory studies,
81.6% of the effluents yielded coefficients of
variation of less than 40% and 74.5% yielded
coefficients of variation of less than 30% (4-11).
EPA considers the single and multilaboratory
precision to be acceptable and the methods to be
suitable for the proposed rulemaking action.
Drilling Fluids Toxicity Test
Although it is also an acute toxicity test, the test
method for drilling fluids (4-30) being proposed
for 40 CFR 136 is a stand-alone method without
reference to the above protocols. A specifically
designed ruggedness test has not yet been
performed on this test method. A criticism of the
method by the regulated industrial community
using the method for compliance, is that the
method is vague or ambiguous at several critical
steps (4-31). A single lab estimate of precision of
4-50
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73% was calculated and a 90% variability was
calculated for multilaboratory variability (mean
estimates). Estimates of precision (CV) made by
EPA at two of its environmental research labs
and with 10 outside contract labs are 35.7% for
single lab precision and 45% for interlaboratory
comparisons (4-32,33).
Chronic Methods for Freshwater
Organisms
Some ruggedness studies of these four test
methods (1000.0; 1001.0; 1002.0; 1003.0) have
been performed. Single lab precision data are
available on all four tests with reference
toxicants and with an effluent for the fathead
minnow embryo-larval survival test. Variability
(CV) ranged from 6-29% for Method 1000.0 on
survival and 6-17% for growth data (4-13). For
Method 1001.0, survival data for fatheads varied
within a single lab by 41-62% for reference
toxicants and maximum precision was obtained
with a trickling filter effluent. For Method
1002.0, maximum precision was also obtained
(values reported in NOEC-LOEC; calculation of
coefficient of variation not possible) in 9 of 10
LOEC calculations and in 6 of 10 NOEC
calculations. For Method 1003.0, three reference
toxicants were tested and variability ranged
from 47-83% for 6-11 replicate tests.
Multilaboratory precision data are available for
3 of the 4 test methods with an effluent (4-13).
Developmental Methods for Future
Consideration
The chronic methods for marine organisms has
been identified by EPA for future consideration
as approved methods. Single lab precision data
are available for both sheepshead minnow tests
as well as the sea urchin method. A
multilaboratory evaluation with the mysid
survival, growth and reproduction test is
planned for reference toxicants and an effluent.
Ruggedness data has yet to be developed, but
additional multilaboratory studies are planned.
Comments received by the EPA during
circulation of the initial draft included the
following:
• A ten laboratory participant multi-
laboratory evaluation of the fathead
minnow larval growth test (which was the
basis for the Menidia and Cyprinodon
methods) has been completed by industry
and EPA labs. Those results should be
considered by EPA for inclusion into the
manual.
• Test standardization between the
freshwater and marine chronic methods is
advisable as well as between the marine
methods. For instance, it was believed that
the number of fish per replicate, the
number of replicates, and the size of the
test containers should be consistent to
allow for minimal equipment and set-up
costs.
• Photoperiods between the freshwater
methods and marine methods are different
(14:10 and 16:8, respectively) and should
be standardized so that a lab can use one
environmental chamber for both types of
testing.
• Number of test concentrations between
marine chronic methods is inconsistent or
not specified. The design of the mysid rapid
chronic toxicity test should be modified to
conform to other EPA tests.
• Additional standard toxicants are needed
and EPA should publish a list of target
toxicity ranges based on multilaboratory
methods.
• Salinity of effluents should be determined
by ionic ratios rather than refractometry
or conductance to avoid false results.
• Reporting of LCi alone is inappropriate.
EMSL-Cincinnati is modifying the
computer programs to calculate LCi, LCio,
and LCso to adjust the results for control
mortality.
• Teratogenicity measurements are
subjective and open to interpretation.
• Drying times and temperatures for larvae
should be standardized to achieve
consistency.
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• The design of the drilling mud acute
toxicity test should be modified to
correspond to other acute toxicity tests.
EPA has considered these comments and made
changes as required before proposing the
methods for comment as part of 40 CFR 136
rulemaking.
Summary of Adequacy
The currently approved biological methods
in 40 CFR 136 are insufficient for performing
the types of analyses required by the various
FWPCA programs. Test methods for
enteroviruses in water and sludge, Ames Test,
acute toxicity test methods for freshwater and
marine organisms, and chronic methods for
freshwater and marine organisms and field
survey methods should be formulated in 40 CFR
136. EPA has recognized this need and proposed
to adopt available, standardized methods to
address these specific needs.
Further standardization for the chronic toxicity
test methods for freshwater and marine
organisms is necessary in order to reduce the
costs of performing the experiments and to
ensure consistent data. Ruggedness, single
laboratory, and multilaboratory precision
studies are still needed for several test methods.
The coefficient of variation (CV) for biological
methods typically ranged from less than 10% up
to 90%. Based on these results, biological
laboratory results are comparable to the
variability observed within and between
laboratories for chemical analyses.
Chapter Four References
1. Environmental Protection Agency's
Methods Equivalency Program for Water
Quality and Water Supply, EPA,
Environmental Monitoring and Support
Laboratory, Cincinnati, OH.
2. Bordner R. and J. Winter, 1978.
Microbiological Methods for Monitoring the
Environment. EPA Office of Research and
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600/8-78-017. 338 pp.
3. Greeson, P.E., et al. 1977. Methods for
Collection and Analysis of Aquatic
Biological and Microbiological Samples. In:
USGS Techniques of Water-Resources
Investigations, Books, Chapter 4A. USGS,
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American Water Works Association, and
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Standard Methods for the Examination of
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5. Berg, G., R. Safferman, D. Dahling, D.
Berman, and C. Hurst, 1984. U.S. EPA
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013. var. pag.
6. Maron, D. and B. Ames, 1983. Revised
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7. Williams, L.R. and J.E. Preston, 1983.
Interim methods for conducting the
Salmonella/Microsomal mutant assay (Ames
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acute toxicity of effluents to aquatic life. 1st
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OH. EPA 600/4-78-012.
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Edition. EPA, Environmental Monitoring
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EPA 600/4- 85-013. 216 pp.
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12. EPA, 1987. Permit Writer's Guide to Water
Quality-Based Permitting for Toxic
Pollutants. Office of Water. Washington,
B.C. EPA 440/4-87-005. 30 pp + app.
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term methods for estimating the chronic
toxicity of effluents and receiving waters to
freshwater organisms. EPA Office of
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Cincinnati, OH. EPA 600/4-85-014.173 pp.
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17. Jacobs, F. and G. Grant, 1978. Guidelines for
zooplankton sampling in quantitative
baseline and monitoring programs. EPA
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Corvallis Environmental Research
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18. Gonor, J. and P. Kemp, 1978. Methods for
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intertidal environments. EPA Office of
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Environmental Research Laboratory,
Corvallis, OR. EPA 600/3-78-087.112 pp.
19. Hornig, C.E., 1978. Macroinvertebrate
sampling techniques for streams in semi-
arid regions. EPA Office of Research and
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20. Middaugh, D.P., M. Hemmer, and L.
Goodman, 1987. Methods for Spawning,
culturing, and conducting toxicity tests with
early life stages of four atherinid fishes: The
inland silverside (Menidia beryllina),
Atlantic silverside (M. peninsulae), and
, California grunion (Leuresthes tenuis). EPA
Office of Research and Development.
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21. EPA, 1976. Bioassay methods for the ocean
disposal permit program. EPA Office of
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Research Laboratory. Gulf Breeze, FL. EPA
600/9-76-010. 96pp.
22. EPA/COE, 1977. Ecological evaluation of
proposed discharges of dredged material into
ocean waters. EPA/COE Technical
Committee on Criteria for Dredged and Fill
Material. U.S. Army Engineer Waterways
Experiment Station. Vicksburg, MS. var.
pag.
23. LaRoche, G., R. Eisler, C.M. Tarzwell, 1970.
Bioassay methods for oil and oil dispersants
toxicity evaluation. J. Wat. Poll. Control.
Fed. 59(1):7-12.
24. EPA, 1982. Pesticide assessment guidelines.
Subdivision E. Hazard Evaluation: Wildlife
and Aquatic Organisms. EPA Office of
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Branch. Washington, D.C. EPA 540/9-82-
024. 86 pp.
25. Dahling, D.R. and B.A. Wright, 1986.
Optimization of the BGM cell line culture
and viral assay methods for monitoring
viruses in the environment. Appl. Environ.
Microbiol. 51:790-812.
26. Melnick, J.L., R. Safferman, V. Rao, S.
Goyal, G. Berg, D. Dahling, B. Wright, E.
Akin, R. Stetler, C. Sorber, B. Moore, M.
Sobsey, R. Moore, A. Lewis, and F. Wellings,
1984. Round robin investigation of methods
for the recovery of poliovirus from drinking
water. Appl. Environ. Microbiol. 47:144-150.
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27. Goyal S., S. Schaub, F. Wellings, D. Berman,
J. Glass, C. Hurst, D. Bradshear, C. Sorber,
B. Moore, G. Bitton, P. Gebbs, and S. Farrah,
1984. Round robin investigation of methods
for recovering human enteric viruses from
sludge. Appl. Environ. Microbiol. 48:531-
538.
28. McDaniels, A.E. and F. Kessler, 198_.
Evaluation of the Ames Test for Detecting
Mutagens in Wastewaters. EPA Office of
Research and Development, Environmental
Monitoring and Support Laboratory.
Cincinnati, OH. DRAFT Report. 38 pp.
29. Dunkel, V., E. Zeiger, D. Brusick, E. McCoy,
D. McGregor, K. Mortelmaus, H.
Rosenkranz, and V. Simon, 1985.
Reproducibility of microbial mutagenicity
assay II. Testing of carcinogens and
noncarcinogens in Salmonella typhimurium
and Escherichia coli. Environ. Mutagen.
7(5):l-248.
30. Federal Register 56(131): 24897-24927.
31, O'Reilly, J.E. and L.R. LaMotte, 1987.
Variability in Drilling Fluids Toxicity Tests.
In: Proc., Tenth Annual EPA Analytical
Symposium on the Analysis of Pollutants in
the Environment. Norfolk, VA. April, 1987.
EPA. Industrial Technology Division.
Washington D.C. IN PRESS.
32. Parrish, P.R. and T. Duke, 1986. Variability
of the acute toxicity of drilling fluids to
mysids (Mysidopsis bahia). In: Proc.,
Symposium on Chemical and Biological
Characterization of Municipal Sludges,
Sediment, Dredge Spoils, and Drilling Muds.
ASTM. Philadelphia. IN PRESS.
33. Bailey, R.C. and B, Eynon, 1986. Toxicity
testing of drilling fluids: assessing
laboratory performance and variability. In:
Proc., Symposium on Chemical aitti
Biological Characterization of Municipal
Sludges, Sediment, Dredge Spoils, and
Drilling Muds. ASTM. Philadelphia. IN
PRESS.
4-54
-------
CHAPTER FIVE
COMPARABILITY OF TESTING METHODS
Introduction and Summary
The explosive demand for environmental
monitoring data over the past ten years has
resulted in a proliferation of analytical methods.
Many of these methods are similar to but
inconsistent with methods already developed.
The consequences resulting from the use of these
methods are that data of varying, and to a large
degree unknown, quality are being generated at
an increasing rate.
This chapter compares methods established
by the EPA and other organizations to methods
established under §304(h). Due to the sheer
number of methods available for any given
analyte, it was impossible to provide detailed
comparisons of all methods.
Detailed comparisons were performed for the
following generic techniques:
• Selenium by graphite furnace atomic
absorption spectrometry (GFAAS)
• Metals by inductively coupled plasma
spectroscopy (ICP)
• Volatile organics by purge and trap gas
chromatography/mass spectrometry
(GO/MS)
• Semivolatile organics by solvent
extraction Gas Chromatograph/Mass
Spectrometry (GC/MS)
• Halbgenated volatile organics by purge
and trap gas chromatography with
electrolytic conductivity detection
(GC/HECD)
• Organochlorine pesticides and PCB's by
gas chromatography with electron capture
detection (GC/ECD)
These six techniques cover a range of widely
used techniques which form the basis for the
measurement of the toxic priority pollutants in
the FWPCA, the Appendix IX compounds under
RCRA and the target analytes of the Superfund
Contract Laboratory Program.
Based on the detailed comparisons of these
six techniques and a general review of other
methods, the following findings were obtained:
• Although many methods are available for
a given analyte, the procedures are
essentially the same. Specific operational
details differ among the methods, typically
for no apparent reason. Although the
various versions of a procedure may
indicate different method performance
characteristics (e.g., lower detection limits,
better precision) the procedural details do
not clearly support these stated differences
in performance.
• The EPA methods for toxic chemicals in 40
CFR 136 are highly developed,
documented and standardized relative to
other methods for environmental
measurements.
• The QA/QC requirement in the methods
vary significantly, are generally deficient
in non-EPA methods, inconsistent among
5-1
-------
EPA programs, and confusing in many
situations (e.g., SW-846).
• Virtually all of the methods reviewed were
based on methods originally developed
under §304(h).
These findings suggest that the EPA
methods that have been enhanced by QA/QC
practices should supersede the non-EPA
methods that have not been so enhanced, and
that the various EPA methods and QC
requirements should be consolidated.
Definition of and Approach to Reviewing
Test Methods
The test methods used by EPA and other
organizations are usually highly technically
detailed and involve dozens of discrete steps. For
example, the Statement of Work (5-1) for
determination of organic analytes under the
Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA;
"Superfund") Contract Laboratory Program
contains 426 pages of mostly single spaced text
defining innumerable steps. As a result, it was
not possible within the time available to
compare in detail all test methods for a given
analyte. Therefore, the comparisons of test
methods in this study are generally based upon
review of condensations of these methods. As
with the selection of the test methods to be
compared and with all condensations, certain
features of the methods are emphasized over
others. These are the features most important to
control the quality of results produced.
The EPA test methods for toxic pollutants
have come under microscopic scrutiny by
Agency scientists, by various offices within
EPA, by EPA contractors, by non-EPA
organizations using these methods, by
manufacturers of analytical equipment, and by
the industries that EPA regulates. In response
to notices in the Federal Register, the Agency
has received many comments on its test
methods, and has strived to modify and expand
its test methods to address the concerns set forth
in the comments. Over the last decade, the
comments and criticisms have been leveled at
EPA methods for determination of toxic organic
and trace metal analytes as well as bioassay
methods, and most recently at the quality
assurance/quality control (QA/QC)
requirements and specifications in these
methods. In this study, EPA has therefore given
principal attention to the comparison of test
methods for determination of the organic and
trace metal analytes and aquatic toxicity.
Background for Comparison of
Testing Methods
EPA methods for determination of
pollutants in environmental samples are
necessitated by'the Agency's requirement to
monitor environmental pollution. This
monitoring can be pro-active, as in the case of
the National Pollutant Discharge Elimination
System (NPDES) program or reactive, as in the
case of clean-up at abandoned hazardous waste
disposal sites. These varying monitoring
requirements result in different characteristics
for the analytical methods developed under
these programs. A brief background of the
evolution of certain of the Agency's methods
resulting from differing monitoring
requirements is described in this sub-section.
Federal Water Pollution Control Act
Section 304(h) of the FWPCA requires the
EPA Administrator to promulgate guidelines
establishing test methods for analysis of
pollutants that must be provided in any
certification pursuant to §401 of the Act or
permit application pursuant to §402 of the Act.
The Administrator has also made these test
methods applicable to monitoring and reporting
of NPDES permits (40 CFR 122, 122.21, 122.41,
122.44, and 123.25), and implementation of the
pretreatment standards issued under §307 of the
Act (40 CFR 403, 403.10 and 403.12). The test
methods for these purposes have been
promulgated at 40 CFR 136. A structure and
history of 40 CFR 136 has been given in the
preamble to the promulgation of the methods (49
FR 43234, October 26,1984).
The methods for organic toxic pollutants in
40 CFR 136 were developed in response to a
Consent Decree (Natural Resources Defense
Council, Inc., et al. vs. Train, 8 ERC 2120,
D.D.C. 1976). These methods comprise a
5-2
-------
methods set, and are designed to determine the
114 organic "priority pollutants" listed in the
Consent Decree. The methods were first
proposed in the Federal Register in 1979 (44 FR
69469, December 3, 1979), and were
promulgated as Appendix A of 40 CFR 136 in the
October 26,1984 notice.
The methods were validated through
interlaboratory studies between proposal in
1979 and promulgation in 1984. These methods
form the basis for almost all subsequent EPA
methods for organic pollutants in water
(including drinking water, groundwater, surface
water, seawater, and waters from all other
sources), and for subsequent American Society
for Testing Materials (ASTM) methods, U.S.
Geological Survey (USGS) methods, and
"Standard Methods for Examination of Water
and Waste water" (Standard Methods). The
methods developed by the RCRA and Superfund
programs for the analysis of soils, wastes and
biological tissue are all based on the FWPCA
methods.
The inorganic methods to support the
FWPCA and Safe Drinking Water Act (SDWA)
were published in Environmental Monitoring
and Support Laboratory (EMSL- Cincinnati),
Methods for Chemical Analyses of Water and
Wastes (5-2), ASTM's Annual Book of Standards
(5-3), USGS's methods manual (5-4), and
Standard Methods (5-5). The methods are
written for analytical chemists and contain most
of the steps necessary to assure a given level of
data quality. However, the EPA method for
metals by Inductively Coupled Plasma
Spectroscopy (ICP), Method 200.7 (5-6) does the
best job of defining the quality control
requirements. While the method for the analysis
of metals by ICP are well defined, the other
inorganic methods lack performance
characteristics and specific criteria for method
performance. EPA has remedied these
deficiencies to some degree as a result of a
settlement agreement (5-7) by publishing
interlaboratory method validation study data for
a number of EPA inorganic methods directly in
40 CFR 136. To date, the Agency has yet to
publish performance criteria for any of the
methods for inorganics in 40 CFR 136.
Superfund Contract Laboratory Program
(CLP) Protocols
The test methods used by the CLP are more
properly called protocols than methods because
they have very explicit contractual and
reporting requirements included within the
methods. These protocols were designed to
supply legally defensible environmental data. In
addition to methods for determination of organic
and inorganic pollutants in waters, the protocols
contain provisions for determination of the
pollutants in other sample matrices. The Agency
conducts approximately 7,000,000
determinations per year on over 90,000 samples
with a wide variety of matrices using these
protocols through contracts with commercial
analytical laboratories.
The significant feature of these protocols is
that substantial evidentiary materials are
embedded in the methods. Therefore, if the
protocol is used for general analytical uses not
involving court proceedings, a large amount of
unnecessary paperwork is delivered at
significant additional cost per analysis. To date,
laboratories performing work for potentially
responsible parties (PRP's), have not been
required to follow the CLP protocols.
Office of Solid Waste Methods
These methods are contained in a
comprehensive document titled "Test Methods
for Evaluating Solid Waste" (SW-846) (5-8).
These methods are primarily designed for
determining if a given waste is hazardous or if
groundwater contamination is occurring and are
prepared to address a wide variety of sample
matrices. The manual separates the analytical
methods into components such as sample
preparation and analysis. For example, the
FWPCA and SDWA methods and the Superfund
CLP protocols give separate, fully contained
methods for the analysis of a sample type, and
include continuous steps for extraction,
concentration, extract cleanup, instrument
calibration, analysis, quality control, and, in the
case of the CLP protocols, data reporting. The
RCRA manual separates these steps into
separate methods and gives separate method
numbers to each step. The major advantage is
5-3
-------
that it tends to force standardization of common
procedures such as determinative steps for
multiple sample types. The major disadvantage
is that the compilation becomes quite large (the
Third Edition of SW-846 is distributed in four
volumes) and accumulates, of necessity, much
extraneous discussion for the user who desires to
analyze for a relatively simple matrix such as
groundwater. In addition, editing the huge
document for consistency is a formidable task;
careful reviews of the Third Edition reveal that
the general quality control requirements
sometimes directly contradict the specific
requirements within a method.
Drinking Water Methods
Under the SDWA, approved analytical
methods are promulgated in 40 CFR 141. The
sources for the approved methods for inorganic
analyses are the same as those under the
PWPCA, which includes EMSL-Cincinnati,
ASTM, Standard Methods, and the U.S.G.S. For
organics, however, EMSL-Cincinnati provided a
new series of organic methods for compliance
monitoring of organic compounds in finished
drinking water and raw source water. EPA's
organic methods for SDWA are known as the
"500 Series" (i.e., 502.1, 502.2, 503.1, 504, 524.1
and 524.2). EMSL-Cincinnati's "600 Series"
methods promulgated for priority toxic organics
under FWPCA, although technically nearly
identical, were considered for the regulation of
volatiles, but were abandoned after public
comment because the analytical objectives were
different and therefore the quality control
requirements were much different. The "500
Series" methods are designed to provide data at
concentration levels at and below the
promulgated maximum contaminant levels
(MCL).
Comparison of Testing Methods
The remainder of this section presents the
detailed method comparisons for the six
techniques discussed previously (4 chemical, 2
biological). For each technique, a comprehensive
table was prepared that documents key method
characteristics (e.g., detection limits,
instrument condition, QA/QC requirements) for
the methods reviewed. Not all of the method
characteristics lend themselves to easy
tabulation. For example, the holding times in
the Superfund program are a contractual
requirement for the analytical laboratory. Thus,
the holding times begin upon receipt at the
laboratory rather than at time of collection.
Comparison of Methods for
Determination ofOrganochlorine
Pesticides
Organochlorine pesticides have been one of
the most important groups of compounds to EPA
since the Agency's founding. Many of the
analytes in this group have caused significant
environmental damage. Among the
organochlorine pesticides are lindane,
heptachlor, chlordane, toxaphene, and DDT.
Most Agency methods for organochlorine
pesticides also measure polychlorinated
biphenyls (PCB's). For these reasons, methods
for determination of these compounds are
available for all of the major water-related
programs within EPA (FWPCA, SDWA,
Superfund, and RCRA), and from other
organizations (ASTM, USGS, and Standard
Methods). Therefore, this technique was selected
to represent a wide variety of the organic
methods available that involve solvent
extraction followed by gas chromatography
analysis.
Table V-l compares the salient
characteristics of eight methods studied for the
determination of chlorinated pesticides and
PCB's in water by extraction and gas
chromatography with electron capture
detection. The major characteristics of these
methods are given in the method title; i.e., they
all use an extraction technique to remove the
pesticide from the wastewater; they all use gas
chromatography for separation and
identification of the analytes; and they all use
electron capture for detection of the analytes.
Gas chromatography is a technique used for
separation of the components of mixtures of
organic compounds; electron capture is an
instrumental measurement technique whereby
the molecule detected captures a free electron,
resulting in a net decrease in current through
the detector. Gas chromatographs with electron
capture detectors are available from more than
5-4
-------
Table V-l Methods for Determination of Chlorinated Pesticides and Polychlorinated Biphenyls (PCB's) in Water by
Extraction and Gas Chromatography with Electron Capture Detection
ivitni luu
Characteristic
Method Number
(if any)
Revision Date
Number of
analytes covered
Format
Sample
Holding time
Preservation
Volume required
Extraction
Solvent
Technique
Concentration
Technique
Final solvent
Final extract
volume
Cleanup
techniques
Gas
chromatograph
Column
temperature
Column
Type
Primary
Confirmatory #1
Confirmatory #2
vvaiBf
Regulations
608
1984
25
EMSL-Ci
< 72 hr or
pH 5 -9
4C +
sodium thio
1 Liter
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Hexane
5 mL
Florisil/sulfur
Iso @ 200
C
Packed
SP-
2250/SP-
2401
OV-1
Not given
uniiKiiiy
Water
505
1986
18
EMSL-Ci
<14 days
4C +
sodium thio
35 mL
Hexane
Micro-
extraction
None
Hexane
2 mL
None
180-260
@ 4 C/min
Capillary
DB-1
Durawax
DX-3
OV-1 7
Lfrirming
Water
508
1986
32
EMSL-Ci
No spec
4 C + mere
chlor
1 Liter
Methylene
chloride
Sep funnel/
tumble
Kuderna-
Danish
MTBE
5 mL
None
60-300 @
4 C/min
Capillary
SPB-5
DB-1701
Not given
Solid Waste
8080
1986
26
No formal
document
No spec
No spec
1 Liter
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Hexane
5mL
Florisil/sulfur
See Method
608
Packed
SP-
2250/SP-
2401
OV-1
Not given
cjupenuna
CLP
CLP-MM
1987
26
No formal
document
< 5 days
4 C, in dark
1 Liter
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Hexane
1 mL
GPC/Alumin
a/sulfur
Isothermal
@192C
Packed/Capi
llary
OV-
17/OV-210
OV-1
OV-210
ASTM
D 3086-85
1985
20
ASTMD
No spec
No spec
1 Liter for
ECD
MeCI2 +
Hexane
Sep funnel
Kuderna-
Danish
Hexane
1 mL
Flor/Alum/S
G/TLC
Isothermal
@200C
Packed
0V-
17/OV-210
OV-210
OV-1
USGS
D 3104-83
1983
24
TWRI
No spec
No spec
1 Liter
implied
Hexane
Sep funnel
Kuderna-
Danish
Hexane
1 mL
Alumina/Silic
a Gel
Not given
Packed
SP-2100
SP-
2250/SP-
2401
Not given
standard
Methods
509
1985
19
No spec
No spec
1 Liter
MeCI2 +
qBB
qHexane
Sep funnel
Kuderna-
Danish
Hexane
10 mL
Florisil
Isothermal
@200C
Packed
OV-1
OV-210
OV-
17/SP-
2401
(Continued)
5-5
-------
Table V-1 (Continued)
Method
Characteristic
Confirmatory #3
Calibration
Technique
Number of points
Linearity
Frequency of
verification
Verification
specification
Qualitative
identification
Retention time
agreement
DDT/Endrin
breakdown
Determination of
Lindane
Concentration
range
Detection limit
Quantitation
limit
Percent recovery
Precision (%
BSD)
Quality
Control/Assuran
ce(QA/QC)
Initial accuracy
Initial precision
Blanks
Frequency
Specification
Surrogate
recovery
Frequency
Specification
Water
Regulations
Not given
Int or ext std
3 minimum
<10% RSD
RF or OF
Daily
+/- 15% RF
orCF
+/-3std
devRT
No spec
0.016-4.0
ug/L
MDL=0.00
4 ug/L
0.012 ug/L
est
80 (Inter-
lab)
22 (Inter-
lab)
Spec in
table
Spec in
table
Each
sample set
No spec
Every
sample
No spec
Drinking
Water
Not given
External
standard
3 minimum
<10% RSD
ofCF
Daily
+/- 15% CF
No spec
Endrin
<50%
Not given
MDL=0.00
3 ug/L
PQL=0.015
ug/L
91 (Single
lab)
7 (Single
lab)
No test
No spec
Daily
-------
Table V-l (Continued)
Method Water
Characteristic Regulations
Matrix spike
recovery
Analytes covered
Frequency
Specification
All
10%
minimum
In table
Drinking
Water
All
10%
No spec
Drinking
Water
All
10%
No spec
Solid Waste
All
10%
minimum
In table
Superfund
CLP
Subset
5%
minimum
In table'
ASTM
No test
No test
No spec
USGS
No test
No test
No spec
Standard
Methods
No test
No test
No spec
Duplicate
analyses
Analytes covered
Frequency
Specification
Statement of
data quality
Safety
No test
No test
No test
Recovery
+/-2SD
Explicit
warnings
No test
No test
No spec
Not
required
Explicit
warnings
Those in
samples
10%
minimum
No spec
Not
required
Explicit
warnings
All
5%
minimum
No spec
Recovery
+/- 2 SD
Not given
Subset
5%
minimum
In table
Not
required
Not given
No test
No test
No spec
Not
required
Explicit
warnings
No test
No test
No spec
Not
required
Not given
No test
No test
No spec
Not
required
Not given
References:
Method 608-Organochlorine Pesticides and PCBs, 40 CFR Part 136 [49 FR 43234, October 1984].
Method 505: "Analysis of Organohalide Pesticides and Aroclors in Drinking Water by Microextraction and Gas
Chromatography", Supplement to "Methods for the Determination of Organic Compounds in Finished Drinking Water and
Raw Source Water", Physical and Chemical Methods Branch, Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati Ohio 45268, September 1986.
Method 508: "Determination of Chlorinated Pesticides in Ground Water by Gas Chromatography with an Electron Capture
Detector", Supplement to "Methods for the Determination of Organic Compounds in Finished Drinking Water and Raw
Source Water", Physical and Chemical Methods Branch, Environmental Monitoring and Support Laboratory, U.S.
Environmental Protection Agency, Cincinnati Ohio 45268, September 1986.
Method 8080: "Organochlorine Pesticides and PCBs", "Test Methods for Evaluating Solid Waste", SW-846, Volume IB:
Laboratory Manual, Physical/Chemical Methods, Office of Wolid Waste and Emergency Response, U.S. Environmental
Protection Agency, Washington, DC 20460, Third Edition, November 1986.
Statement of Work for Organics Analysis, Multi- Media, Multi-Concentration, USEPA Contract Laboratory Program,
Analytical Support Branch, Office of Emergency Response, U.S. Environmental Protection Agency, Washington DC 20460,
October 1986.
ASTM Standard D3086-85: "1986 Annual Book of Standards", Section 11: Water and Environmental Technology, Volume
11.02: Water, American Society for Testing Materials, 1916 Race St, PhiladelphiaPA 19103,1986.
"Organochlorine and organophosphorus compounds, total recoverable (O-3104-83) and dissolved (O-l 104-83), gas
chromatographic", "Methods for the Determination of Organic Substances in Water and Fluvial Sediments", U.S. Geological
Survey Techniques of Water-Resources Investigations, Book 5, Laboratory Analysis, Chapter A3, Open-File Report 82-1004,
U.S. Geological Survey, Room 5A420, National Center, 12201 Sunrise Valley Drive, Reston, VA 22092,1983.
Section 509A, "Organochlorine Pesticides", "Standard Methods for the Examination of Water and Wastewater", Prepared and
published jointly by American Public Health Association, American Water Works Association, Water Pollution Control
Federation, Publication Office: American Public Health Association, 1015 Fifteenth St NW, Washington DC 20005,
Sixteenth Edition, 1985.
5-7
-------
five major instrument manufacturers and as
many as 30 minor manufacturers.
The data in Table V-l reveal that all of the
methods use nearly identical materials,
equipment, and operating conditions. The most
significant difference is in the use of capillary
GC columns in the method chosen to represent
the most current drinking water methods. The
Agency is actively pursuing the incorporation of
capillary column technology into all appropriate
methods.
However, the methods are shown to provide
different performance. For example, the method
detection limit for a typical analyte, lindane,
varies from 0.001 to 0.01 ug/L. Furthermore the
methods use different detection limit terms
(MDL, DL, PQL, CRDL, MQL).
The QA/QC requirements vary from no
requirements to requirements that specify the
type, frequency and acceptance criteria for all
QC samples. For example, calibration
requirements are specified as "daily", "each
shift" and "each 72 hours" or in some cases not
specified.
The data in Table V-l also reveal that
although there are numerous inconsistencies
among the EPA methods, they are more highly
developed than non-Agency methods. Major
deficiencies exist in the calibration and quality
assurance/quality control (QA/QC) section of the
non-EPA methods. Unless these details are
carefully specified in the methods, laboratories
performing analyses will produce results of
unknown and, probably, less than optimal
quality.
Comparison of Methods for the
Determination ofHalogenated Volatile
Organics
Halogenated volatile organic compounds are
a group of low molecular weight compounds that
are of concern because of their widespread use
and toxic and carcinogenic effects. Many of the
compounds in this group have been detected in
drinking water supplies. The compounds in this
group typically contain one to six carbon atoms
with one or more halogenated (chlorine,
bromine, fluorine or iodine) atoms. Examples of
these compounds include vinyl chloride,
chloroform, trichloroethylene and ethylene
dibromide.
Compounds in this class typically have
boiling points of less than 200°C and water
solubilities of less than 1%. These two physical
properties enable the compounds to be measured
by a technique involving: 1) gas stripping the
compound from water (purging); 2) trapping the
compounds on a solid sorbent (trapping); 3)
transferring the compounds from the solid
sorbent to a gas chromatograph with high
temperature and gas flow (desorbing); and 4)
separating and identifying the compounds by
means of a gas chromatograph (GC). This
technique, termed "purge and trap GC" has been
adapted into many Agency methods.
Compounds which can be purged, trapped,
desorbed and chromatographed also include non-
halogenated compounds such as benzene and
carbon disulfide. Described -elsewhere in this
chapter is a technique using purge and trap GC
with a mass spectrometer (MS) as a detector.
Purge and trap GC/MS techniques can measure
a broad range of volatile compounds, including
halogenated volatiles.
However, GC/MS techniques have several
limitations, including the cost and complexity of
the instrumentation and the limited sensitivity
of the MS detector. An alternative detector, the
Hall electrolytic conductivity detector (HECD),
can be coupled with the purge and trap GC
technique to selectively measure halogenated
species. This detector system, developed
commercially by Coulson and Hall, is based on
the pyrolysis of halogenated organics in a
hydrogen atmosphere to inorganic acids (e.g.,
HX) extraction of the monitored species from the
gaseous reaction products stream into the
conductivity solvent and the detection of the
monitored species by the change in resistance of
the conductivity solvent.
As shown in Table V-2, six methods for
halogenated volatile organics were reviewed. A
review of the operational details of the methods
reveals that all of the methods use virtually
identical reagents, equipment and operating
conditions. The only significant difference in
these methods is in the use of a capillary GC
5-8
-------
Table V-2 Comparison of Methods for the Determination of Halogenated Volatile Organics in Water by Purge and
Trap Gas Chromatography with Electrolytic Conductivity Detection
Method Water DrinkingWater DrinkingWater SolidWaste ASTM Standard
Characteristics Regulations Methods
Method Number
Revision Date
Number of
Analytes
Sample
Collection
Sample
Preservation
Holding Time
Purge Gas
Purge Rate,
mL/min.
Purge time,
minutes
Trap Size
Trap Packing
Desorb temp.,°C
Desorb time,
min.
GC Column
Type
Primary Column
GC Conditions
Confirmatory
Column
Calibration
Technique
Number of
Calibration
points
601
1984
29
25 mL minimum
volume
4°C
14 days
N2orHe
40
11.0
25cm
1.0cm 3%OV-1
7.7cmTenax7.7
cm Silica Gel 7.7
cm charcoal
180
4
Packed
1% SP-1000
3 min. at 45°C
8°C/min.
to220°C
n-Octane on
Porasil C
Internal or
External
3
502.1
1896
38
Duplicate
samples, 40- 120
mL
4°C,l:lHClto
pH<2
14 days
N2orHe
40
11.0 + 0.1
25cm
1/3 Tenax
1/3 Silica Gel
1/3 Charcoal
180
4.0 ± 0.1
Packed
1% SP-1000
3 min. at45°C
8°C/min. to
220°C
n-Octane on
Porasil C
Internal or
External
5
502.2
1986
58
Duplicate
samples, 40-120
mL
4<>C,l:lHClto
pH<2
14 days
N2 or He
40
11.0 + 0.1
25cm
1/3 Tenax
1/3 Silica Gel
1/3 Charcoal
180
4.0 ±0.1
Capillary
VOCOL
8 min. at 100°C
4°C/min. to
180°C
NS
Internal or
External
5-
8010
1986
39
Duplicate
40 mL
4 drops cone.
HC1,4°C
14 days
N2orHe
- 40
11.0 + 0.1
1/3 Tenax
1/3 Silica Gel
1/3 Charcoal
180
4
Packed or
1% SP-1000
3min.at45°C
8°C/min. at
220°C
n-Octane on
Porasil C
Internal or
External
5
D3871-84
1984
NS
NS
4°C
a few hours if
possible, or 15
days
N2 or He
40
12 or longer
150 mm
100 mm Tenax
50 mm Silica Gel
180 ±5
4
Packed
Capillary
Suitable
Packing
4 min. at 60°C
8°C/min. to
170°C
NS
External
NS
514
1985
NS
Duplicate
4°C
as soon as
possible
N2 or He
40
11.0
25cm
lcm3%OV-l 15
cm Tenax
8 cm Silica Gel
180
4.0
Packed
0.2% Carbowax
1500
3 min. at 60°C
8°C/min. to
160°C
n-Octane on
Porasil C
External
NS
(Continued)
5-9
-------
Table V-2 (Continued)
Method Water
Characteristics Regulations
Linearity
check
Calibration
Frequency
Calibration
Specification
Retention time
Specification
Identification
Specification
second Column
Confirmation
Method
Performance
Data,
Detection
Limits ug/1
Accuracy %
Precision, SD
QA/QC
Requirements
Initial
Demon-
stration
Accuracy
Check
Accuracy
Specifi-
cation
Recovery
Check
Recovery
Specifi-
cation
Requirements -
Ongoing
Blanks
Spikes
Duplicate
QC Checks
QC Accept-
ance
Criteria
Certification
PE Samples
±10% RSD
Daily
Acceptance
Criteria for
each
parameter
NS
Retention time
agreement
within 3 T
Can be used
Trichloro-
ethylene MDL,
0.12
87est
20est
NS
4 QC check
samples
Compare to
table
4 QC check
samples
Compare to
table
Daily
10% or
I/month
Recommended
Varies
Provided
NS
Recommended
Drinking
Water
±15% RSD
Daily
RF ± 20%
< 10% over 8
hours
NS
Can be used
MDL, 0.001
\
92est
29est
7 replicates
at 2 ug/1
MDL Study
90-100%
MDL Study
<35% RSD
Daily
NS
NS
10%
60-140%
Required in
program
Recommended
Drinking
Water
±15% RSD
Daily
RF±20%
< 10% over 8
hours
NS
NS
MDL, 0.0
96
3.5
7 replicates
at 2 ug/1
MD1 Study
80-120%
MDL Study
< 30% RSD
Daily
NS
NS
10%
60-140%
Required in
program
Recommended
Solid Waste
±20% RSD
Daily
RF + 15%
NS
± 3 T of three
absolute
retention times
Normally is
required
PQL, 1.2
601 Data
601 Data
NS
4 QC check
samples
601 Data
4 QC check
samples
601 Data
Daily
One per batch
Recommended
Varies
Provided
NS
Recommended
ASTM
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Standard
Methods
NS
NS
NS
NS
NS
Required for
unknown
samples
LOD for each
sample
NS
NS
NS
NS
NS
NS
ND
Daily
NS
NS
Daily
NS
NS
NS
(Continued)
5-10
-------
Table V-2 (Continued)
References
Method 601: "Purgeable Halocarbons", 40 CFR Part 136
Method 502.1: "Volatile Halogenated Organic Compounds in Water by Purge and Trap Gas Chromatography," Physical and
Chemical methods Branch, Environmental Monitoring and Support Laboratory, USEPA.Cincinnati, OH,
September 1986.
Method 502.2: "Volatile Organic Compounds in Water by Purge and Trap Capillary Column Gas Chromatography with
Photoionization and Electrolytic Conductivity Detectors in Series", Physical and Chemical Methods, Branch,
Environmental Monitoring and Support Laboratory, USEPA, Cincinnati, OH, September 1986.
Method 8010: "Halogenated Volatile Organics", "Test Methods for Evaluating Solid Waste, SW-846, Third
Edition, Volume IB "Office of Solid Waste and Emergency Response, USEPA, November 1986.
ASTM Standard
D3871-84: "Organic Compounds, Purgeable, Headspace Sampling", "1987 Book of Standards", Section ll:Water and
Environmental Technology, Volume 11.02: Water, American Society for Testing Materials, Philadelphia, PA.
Section 514: "Halogenated Methane and Ethane, by Purge and Trap", "Standard Methods for the Examination of Water and
Wastewater", APHA/AWWA, Sixteenth Edition, 1985.
column in Method 502.2. This method is the
most recently developed of the six methods.
Because of the improved characteristics of this
method, it is expected that the other methods
will evolve toward this technique.
A review of these methods reveals trivial
differences that may or may not affect the
performance. For example, all methods but one
specify an eleven minute purge time. One
method, ASTM Method D-3871-84, specifies a
twelve minute purge time. The methods all use a
25-cm trap. However, the packings and relative
amount of each packing varies. As in the other
methods, the QA/QC requirements vary
tremendously.
Although most of the methods specify a
holding time of 14 days, the preservation varies
from 4°C to 1:1 HC1 to pH <2 to "4 drops of
concentrated HC1". The methods are stated to
provide different levels of performance. For
example, the "detection limits" (MDL, PQL, etc.)
for trichloroethylene ranged from 0.001 to 1.2
ug/L. As in the other examples, the EPA
methods were more developed and the method
details, especially QA/QC requirements, were
more fully documented than the non-EPA
methods.
Comparison of Methods for the
Determination of Organic Compounds by
Gas Chromatography/Mass
Spectrometry
The use of gas chromatography/mass
spectrometry (GC/MS) techniques for the
analysis of organic constituents in water has
gained widespread use because of the ability of
the mass spectrometer to detect and measure a
large variety of compounds. Furthermore, the
technique can be used to deduce the structure of
a compound based on mass fragmentation
patterns. This latter aspect of the technique is
particularly important in the analysis of
samples containing hundreds of contaminants.
Although many specialized GC/MS
techniques have been developed (e.g., the
methods for dioxins) the predominant use of
GC/MS techniques is for the general analysis of
a sample for a specific list of compounds. GC/MS
techniques usually involve the following steps:
• isolation of the target analytes from the
sample matrix,
• concentration of the target analytes,
• separation of the components on a gas
chromatograph, and
• detection and quantitation of the analytes
with the mass spectrometer.
These general operations are used for both
the "analyzed for" approach and the approach
used to deduce the structure of unknown
compounds.
However, the "analyzed for" approach adds
two additional steps: 1) calibration with known
reference materials; and 2) additional criteria
for compound identifications. These two steps
can result in reliable identification and
quantitation of specific compounds when
5-11
-------
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5-14
-------
Table V-3 (Continued)
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itographic/mass spectrometr
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nation of Water and Wastewi
tion, Publication Office: Ame
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"Purgeable organic compounds, total reco
Determination of Organic Substances :
Book 5, Laboratory Analysis, Chapter
Valley Drive, Reston, VA 22092, 1983.
Section 514: "Halogenated Methanes and
Spectrometric Method," "Standard Me
Water Works Association, Water Pollu
Washington DC 20005, Sixteenth Edit
5-15
-------
standardized methods are properly used. GC/MS
is a powerful tool in its ability to provide
structural information. However, there are
varying degrees of confidence in the ability of
this technique to unequivocally "identify" an
unknown compound. For this reason, the
"analyzed for" approach is generally preferred to
techniques oriented at identifying unknown
compounds.
Two general techniques are used for GC/MS
analyses. These techniques, were developed
based on the volatility of the compounds.
Compounds of high volatility and low water
solubility are termed "volatile" organics and
typically measured by "purge and trap" GC/MS.
The concepts of purge and trap GC were
discussed previously. The second technique
involves the solvent extraction of compounds
from the sample matrix with subsequent
analysis. Compounds mea'sured by this
technique have been defined as "semivolatile" or
"extractable" compounds. Due to pH
adjustments that are sometimes incorporated in
the solvent extraction step, subcategories of
analytes have evolved that reflect the
fractionation of the bases and neutral organics
(B/N) together, separate from the acid analytes.
Tables V-3 and V-4 compare the methods
that have been developed for the determination
of volatile and semivolatile organics by GC/MS.
Table V-3 compares the characteristics of eight
methods which use the purge and trap GC/MS
technique developed in Method 624 for volatile
organics. As shown in this table, the methods
have virtually identical operational conditions.
However, the methods have different
specifications for "identifying" a compound. For
example, Method 624 specifies that the retention
time must agree within 30 seconds from the
standard retention time, the key fragment ions
must maximize within one scan and the relative .
ion intensities must be within ±20% of the
reference spectra. Method 8240 specifies a
relative retention time (±0.06) has no
specification for maximization of key ions and
specifies that absolute ion intensities must be
±20%.
Other similar "differences" are documented
in Table V-3. It is unclear as to whether any of
these differences contributed to the differences
in method performance (detection limits,
precision, etc.) that are stated in the methods.
Table V-4 compares six GC/MS methods for
semivolatile organics. As in the other tables, the
methods shown in this table have similar
operational analytes, and, as in the other tables,
some differences are contained in the methods.
For example, the mass spectral agreement
criteria are specified as ±20% of the standard,
±50% relative abundance, ±20% absolute
abundance and >950 FIT.
Comparison of Methods for Determining
Metals by Graphite Furnace and ICP
Emission Spectroscopy
Many metals such as lead, cadmium,
selenium, arsenic, etc., are of environmental
concern and have been tested for years. Methods
for the determination of metals are included
among EPA's 304(h), SDWA, Superfund and
RCRA method compilations as well as from
other organizations such as ASTM, USGS and
Standard Methods. Table V-5 compares the
salient characteristics of methods for the
determination of metals in water by acid
digestion and analysis with graphite furnace
atomic absorption spectrophotometry (GFAAS).
Table V-6 compares the sample preparation and
analysis for metals by spectroscopy.
The three major EPA programs are listed in
the tables along with the comparable methods
from ASTM and Standard Methods. The
FWPCA and SDWA both use MCAWW methods
and, therefore, are combined in Tables V-5 and
V-6. Table V-5 lists the general atomic
absorption (AA) methods with the number of
analytes covered in the general method. The
method for determining selenium (Se) in water
was selected as a representative of the
individual "200" series AA methods. Table V-6
compares the ICP methods for all the analytes.
Cadmium was selected as a representative
metal.
The major characteristics of the AA methods
are the same. They use acid digestion with nitric
acid and hydrogen peroxide, the same matrix
modifiers and instrument conditions, and have
nearly identical ranges and detection limits.
There are small differences in the digestions
5-16
-------
Table V-4 Methods for Determination of Semi volatile Organic Compounds in Water by Gas Chromatography/Mass
Spectrometry
Method Characteristic
Method Number (if any)
Revision Date
Number of analytes covered
Format
Sample
Holding time,
Preservation
Volume required
Extraction
Fractions
Solvent
Technique
Concentration
Technique
Final solvent
Final extract volume
Cleanup techniques
Gas chromatograph
Column temperature
Initial
Program
Final
Column
Type
Base/neutral
Acid
Semivolatile (B/N + acid)
Calibration
Technique
water
Regulations
608
1984
81
EMSL-Ci
< 7 days
4 C + sodium
thio
• 1 Liter
B/N; Acid
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Methylene
chloride
ImL
None
4 min @ 50 C
50-270@8
C/min
270 until
elution
Packed
3%SP-2250
1%SP-
1240DA
Not applicable
Internal
standard
ITD
1625, Revision
C
1986
176
EMSL-Ci
< 7 days
4 C + sodium
thio
35 mL
B/N; Acid;
Semi-
Methylene
chloride
Continuous
Kuderna-
Danish
Methylene
chloride
ImL
GPC
5 min @ 30 C
30-280® 8
C/min
280 until
elution
Capillary
0.25 mm DB-5
0.25 mm DB-5
0.25 mm DB-5
Isotope
dilution
Solid Waste
8270
1986
118
No formal
document
< 7 days
4 C + sodium
thio
1 gallon
B/N; Acid;
Semi-
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Methylene
chloride
ImL
GPC; many
other
4 min @ 40 C
40 - 270 @ 10
C/min
270 until
elution
Capillary
.25 or .32 mm
DB-5
.25 or .32 mm
DB-5
.25 or .32 mm
Internal
standard
Superfund
CLP-MM
.. 1987
64
No formal
document
< 5 days
4 C, in dark
1 Liter
B/N; Acid;
Semi-
Methylene
chloride
Sep
funnel/cont
Kuderna-
Danish
Methylene
chloride
ImL
GPC
4 min @ 40 C
40 - 270 @ 10
C/min
10min@270
Capillary
.25 or .32 mm
DB-5
.25 or .32 mm
DB-5
.25 or .32 mm
DB-5
Internal
standard
USGS
,OT3117&
1983
59
TWRI
<48hr
4C
1 Liter implied
B/N; Acid;
Semi-
Methylene
chloride
Sep funnel
Kuderna-
Danish
Methylene
chloride
ImL
Not given
2.5 min @ 45
45 - 300 @ 6
C/min
15 min @ 300
C
Capillary
0.20 mm SE-54
0.20 mm SE-54
0.20 mm SE-54
Internal
standard
standard
Methods
516
1985
13
APHS
< 1 week
4 C, in dark
1 Liter
B/N; Acid
Not specified
Not specified
Not specified
Not specified
Not specified
Not given
Not given
Not given
Not given
Not given
Not given
Not given
Not given
Not given
(Continued)
5-17
-------
Table V-4 (Continued)
Method Characteristic
Number of points
Linearity
Frequency of verification
Verification specification
Qualitative identification
Retention time agreement
Absolute
Relative
m/z's must maximize
Mass spectral agreement
Average Characteristics for
Determination of
Compounds Listed
Concentration range (min-
max)
Detection limit (min-max)
Quantitation limit (min-
max)
Percent recovery (average)
Precision (average % RSD)
Determination of
Naphthalene as a Specific
Example of Method
Characteristics
Concentration range
Detection limit
Quantitation limit
Percent recovery
Precision (% RSD)
Quality Control/Assurance
(QA/QC)
Tuning
Initial accuracy
Initial precision
Water
Regulations
3 minimum
<35% RSD of
RF
Daily
+/-20%RF
<+/-30sof
std
Not given
< +/- 1 scan
+/- 20% of std
5 - 1300 ug/L
MDL: 0.9-36
ug/L
4 - 100 times
MDL
80 (est; Inter-
lab)
30 (est; Inter-
lab)
Not given
MDL: 1.6 ug/L
4.8 ug/L
78 (Inter-lab)
29 (Inter-lab)
DFTPP
Spec in table
Spec in table
ITD
5
< 20% RSD of
RF
Each 8 hr shift
Specs in table
No spec
Specs in table
<2 consec
scans
+/-50%rel
abund
10 - 200 ug/L
MDL: .002-15
ug/L
10 - 200 ug/L
98 (est; Inter-
lab)
15 (est; Inter-
lab)
20 - 200 ug/L
ML: 10 ug/L
10 ug/L
99 (est; Inter-
lab)
14 (est; Inter-
lab)
DFTPP
Spec in table
Spec in table
Solid Waste
5 minimum
<30%RSDRF
12 hour
+/- 30%
No spec
+/- 0.06 RRT
No spec
+/- 20 Abs
abund
Method 625
data
Not given
PQL: 10 - 50
Method 625
data
Method 625
data
Method 625
data
Not given
PQL: 10 ug/L
Method 625
data
Method 625
data
DFTPP
Method 625
data
Method 625
data
Superfund
5
< 30% RSD of
RF
12 hour
+/- 25% RF
No spec
+/- 0.06 RRT
No spec
+/-20Abs
abund
5 - 160 ug/L
Not given
CROL:10-50
ug/L
Not given
Not given
5 -160 ug/L
Not given
CRQL: 10 ug/L
Not given
Not given
DFTPP
No test
No test
USGS
3
Not given
Not given
Not given
25 scan
window
No spec
No spec
No spec
Not given
Not given
Not given
81 (est; One
lab)
30 (est; One
lab)
Not given
DL: 1 ug/L
Not given
81 (Single lab)
17 (Single lab)
Not given
No test
No test
Standard
Methods
Not given
Not given
Not given
Not given
No spec
1 - 2 percent
No spec
> 950 FIT
Not given
Not given
Not given
95 (est; One
lab)
12 (est; One
lab)
Not given
Not given •
Not given
95 (Single lab)
4 (Single lab)
Not given
No test
No test
(Continued)
5-18
-------
Table V-4 (Continued)
Method Characteristic
Measurement of detection
limit Not required
Blanks
Frequency
Specification
Surrogate recovery
Frequency
Specification
Matrix spike recovery
Analytes covered
Frequency
Specification
Duplicate analyses
Analytes covered
Frequency
Specification
Statement of data quality
Samples
Laboratory
Safety
Water
Regulations
Required
Each sample
set
No spec
Every sample
No spec
All
10% minimum
In table
Not required
No spec
No spec
Recovery +/-2
SD
Not required
Explicit
warnings
ITD
Not required
Each sample
set
<10ug/L
Every sample
In table
All
100% (labeled)
In table
Not required
No spec
No spec
Recovery +/- 2
SD
Recovery +/-2
SD
Explicit
warnings
Solid Waste
Not required
Each set or 5%
No spec
Every sample
In table
All
5% minimum
In table
All
5% minimum
No spec
Recovery +/- 2
SD
Not required
Not given
Superfund
CRDL
required
Each sample
set
CRQL
Every sample
In table
Subset
5% minimum
In table
Subset
5% minimum
In table
Not required
Not required
Not given
USGS
Not required
Each sample
set
No spec
No test
No spec
No test
No test
No spec
No test
No test
No spec
Not required
Not required
Not given
Standard
Methods
Not required
Not required
No spec
No test
No spec
No test
No test
No spec
No test
No test
No spec
Not required
Not required
Not given
References:
"Method 625-Base/Neutrals and Acids", 40 CFR Part 136 [49 FR 43234, October 1984].
Method 1625, Revision C: "Semivolatile Organic Compounds by Isotope Dilution GCMS", Industrial Technology Division (WH-
552),USEPA,401 MStSW,
Washington, DC 20460
Method 8270: "Gas Chromatography/Mass Spectrometry for Semivolatile Organics: Capillary Column Technique", "Test
Methods for Evaluating Solid Waste",
SW-846, Volume IB: Laboratory Manual, Physical/Chemical Methods, Office of Wolid Waste and Emergency Response, U.S.
Environmental Protection Agency,
Washington, DC 20460, Third Edition, November 1986.
Statement of Work for Organics Analysis, Multi-Media, Multi-Concentration, USEPA Contract Laboratory Program,
Analytical Support Branch, Office of
Emergency Response, U.S. Environmental Protection Agency, Washington DC 20460, October 1986.
"Acid extractable compounds, total recoverable, gas chromatographic/mass spectrometric (O3117-83)", and "Base/neutral
extractable compounds, total
recoverable gas chromatographic/mass spectrometric (O-3118-83)", Methods for the Determination of Organic Substances in
Water and Fluvial Sediments",
U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, Laboratory Analysis, Chapter A3, Open-File
Report 82-1004, U.S.
Geological Survey, Room 5A420, National Center, 12201 Sunrise Valley Drive, Reston, VA 22092,1983.
Section 516, "Organic Contaminants, Gas Chromatography/Mass Spectrometry", "Standard Methods for the Examination of
Water and Wastewater", Prepared and
published jointly by American Public Health Association, American Water Works Association, Water Pollution Control
Federation, Publication Office:
American Public Health Association, 1015 Fifteenth St NW, Washington DC 20005, Sixteenth Edition, 1985.
5-19
-------
Table V-5 Comparison of Methods for the Determination of Seleniumin in Water by Graphite Furnace Atomic
Absorption Spectrophotometry (GFAAS)
Method Characteristic
Method Kumbor
Ravision Data
General Method
(GFAAS)
No. Analytes Covered
Sample
Holding Time
Preservation
Digestion
Acids, Reagents
Concentration
Instrument Conditions
Specified
Backgound Correction
Matrix Modifier
Calibration
Number of Points
Frequency
Verification Specs.
Determination of Se
Cone. Range (mg/1)
Detection Limit (mg/1)
% Recovery
Precision
QA/QC Blanks
Frequency
Drinking Water
&MCAWW
270.2
1978
200.0
29
6mos.
HNO3
HNO3iH2O2
Cone., 30%
Yes
Recom-mended
Ni(NO3)2
4,5
-
±10%
5-100
2
94-112%
4-14%
Each calib.
EPA
Solid Waste
SW-846
7740
1986
7000
11
6mos.
HNO3
HN03,H202
Cone., 30%
No
Required
Ni(N03)2
4,5'
Hourly
±20%
-
2
94-112%
4-14%
Each batch
Superfund-CLP
CLP-SOW787
270.2 CLP-M
1987
IFB - Ex. D & E
9
6mos.
HNO3
HNO3_ H2O2
(1 + 1), 30%
Yes
Required
Ni(N03)2
4
Daily
+ 10%
5-100
2
97%b
7%b
10%
Othera
ASTM Standard
Methods
D3859
1985
D3919
13
6mos.
HNO3
Cone., 30%
No
Recom-mended
Ni(NO3)2
4
Every New
Run
-
2-100
2
92%
3-30%
-
323A
1985
304
17
6mos.
HNO3
Cone., 30%
No
Recom-mended
4
Daily
-
5-100
2
-
6-18%
Each batch
(Continued)
Note a USGS does not list the method in its manual.
b ASTM STP 925, (1986), Quality Control in Remedial Site Investigations.
c SW-846 (1986) Manual often contains several conflicting requirements between the chapters on Quality
Control, General Method and Specific Methods
5-20
-------
Table V-5 (Continued)
Method Characteristic
EPA
Drinking Water Solid Waste SW- Superfund-CLP
MCAWW 846 CLP-SOW787
Othera
ASTM
Standard
Methods
Specification
Calibration Checks
Frequency
Specification
Analytical Spike
(post-digest)
Frequency
Specification
Replicate Injections
Matrix Spike Sample
(Pre-digest)
Analytes Covered
Frequency
Specifications
Duplicate Sample
Analytes Covered
Frequency
Specification
Duplicate Matrix Spike
Frequency
Specification
±10%
5%
±10%
10%, 6.6%°
±20%
Each Matrix All Complex
Matrices
Recom-mended Recommended
All
5%, 10%°
All
10%
All
5%, 20%
10%, 5%°
±5ppb
10%
±10%
100%
Each Matrix
±15% ±10%
Two-Required Recom-mended Two-Required
All
±25%
All
±20%
Note a USGS does not list the method in its manual.
b ASTM STP 925, (1986), Quality Control in Remedial Site Investigations.
c SW-846 (1986) Manual often contains several conflicting requirements between the chapters on Quality
Control, General Method and Specific Methods.
References ' ,
Methods for Chemical Analysis of Water and Wastes (MCAWW) EPA - 600/4-79-020, (1979)
Test Methods for Evaluating Solid Waste (SW-846), 3rd Edition (1986)
Statement of Work for Inorganic Analyses, MultiMedia, Multi-Concentration, USEPA
Contract Laboratory Program, (1987)
1987 Annual Book of ASTM Standards, Volume 11.01-11.02: Water, American Society for
Testing Materials, (1987)
Standard Methods for the Examination of Water and Wastewater, 16th Edition, (1985)
Methods for Determination of Inorganic Substances in Water and Fluvial Sediments,
U.S. Geological Survey, Books, Chapter Al (1979)
regarding the amount and concentrations of
acids used. The major differences occur in the
QC and calibration requirements. The number
of standards required for calibration vary from
four to five at frequencies ranging from hourly
and daily to "unspecified". The calibration
verification criteria ranged from +10% and
± 20% to unspecified.
5-21
-------
Table V-6 Comparison of Methods for the Determination of Metals in Water by Inductively Coupled Plasma
(ICP)Spectroscopy EPA Others
Method Characteristic
Method Number
Revision Date
No. Analytes Covered
Sample
Holding Times
Preservation
Digestion
Acids, Reagents
Concentration
Background Corrections
Interelement Corrections
Linearity Check
Calibration
Number of Points
Frequency
Verification Spec
Determination of Cd
Concentration Range
Detection Limit (ug/1)
% Recovery
Precision
QA/QC
Accuracy Check
Accuracy Specification
Initial Precision
Blanks
Frequency
Specification
Calibration Checks
Frequency
Specification
Low Level Check
Interference Checks
Type
Frequency
Specification
Replicate Exposures
Serial Dilution
Frequency
Specification
Matrix Spike (Pre-Digest)
Analytes Covered
Frequency
Specification
Drinking Water
MCAWW
200.7
1979
25
6mos.
HNO3
HNOg.HCl
(1 + 1), (1 + 1)
Required
If needed
• ' -
2min.
-
±5%
-
4
93-116%
12-16%
weekly
±5%
±5%
10%
± 2 std. dev.
10%
±5%
-
Spiked Sample
Every
calibration
±1.5 Std. dev.
Recommended
Each matrix
±5%
-
-
-
Solid Waste
SW-846
6010
1986
25
6mos.
HNO3 .
HNO3, HC1
Con., (1 + D
Required
Required
-
3,5°
-
± 10%
-
4
93-116%
12-16%
weekly
±10%
±5%
10%
± 3 std. dev.
10%
±10%
-
Spiked Ck. Soln
Every 8 hours
±20%
Min. two
Each matrix
±10%
All
20%, 5%°
±20%
Superfund-CLP
CLP-SOW 787
200.7 CLP-M
1987
25
6mos.
HNO3
HNOs, HC1
(1 + 1), (1 + 1)
Required
Required
±5%
3 min.
daily
± 10%
-
4
97%b
14-16%b
daily
± 10%
10%
± CRDL(5 ppb)8
10%
±10%
2xCRDL(10ppb)
Program Ck. Std.
Every 8 hours
±20%
Min. two
5%
±10%
All
5%
±25%
ASTM
D4190 (DCP)d
1982
16
6mos.
HNO3
HNO3, HC1
Con., Con.
-
-
-
5
each run
-
50-1000 ppb
97%b
11% (100 ppb)
-
-
-
-
-
-
_
.
-
-
-
-
-
-
Standard
Methods
305
1985
25
6mos.
HNO3
HNO3) HC1
Con., (1 + 1)
Required
Recommended
-
-
-
-
-
4
-
-
-
-
-
-
_
• -
-
-
-
-
-
-
(Continued)
5-22
-------
Table V-6 (Continued))
Method Characteristic
EPA
Drinking Water Solid Waste
MCAWW
SW-846
Superfund-CLP
CLP-SOW 787
Othera
ASTM
Standard
Methods
Duplicate Sample Analyses
Analytes Covered
Frequency
Specification
Duplicate Matrix Spike
Frequency
Specification
Matrix Spike (post-digest)
Frequency
Specification
Each matrix
±10%
All
20%, 5%<=
All
±20%
10%, 20%=
± 20%
Each matrix Pre-Dig. Spike
Fails
± 25%
Note a USGS does not list the method in its manual.
b ASTM STP 925, (1986), Quality Control in Remedial Site Investigations.
c SW-846 (1986) Manual often contains several conflicting requirements between the
chapters on Quality Control, General Method and Specific Methods.
d Direct Current Plasma only.
e CRDL in the CLP Contract Required'Detection Limit (5 ug/1 for Cd)
The number, frequency, and specifications
for blanks are different among methods, the
frequency and specifications of calibration
checks are different, and the analytical spike
and the number of injections are different as are
the requirements for matrix spikes, duplicate
samples, and duplicate matrix spikes. In the
SW-846 manual for solid waste, the QC
requirements are sometimes inconsistent
between AA methods for the individual metals.
The comparison of TCP methods shows the
same results found for AA. The methods are
nearly identical, including the same acids for
digestion. Again, however, there are small,
apparently unnecessary, differences in the
amounts and concentration of the acids. The
concentration range, detection limits, and
general percent recovery and precision
statements are also the same among methods.
The major differences in the ICP methods, as
with the AA methods, occur in the quality
control requirements. The number of standards,
the frequency, and verification specification in
the calibration methods are different. Although
the frequency of the blanks for ICP are similar
among methods, the criteria range from ±2
standard deviations (std. dev.) for MCAWW and
±3 standard deviations for RCRA to ± detection
limit for Superfund. Calibration checks,
interference checks, serial dilutions, and
replicate exposure requirements are all different
as are the specifications for duplicates, matrix
spikes and duplicate matrix spikes. The QC
requirements for the ICP methods in ASTM and
Standard Methods are non-existent. The data in
Tables V-5 and V-6 reveal that all the methods
use nearly identical materials, equipment and
operating conditions but have differences in
digestion methods.
Major deficiencies exist in the QA/QC
requirements of the non-EPA methods and there
is inconsistency among EPA programs,
particularly within the solid waste program. The
data also indicate that the EPA inorganic
methods are more highly developed than non-
EPA methods, with Superfund's Contract
Laboratory Program being the most complete for
frequency and specification requirements. EPA
has found that unless detailed QA/QC
requirements are contained in the methods and
followed correctly, laboratories performing
analyses will produce results of unknown and
5-23
-------
often less than optimal quality. Consistent
detailed methodology and QC requirements
should be developed by EPA for the analysis of
inorganics to ensure that data from the various
programs are comparable and with a known and
stated quality.
Biological Methods
Numerous organizations establish test
protocols for biological methods, including the
American Public Health Association (APHA);
the American Society for Testing and Materials
(ASTM); States, and individual testing
laboratories. Although there are often many
similarities between these methods, the precise
requirements may be significantly different and
could result in variability in the test results. In
reviewing single and multilaboratory precision
studies in the previous chapter, several
investigators performing "round robin"
evaluations attributed variable test results to
either use of different protocols or variable
interpretation of language in the same protocol.
To examine the extent of these potential
differences, the acute toxicity test method for
Daphnia spp. in effluents, developed by APHA,
ASTM, and EPA, is compared in Table V-7. This
is one of the few biological tests that exist in a
similar fashion from several organizations.
There was considerable difference in the
format used for writing the method. The APHA
method required constant reference back to
previous sections that appeared to be general
guidelines for any toxicity tests and not specific
to this test. The APHA method left several
analytes (e.g., length of test) in question, even
after careful review of the applicable section. All
three methods used a different definition of
death and suggested different methods for
determining death. This could considerably alter
the LCgo since only those data collected at the
end of the test period are used to calculate the
LCso- Control mortality restrictions were
roughly equivalent. Only the EPA method
required a standard reference toxicant. The
number, size, and amount of test solution in each
test container was significantly different. APHA
had few clear specifications for water quality in
the test solutions or required conditions during
the test. Of the three methods, EPA's method
was the most thorough method with the clearest
specifications and instructions for performing
the test. Any comparisons among methods
developed for the various program offices of EPA
or between EPA and other federal agencies is
largely nonproductive. The targeted sample
matrix for each method (e.g., dredged material,
oil dispersants, municipal sludge) is typically so
dissimilar as to mandate a matrix specific
method. These methods have different goals due
to the wording of the authorizing legislation or
the site or disposal specific analytes (e.g.,
dilution rates).
While no significant benefits are gained by
additional comparisons of specific techniques,
comparisons of terminology and standardization
of terminology used in biomonitoring would be
useful. For instance, in aquatic toxicity testing,
the definition of critical terms such as "death",
"chronic", or "strain" are quite confused due to
slightly different wording in the definition or
different techniques associated with the concept
(e.g., how to demonstrate or determine death).
5-24
-------
Table V-7 Comparison of Daphnia spp. Acute toxicity test procedure from three sources
Parameter
1 . Test organism
a. species
b.age
EPA (1985)
a. Daphnia pulex
(preferred)
b. 1-24 h neonates
ASTM(1987)
a. D. pulex or magna
b. <24hneonotes
APHA(1985)
a. Daphnia
b. < 24 h neonates
2. Test conditions
a. temperature
b. dissolved oxygen
c. dilution water
,d.pH
a. 20+oC
b. >40% of saturation
a. 20 +
b. not specified; within
10% of natural
:. receiving water, surface c. receiving, surface,
water, ground water,
synthetic water (mod.
hard for D. magna; mod
or soft for D. pulex)
d. 6.0-9.0
ground, reconstituted
d. no specification
a. 20oC, 25oC (?) + loC
b. within 10% if naturals:
>60% saturation; no
problem if 15%
c. receiving water;
reconstituted
d. pH = receiving water
p,H adjust if necessary to
+0,4
e. light intensity
f. photo period
g. cover
h. aeration
i. size of container
j. no. per container
k. no. of replicates
1. amount of test solution
m. no. of concentrations
n. feeding scheduling
o. test duration
p. endpoint
3. Data
a. standard toxicant
b. frequency of observations
c. method for calculating
d. control mortality
e. 50- 100 ft. candles
f.8-16hlightf24h
g. none
h. none unless DO below
40% saturation
i. 100 ml beaker
j.10
k. 2 1. 50 ml
1. 100 ml
m. screening - 1 to 4;
definitive = 1 to 4
n. no feeding during 48
hr., every other day if
longer
o. screening = 24 h
p. LC50
a. yes
b. 0,1,2,4,8 hrs; daily
c. choice of manuals or
several computer
programs
d. <10%
e. < 800 lux = 74 ft.
f. 16L:8D
g. none
h. not discussed
i. 250 ml beaker
j.5
k.41. = 200ml
m. 5 + control
n. no feeding
o. 48 h
p. LC50
a. no
b. 24,48 hr
c. manual or computer -
various procedures
d. <10%+d. <10%;
prefer <5%
e. no specification
f. no specification
g. no specification
h. no specification
i 125 mL
j.10
k.2
1. 100 mL
m. 5 + control
n. no feeding
o. 5 days or as long as live
= short term tes;t long
term test = 2 1-30 days
p. LC50
a. no
1,2,4,8, 16 hr; 24 hr-
afterwards
c. various manual
procedures
5-25
-------
Chapter Five References
1. Statement of Work for Organics Analysis,
Multi-Media, Multi-Concentration, USEPA
Contract Laboratory Program, Analytical
Support Branch, Office of Emergency
Response, U.S. Environmental Protection
Agency, Washington, D.C. 20460. October
1986.
2. Methods for Chemical Analysis of Water and
Wastes, Environmental Monitoring and
Support Laboratory, Cincinnati, OH, EPA
600/4-70-020.
3. Annual Book of ASTM Standards, Volume
11: Water, American Society for Testing and
Materials, Philadelphia, PA 19103.
4. Methods for Determination of Inorganic
Substances in Water and Fluvial Sediments,
U.S. Department of the Interior, U.S.
Geological Survey, Techniques of Water-
Resources Investigation, Book 5, Chapter
Al, 1979.
5. Standard Methods for the Examination of
Water and Wastewater, American Public
Health Association, 1015 Fifteenth Street,
N.W. Washington, D.C. 20036.
6. Appendix C to 40 CFR 136.
7. National Resources Defense Council v. Train
(8 ERC 2120,'D.D.C. 1976).
8. Test Methods for Evaluating Solid Waste,
SW-846. Office of Solid Waste and
Emergency Response.
5-26
-------
CHAPTER SIX
ADEQUACY AND COMPARABILITY OF QUALITY
ASSURANCE AND QUALITY CONTROL PROGRAMS
AND PROCEDURES
Introduction and Summary
While a fully validated and standardized
method is desirable, it alone is not sufficient for
the generation of valid data. A quality assurance
and quality control (QA/QC) program including
QA/QC procedures incorporated into methods
are essential to detect and correct problems in
the measurement process and to assure that the
results generated are of a known and acceptable
quality. The basic concepts of quality control,
the techniques used to control errors, and
quality assurance, the mechanism used to verify
that the QC activities are acceptable, are
described in detail in the literature (6-1 to 6-5).
The QA/QC procedures contained in 40 CFR 136
methods were reviewed to determine their
adequacy to control and document the quality of
data produced for Federal Water Pollution
Control Act (FWPCA) programs. These
procedures were also compared to the procedures
developed for other programs. Many QA/QC
requirements developed by the Agency are not
contained within the methods, but, are
mandated by the program. These requirements
were also reviewed.
Collaborative method validation studies
have been conducted, reports completed, and
precision and accuracy generated on 63 of the
175 EPA methods in 40 CFR 136. For 14 of these
methods which cover the 114 priority pollutants
the data from the studies have been used to
establish minimal QC performance criteria for
users of the methods. The need exists to generate
this type of information for other analytes in 40
CFR 136 and for those matrices that have not
been so validated.
The quality assurance activities established
under EPA's legislatively mandated programs
differ, and are lacking in some aspects. In
addition, the quality control procedures
contained in analytical methods addressing the
same analytes are unnecessarily different, often
conflicting and in many cases, insufficient. The
Agency should attempt to establish uniform
quality assurance criteria for all of its
regulatory program efforts. Both chemical and
biological methods established under each
program office for a group of analytes should
have consistent quality control requirements to
enhance data quality and reduce costs for the
regulated community. The laboratory approval
and certification activities in the Agency are
diverse, duplicative, and inconsistent among its
operating programs. These differences result in
much greater costs to the regulated communities
and much greater complexity in regulations, for
no useful purpose. The Agency should determine
the feasibility of establishing a single uniform
certification function within its QA program for
all monitoring and regulating activities.
6-1
-------
Quality Assurance Programs
Analytical methods developed by EPA
contain specific QA/QC procedures related to
activities such as calibration, laboratory control
samples, spike samples, etc. However,
incorporation of QC requirements into the
methods is not sufficient to ensure the
generation of valid data. In recognition of the
need to provide additional guidance, each
program has incorporated additional QA/QC
activities to enhance the quality of the
analytical data.
Before one can understand the past
activities and future needs in QA/QC, one must
understand the history of QA/QC in the Agency
and the several levels now operating.
National Quality Assurance Program
EPA established a formal Quality Assurance
(QA) Program in 1972 with the responsibility for
QA assigned to the Office of Acid Deposition,
Environmental Monitoring, and Quality
Assurance (OADEMQA) within the Office of
Research and Development (ORD). Technical
responsibility for QA was assigned to three
OADEMQA laboratories by matrix area:
Water and Wastes
Air
Environmental Monitoring
and Support Laboratory -
Cincinnati, OH (EMSL-
Cincinnati)
Environmental Monitoring
Systems Laboratory -
Research Triangle Park, NC
(EMSL-RTP)
Radiochemistry Toxic and
Hazardous Materials
Environmental Monitoring
Systems Laboratory - Las
Vegas, NV (EMSL-Las
Vegas)
EMSL-Cincinnati provides the following QA
support to the Agency's water and waste
programs including the programs under the
FWPCA:
1.Collaborative Method Validation Studies
2.Method Equivalency Program
S.Intra-laboratory Quality Control Support:
• Manuals/Guidelines for Quality Control
• Quality Control Sample Program
• The Repository for Toxic and Hazardous
Materials (calibration standards for trace
organics)
4.1nterlaboratory QC Support:
• Performance Evaluation (PE) Studies
Mandatory QA Requirement
In 1979, the Administrator established
requirements for QA in the Agency:
May 30,1979:
.. .1 am making participation in the quality assurance
effort mandatory for all EPA supported or required
monitoring activities... Monitoring is defined as all
environmentally related measurements which are
funded by the EPA or which generate data mandated by
EPA.
June 14,1979:
In order to assure.. .usable data of known quality, I am
making.. Quality Assurance Requirements mandatory
for all EPA contracts, grants, cooperative agreements,
and interagency agreements that involve
environmental measurements.
The Agency requires the development of
Quality Assurance Project Plans covering each
activity of a project. The Quality Assurance
Management Staff (QAMS) has been established
in the Office of Acid Deposition, Environmental
Monitoring, and Quality Assurance
(OADEMQA) to develop, coordinate, and direct
the implementation of these efforts.
QA Within Programs of the Agency
Although the concepts of standardized
methodology and standardized QA across
Agency programs are accepted and can be shown
to be more efficient than separate efforts, each
water and waste program differs somewhat in:
analytes, concentrations of analytes, sample
matrices, and interferences; and in legislative
timetables for regulation and compliance. As a
6-2
-------
result, the Agency's operating programs have
established conceptually similar but not
identical methods of analyses and QA/QC
requirements.
Quality Control Within Methods
As regulations progressed, the three EMSL
laboratories realized that the key to ensuring
proper application of QC was to make QC an
integral part of the analytical method which is
required for use under regulations.
Consequently, the methods for toxic organic
analytes in 40 CFR 136 became the first water
methods to contain a quality control section
requiring start-up and ongoing performance
demonstrations and to provide performance
criteria. The Comprehensive Environmental
Response Compensation and Liability Act
(CERCLA, Superfund) Contract Laboratory
Program (CLP) program followed with a similar
response.
Laboratory Certification/Laboratory
Accreditation
Any discussions of laboratory approval,
accreditation or certification first require a
definition of terms. EMSL-Cincinnati,
responding to the QA/QC needs of the Office of
Water, uses the following definitions:
Laboratory a generic term used in a variety of
Accreditation ways by different organizations to
describe some form of approval.
Laboratory the official EPA approval by a
Certification regulating authority based on exact
Agency criteria, for a laboratory to
perform some required function.
There is only one Certification Program in
EPA, that for certification of laboratories
regulated under the Safe Drinking Water Act
(SDWA) and its amendments. The certification
requirements include critical elements on
sampling, sample preservation, and analytical
methods, laboratory facilities, personnel,
instrumentation, quality control, data reporting,
successful participation required in evaluation
studies for each analyte to be certified, and
lastly, an on-site inspection of the laboratory
operations based on the above criteria.
Laboratory Performance Evaluation
In order to assure that laboratories are
performing in accordance with requirements in
the program or the methods, the Agency
established external laboratory evaluation
procedures. The external laboratory evaluations
include formal laboratory certification,
laboratory approval blind performance
evaluation samples, and/or on-site laboratory
audits. While there is no doubt that these
programs have improved the quality of data
generated and that some overlap is desirable,
there are inconsistencies and deficiencies in the
various QA programs. The external laboratory
evaluation programs established in the
regulatory program of the Agency are
summarized below.
FWPCA - There is no formal EPA
certification program established under
FWPCA. Wastewater treatment facilities are
regulated under the National Pollution
Discharge Elimination System (NPDES), one of
the most extensive monitoring networks
operated by the Agency. Within this system,
dischargers monitor themselves and are
required to immediately report any NPDES
permit violations. Enforcement actions initiated
by reported self-monitoring data are legally and
technically equitable only if the data generated
within the NPDES system are of known quality
and are intercomparable. The Discharge
Monitoring Report Quality Assurance (DMR-
QA) program was instituted in 1980 to evaluate
data quality from NPDES permittees. The
primary mechanism in the DMR-QA program is
the performance evaluation study. A
performance evaluation study is conducted
annually to measure the ability of discharger
laboratories to generate good quality DMR data
submitted by the 7500 major industrial
wastewater dischargers to show compliance with
their NPDES permits. The DMR-QA program
provides a cost-effective mechanism by which
this data quality is monitored.
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Performance evaluation samples contain 29
of the most frequently occurring analytes listed
on NPDES permits. Acceptance criteria are
derived from analyses of these samples by EPA
and state enforcement laboratories. Samples are
distributed as unknowns to approximately 6500
laboratories representing 7500 major
dischargers. Results are used to evaluate quality
of self-monitored data. Quality control samples
and other corrective actions are taken to bring
poor performers back to acceptable levels and to
help to maintain enforcement and compliance
laboratories in control and intercomparable.
In the first two studies for the DMR-QA
program, (1980 and 1982) 73-76 percent of the
data were acceptable. The performance level has
improved year by year to the present 86.5
percent acceptability.
Within available resources, the regions and
states use DMR-QA results to flag laboratories
with the most serious problems for follow-up
such as on-site visits. However, although there
may be some follow-up action from the states or
EPA regional offices on poor performance by
laboratories, direct action is not required. Only a
few states (e.g., Wisconsin) perform formal
compliance inspections of laboratories with
recurring problems.
Although the most commonly regulated
contaminants are addressed in the DMR- QA
studies, these are only 29 out of the 252 analytes
in 40 CFR 136. It is recognized that if resources
were available, the studies should challenge
analysts for at least representative compounds
in each major pollutant category under
regulation, the studies should be performed at
least twice per year and that the group tested
should be expanded to include the 5000-6000
"major-minor" dischargers, for a total of 13,000-
14,000 permittees.
Laboratory Performance Evaluation
Under Other Environmental Programs
SDWA - Under the SDWA, a formal
certification program has been instituted to
certify laboratories analyzing drinking water for
compliance with the SDWA and the Drinking
Water Regulation promulgated in 40 CFR 141 &
142. A certification manual, currently in
revision, includes critical elements for
certification, requirements to maintain
certification, and methods to downgrade the
laboratory certification status. Laboratories are
certified for microbiology, chemistry or
radiochemistry on an analyte-by-analyte basis.
In order to be certified, a laboratory must
fulfill the following initial requirements: 1)
satisfactory analysis of performance evaluation
(PE) samples for those analytes for which it
seeks certification; 2) acceptable on-site
inspection; and 3) meet the minimal
requirements stated in the certification manual
(i.e., acceptable QA plan, use of approved
methods, qualified personnel, and adequate
equipment). This certification is valid for up to
three years and in order to maintain it, the
laboratory must satisfactorily analyze one PE
sample per year, use approved analytical
methodology, notify the certifying authority of
any major changes in the laboratory, and pass
an on-site evaluation every three years.
Provisional certificates are also issued to
laboratories which met most of the criteria and
can demonstrate that they can produce valid
data. These laboratories have up to one year to
correct deficiencies. A one time extension of six
months can be granted if progress is made in
correcting the deficiencies. The mechanisms for
provisional certification and de-certification are
specified in the certification manual.
While these requirements provide some
measure that the data generated are of a known
and acceptable quality, the individual criteria
vary among state to state certification programs.
The periodic checks (PE samples and on-site
inspections) for maintaining the certification are
not designed to monitor laboratory ongoing
performance.
Resource Conservation Recovery Act
(RCRA) - Although the EPA program (Office of
Solid Waste) establishes performance criteria
and evaluates laboratory performance, it has no
formal evaluation program for laboratories
performing analyses under RCRA regulations.
The Office of Solid Waste (OSW) sends out
quarterly PE samples (through EMSL-
Cincinnati) to EPA contractors and state
laboratories performing RCRA analyses. The
state RCRA requirements for laboratories vary
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from state to state. Several states, such as New
Jersey, allow laboratories to perform RCRA
analyses if they are certified by the state to
perform water and wastewater analyses or if the
laboratories either participate in the EPA
Superfund CLP or are contracted specifically by
the state. Other states, such as California, have
certification programs for solid waste analyses
that involve performance evaluation samples,
acceptable analytical methods and QA
programs, as well as on-site inspections. There is
no uniformity in the QA programs developed in
the fifty states.
CERCLA - Superfund's CLP has developed
an extensive QA program for contract analytical
laboratories performing analytical services for
EPA. Although the CLP does not have a formal
certification program, it has stringent
requirements which a laboratory must meet
before a contract is awarded:
• The laboratory must satisfactorily analyze
a set of at least two PE samples (water and
solids) designed as typical waste samples.
• The laboratory must submit with its bid for
a contract all the laboratory's standard
operating methods (SOP's), a list of
equipment to be used on the contract, and
resumes to show staff qualifications.
• The laboratory must pass a pre-award on-
site laboratory inspection designed to
assess the laboratory's sample capacity
and ability to meet the terms and
conditions of the contract.
Once a laboratory has received a CLP
contract to perform organic or inorganic
analyses, an ongoing QA program is required
which assesses the performance of the
laboratory with quarterly (at a minimum) PE
samples, routine on-site audits, and detailed
audits of all data reported. Historically, 50-70%
of the laboratories have failed to pass the pre-
award PE samples. The laboratories with CLP
contracts are generally regarded as among the
better laboratories in the country. With the
constant monitoring for lab performance and the
high level of QA/QC, the CLP reputation gives
Agency programs a strong "comfort factor"
choosing CLP laboratories for other analytical
services. The CLP has become a de-facto
certification program for the laboratories
performing analysis of waste samples.
However, since the controls in the CLP are
only monitored for those laboratories under
contract and providing analytical services to the
Agency, there is no assurance that data
generated by industry, or by CLP laboratories on
non-CLP samples are of the same quality. Fully-
qualified laboratories which may choose not to
compete for purely business reasons, or were not
selected for CLP contracts may be implied to be
second class.
The Superfund program sends out blind PE
samples to about 70 CLP laboratories through
EMSL-Cincinnati and EMSL-Las Vegas. These
samples simulate typical natural matrices such
as mining waste. The PE samples are sent to
laboratories who take part in the pre-award
process, to determine which contractors are
capable of performing chemical analyses on toxic
wastes within established limits. Even when
laboratories know they are being tested and
presumably use their best people and
equipment, some cannot successfully analyze PE
samples. The percentages of laboratories passing
organic and inorganic samples are nearly the
same. Although validated methods and rigorous
QA/QC requirements are critical for valid
results, they cannot ensure reliable results. In
addition QC requirements should be built into
Agency programs and methods, and the QC
records should be available with the data
results.
Other Quality Assurance Support
The Agency provides other QA support for
data generated by the user community:
• Method validation studies,
• Manuals and guidelines on sampling,
analyses, and quality control,
• Analytical reference materials.
This section describes the QA support
developed for FWPCA methods and for methods
developed in RCRA, SDWA, and CERCLA
programs.
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Method Validation Studies
The formal collaborative study design has
evolved over the past 10-12 years. At present,
EMSL-Cincinnati conducts method validation
studies (MVSs) inhouse and extramurally for
water analytes. A prime contractor is assigned
the task order for preparation of spiking
solutions, water samples, instructional
materials, verification analyses, formal conduct
of the study, and screening of the study data
from participating laboratories. EMSL-
Cincinnati obtains the participating
laboratories through the competitive
procurement process based on technical
qualifications, performance evaluation, and
costs. The prime contractor conducts the study,
EMSL-Cincinnati evaluates the results of using
computerized data treatment, and prepares the
final reports.
EMSL-Cincinnati processes data from the
participating laboratories using a computer
program entitled, "Interlaboratory Method
Validation Study (IMVS)," which follows the
American Society of Testing and Materials
(ASTM) - D2777 guidelines. The IMVS program
uses two outlier removal tests, the Youden
laboratory-ranking test and a repetitive
Thompson t-test, both at the 5 percent
significance level. The retained data are
processed to provide statistics such as the bias,
overall precision and single analyst precision.
The IMVS program computes a weighted linear
regression equation for accuracy as a function of
the true value, and for single analyst and overall
precision as functions of the mean recovery of
the analyte. Finally, the IMVS program
compares each of the industrial and municipal
water types against reagent water and indicates
which of the water types exhibit a matrix effect.
Method validation studies have been
conducted, reports completed, and precision and
accuracy generated on the methods listed in
Table VI-1. The data from these studies have
been used to establish performance criteria
limits for all of the 600 series methods. The need
exists to generate this type of information for
those analytes and listed in 40 CFR 136 that
have not been so validated.
Table VI-1. Approved EPA Methods in 40 CFR 136
Supported by Formal EMSL-Cincinnati Method
Validation Studies
Analytes
EPA Method*
pH 150.1
Specific Conductance 120.1
Non-Filterable Residue 160.2
Total Hardness 130.1
Sodium 273.1
Potassium 258.1
Alkalinity/Acidity 310.1/305.1
Chloride 325.3
Sulfate 375.4
Ammonia-Nitrogen 350.2
Nitrate-Nitrogen 352.1
Kjeldahl-Nitrogen 351.3
Orthophosphate 365.2
Total Phosphorus , 365.41
BOD 405.1
COD 410.2/410.1
TOC 415.1
Aluminum . 202.1., 202.2
Arsenic 206.3
Cadmium 213.1,213.2
Chromium 218.1,218.2
Copper 220.1,220.2
Iron 236.1,236.2
Lead 239.1,239.2
Manganese 243.1,243.2
Mercury 245.1,245.2
Selenium 270.3
Zinc 289.1,289.2
Trace Metals - ICP (27) , 200.7
Purgeable Halocarbons (28) 601
Purgeable Aromatics (7) 602
Phenols (11) 604
Benzidines (2) 605
Phthalate Esters (6) 606
Nitrosamines(3) 607
Pesticides and PCBs (24) . 608
Nitroaromatics and Isophorone (4) 609
Polynuclear Aromatic Hydrocarbons 610
(16)
Haloethers (5) 611
Chlorinated Hydrocarbons (9) 612
2,3,7,8-Tetrachlorodibenzo-p-Dioxin 613
(1)
Purgeables(31) 624
Base/Neutrals, Acids, and Pesticides 625
(64)
Cyanide, Total 335.2
Cyanide, Amenable to Chlorination 335.1
Method validation studies have been
completed or are in progress on the following
analytes and methods in other EPA legislation:
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Table VI-2. Method Validation Studies Completed for
Other EPA Legislation
Analytes
EPA Method #
PCBsinOils
Maximum Trihalome thane 510.1
Potential
Total Organic Halides (TOX) QSW-9020
Ignitable Organics OSW-1010
Chlorophyll (Spectrophotometric
and Fluorometric)
Macroinvertebrate Organisms
Petroleum Hydrocarbons in Brine 418.1
Table VT-3. Method Validation Studies - In Progress for
Other EPA Legislation
Trace Metals iri Water and Sludges
Volatile Organics (GC/MS)
Semi-Volatile Organics (GC/MS)
Volatile Organics (GC/MS)
EDB/DBCP
Pesticides/PCBs
Aldicarbs/Carbofurans
Volatile Organics (GC/PID/ECD)
Chlorinated Herbicides
OSW 3005,3010 and
3050
OSW 8240/5030 (in
conjunction with
524.2)
OSW 8270/3510
DW-524.2
DW-504
DW-525
DW-531
DW-502.2
DW-515
Manuals and Guidelines
Manuals and guidelines are an integral part
of EMSL-Cincinnati's §304(h) quality assurance
(QA) program. As the state-of-the7art changes,
manuals/ guidelines are revised for sampling,
sample preservation and analyses of
waters/wastewaters for physical and chemical
pollutants and biological forms commonly found
in the environment. By setting and enforcing
standards and limits, the Agency can ultimately
enhance the quality of the environment. The
guidance provided in the manuals such as the
examples below supports these requirements.
1. Handbook for Sampling and Sample
Preservation of Water and Wastewater,
EPA-600/4-82-029, EMSL-Cincinnati, 1982.
The quality of the data generated by
monitoring activities is only as good as the
sample collected, its preservation and
analysis. Therefore, guidance is provided on
collecting representative samples in
ambient waters, and wastewaters,
measuring flow rates to meet National
Pollutant Discharge Elimination System
(NPDES) mass loading requirements,
statistical methods for sampling, automatic
and manual sampling techniques, and
preservation techniques.
2. Methods for Chemical Analysis of Water and
Wastes, EPA-600/4-79/020, EMSL-
Cincinnati, Revised March, 1983.
Guidance is provided for analytical methods
to monitor water supplies, waste discharges,
and ambient waters. The objective of the
manual is to provide the best analytical
methods currently available for use in
environmental monitoring, compliance
monitoring, enforcement, and research
activities of the Agency for water and
wastewater.
3. Handbook for Analytical Quality Control
(QC) in Water and Wastewater Laboratories
- EPA-600/4-79-019, EMSL-Cincinnati,
1979.
Continuing QA/QC programs must be
established in the monitoring laboratories to
assure the reliability and veracity of field
and analytical data generated in water and
wastewater pollution control activities. This
. handbook addresses those QC activities and
provides general guidelines to establish the
integrity of the data. It includes laboratory
services, instrumentation selection,
glassware, reagents, solvents, gases, QC
charts, data handling and reporting,
laboratory safety, and other guidance.
Reference Materials
Reliable reference materials are essential to
assure the generation of quality data. The
quality control samples, analytical method
standards and performance evaluation samples
prepared by EMSL-Cincinnati provide QA
support for a variety of EPA programs.
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Quality Control Samples
Water and wastewater laboratories
generating data for enforcement, compliance, or
to study long-term pollution trends must provide
reliable data of the known quality to assure that
a proper decision is made. One support activity
is the provision of QC samples to the analysts as
independent checks on analytical technique,
calibration standards, and understanding of the
analytical protocol.
Analytes contained in the QC sample
program address the priority pollutants under
the Consent Decree and other inorganic and
physical analytes regulated under NPDES.
Chemicals are purchased from commercial
sources, checked for their identity and purity,
purified if necessary, and combined with other
compatible analytes. The analytes are normally
dissolved in water or a water-miscible solvent
such as acetone, methylene chloride or
methanol, and flame sealed in all glass ampuls,
then monitored for stability over a 90-day
period. Upon successful conclusion of the
stability studies, the QC samples (1-15 analytes)
are produced in 3,000 to 10,000 ampul batches.
Random samples from the production lot are
analyzed by the producing contractor then sent
to independent analytical laboratories to verify
the true concentration for each analyte. Upon
verification, new sample series are added to the
QC sample list published in the semi-annual
EPA QA Newsletter prepared by EMSL-
Cincinnati. User instructions direct the analyst
to dilute a specified volume in a water or
wastewater. The true value for each analyte
therein is provided with the 95 percent
confidence limits (C.L.) within which the
analyst's results should fall. The 95 percent C.L.
for each analyte are developed from EPA method
validation studies or EPA performance
evaluation studies.
The ampul concentrates are designed for
storage and shipment at ambient temperatures.
Annual checks are conducted on each analyte by
independent referee laboratories to assure that
no degradation or change has taken place. There
are 25 QC sample series containing about 235
analytes to support FWPCA programs, which
are available to EPA, state, local, EPA contract
laboratories and the commercial sector. The
annual distribution rate for FWPCA programs
use is about 75,000 ampuls. There are specific
requirements in the 600 series methods in Table
VI-1 that use these samples to demonstrate
acceptable performance. Other federal and state
programs which specify the use of these QC
samples have varying frequency and use
requirements.
In addition to the QC samples supplied for
FWPCA methods, QC samples are designed to
support the other Agency water programs as
well as RCRA, Superfund, and Toxic Substances
Control Act (TSCA). Some QC samples are
produced as natural matrix samples. These
samples contain the pollutants as they occur
naturally or as they are added through actual
pollution in the environment. Solid samples are
collected from a waste site, a river, estuary, or
lake. They are dried, homogenized, and
reference values established by independent
referee laboratories. Such samples include PCBs
in sediments and fish, metals in fish, inorganics
and general organics in municipal digested
sludge and organic pollutants in Chesapeake
Bay sediment. A complete list of the QC Sample
Series and analytes is provided in the Table in
the Appendix. Such reference samples are
important to non-point source monitoring,
ocean-dumping and marine/estuarine programs
as well as RCRA.
The Repository for Toxic and Hazardous
Materials
The EPA Repository for Toxic and
Hazardous Materials was established to provide
calibration standards to EPA, state, local, and
EPA contract laboratories utilizing §304(h)
methods. The Repository is a "permanent"
source of organic calibration standards. The
highest purity chemicals are procured or
synthesized if unavailable or too costly, and
provided to the requestor with a certified purity
for each of the calibration materials.
The Repository purchases chemicals in neat
form from the commercial sector and analyzes
each to verify identity and purity. The purity is
established primarily using gas chromatography
(GC) with a capillary column followed by a flame
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ionization detector. If the purity is greater than
or equal to 99 percent, it is classified as a quality
assurance standard (QAS) material. Purity in
the range of 95 to 99 percent is classified as a
quality assurance reagent (QAR) material and
those multi-peak compounds such as PCBs and
toxaphene are classified as quality assurance
technical (QAT) grade materials. A major
activity of the Repository is to upgrade as many
analytes as possible into the QAS category
through such purification techniques as high
performance liquid chromatography (HPLC),
spinning band distillation or recrystallization
techniques. Upon establishment of the purity,
samples are sent to independent referee
laboratories to confirm the purity of the neat
chemical. After purification, an average of 5,000
ampuls are produced for a single analyte in a
suitable solvent at a concentration ranging from
1500 to 10,000 ug/mL. The single-analyte
solutions are sent to independent referee
laboratories to confirm the final concentrations.
Upon verification, the new calibration
standards are added to the list of available
standards in the EPA QA Newsletter. Some 108
organic compounds of the 114 priority pollutants
specified in the Consent Decree are available as
"certified" calibration standards. Approximately
51,000 standards were distributed in FY87 to
871 requesters to support analyses performed
under the FWPCA. See the list of calibration
standards in the Appendix.
Performance Evaluation Samples
To assure the legal defensibility and
reliability of data generated, environmental
monitoring activities must have viable
intralaboratory and interlaboratory QA
programs. An interlaboratory QA program
includes use of unknown samples to challenge
the ability of laboratories to perform acceptable
analyses of regulated chemicals in a formal
study.
In the performance evaluation studies
conducted by EPA for water programs, stable
concentrates of regulated analytes are produced
at two levels, verified for true values,
homogeneity, and stability over time, and
distributed to participants for dilution with
reagent water and analyses. Analytical results
returned through state and regional program
offices to EMSL-Cincinnati, where the data are
computer-processed to determine performance
acceptability. Statistics are accumulated over a
number of studies and pooled to establish
relationships (regressions) between test
concentration and method performance. PE
study limits on a given study are developed from
EPA/state laboratory data in the current study
or from previous studies. If limits from the
current study are not completely enclosed within
the limits based upon the previous six studies,
the current study limits are used to evaluate the
study data. A performance evaluation study
report for each laboratory is sent to the ten EPA
regional offices and through them to the
regulating state authorities who use the results
to confirm good laboratory performance, to
identify problems and provide technical
assistance on analytical techniques, calibration,
and QC methods to the participating
laboratories. Ultimately, these studies upgrade
data quality.
There are three major types of PE studies for
water and wastewater conducted by EMSL-
Cincinnati: (1) Water Pollution (WP) PE studies
with 900-1100 laboratories/study which are
conducted to support the FWPCA, (2) the major
discharger PE studies conducted with about
6500 laboratories/study conducted specifically
for the Discharge Monitoring Report - QA
(DMR-QA) supporting the NPDES program, and
(3) Water Supply (WS) Studies with 1200-1500
laboratories/study conducted to support the
Drinking Water Certification Program.
The 95 percent confidence limits were
selected as acceptance limits for the Drinking
Water Program's WS studies, while 99 percent
limits were selected for WP and DMR-QA
Studies. As a result, the overall performance
levels of participant laboratories over time in
the three study types have generally reflected
the 4 percent difference (99-95) between the two
sets of limits.
From an initial 83 percent overall acceptable
data in the first WP study, the next two studies
showed a slight decline as other laboratories
participated for the first time. However,
performance then showed only a slow
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improvement to an 85 percent acceptance level
which has remained relatively constant to this
time. The DMR-QA studies showed a significant
improvement initially and have remained
relatively constant at about 84 percent
acceptable data for the past four years. The WS
studies began with 63 percent acceptable data in
1978 and have improved to an 80-81 percent
over the last three years. The EPA will need to
make additional effort and resource
commitments for follow-up activities if the
acceptance levels are to be further improved.
Quality Control Requirements
Quality control procedures are the practices
used on an ongoing basis to make certain that
the analytical method performed properly and to
define the quality of the data that was
generated. The quality control (QC)
requirements in the methods promulgated by
EPA or required by the various EPA programs
can be divided into the following groups:
• Method performance testing,
• Instrument calibration and verification,
• Blank analysis,
• Ongoing method performance checks,
• Sample-specific QC, and
• Data reporting requirements.
Method performance testing involves the
demonstration, prior to the analysis of any
samples, that the laboratory is capable of
performing the method.
Instrument calibration involves the initial
calibration of the instrument using multiple
standards at a specified frequency to define the
relationship of concentration to instrument
response and to ensure the instrument is capable
of producing acceptable quantitative data.
Instrument calibration should include
verification of accuracy and precision using
quality control samples. Ongoing instrument
performance involves continuing use of
calibration standards to monitor instrument
performance and calibration stability during the
analytical runs. Blanks include field blanks,
calibration blanks, reagent or preparation
blanks and spiked blanks to check for
contamination and/or carryover in the
analytical process and instrument baseline drift.
Ongoing method performance checks involve
the use of quality control samples and standards
to verify that the method and instrument were
used properly. Laboratory control samples
(LCS), method blanks and surrogates are carried
through the entire analytical method to monitor
method performance.
Sample-specific quality control includes
matrix spikes, duplicate matrix spikes and
duplicate sample analyses to determine the
method performance on the samples. The matrix
spikes give an indication of the accuracy of the
method for each compound in the matrix of
interest. Duplicate samples and matrix spike
duplicates indicate the precision of the analysis
in the matrix which includes errors due to
analytical imprecision and sample non-
homogeneity.
The frequency of these QC requirements, the
acceptance criteria or specifications, and the
corrective action required vary significantly
between the methods established by different
EPA programs. A summary comparison of the
QA/QC requirements for the organic and
inorganic methods for the various EPA
programs is summarized in Tables V-l through
V-5 and VI-4, Frequency of QC Sample Checks.
Method Performance Testing
Prior to the analysis of any samples, many
methods require testing to demonstrate the
proficiency of the laboratory to properly perform
the method. These initial start-up tests may also
include an instrument or method detection limit
determination study. With the exception of the
Superfund CLP program, laboratories are not
required to submit the data to a regulatory
agency to prove the test was done. The external
lab evaluation generally consists of formal
certification programs, blind performance
evaluation samples, and/or on- site laboratory
-audits.
FWPCA. Initial start-up tests are contained
in seventeen methods in 40 CFR 136. In the 600
Series for organics, each analyst must analyze
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four aliquots of a QC check sample (available
from EMSL-Cincinnati or prepared by the
laboratory) and generate statistics to show that
the test results are within the acceptance
criteria for precision and recovery listed in the
methods. Problems that cause an analytical
result to be out of acceptance limits must be
corrected. The analytical methods for inorganics
do not as yet require initial QA tests.
SDWA. The 500 series methods that have
been approved in 40 CFR 121.24 for the
determination of volatile organic chemicals have
incorporated a formal QC program that specifies
rigid start-up acceptance criteria that have not
been directly derived from interlaboratory
method validation data. The laboratory is
required to analyze seven replicate samples
containing the target analytes at defined spike
concentrations (typically one-fifth the MCL).
The results from these analyses are used to
calculate an MDL as specified in Appendix B to
40 CFR 136. The results are also compared to
acceptance criteria specified both for the average
recovery and the standard deviation. For
example, Method 502.1 requires that the
average recovery be between 90% and 110% of
the true value and the standard deviation must
be less than 35%.
RCRA. The initial internal laboratory
validations required for the RCRA program, are
contained in the methods specified in the SW-
846 manual. For organics, where corresponding
600 series methods exist, the initial laboratory
requirements are the same as those in the 600
Series promulgated under the CWA. For
example, the requirements and acceptance
criteria for Methods 8250 (GC/MS for semi-
volatile organics - packed column techniques)
and 8270 (GC/MS for semi-volatile organics -
capillary column techniques) are not only
identical to each other but are taken directly
from Method 625 (40 CFR 136). Where no
corresponding 600 series method exists (e.g.,
8015, 8280), there are no initial performance
requirements. For inorganic compounds there
are no initial laboratory tests required under the
RCRA program.
CERCLA. Under Superfund's Contract
Laboratory Program, the laboratories
contracting for organic and inorganic analyses
must show that they can initially meet all the
QC requirements (i.e., tuning, calibrations)
specified in the contracts when analyzing the
pre-award performance evaluation samples. In
addition, the laboratories must determine and
submit instrument detection limits for all the
analytes on all the instruments to be used on the
contract. For inorganics, the inter-element
corrections and linear ranges used for the ICP
are also submitted. The raw data for the initial
tests must be submitted with the pre-award PE
samples before a contract can be awarded.
Instrument Calibration and Verification
A review of the calibration requirements
revealed differences in the methods developed
within each Agency program. These differences
included different numbers of calibration points,
different frequencies of use and different
acceptance criteria. As an example of the
differences, the calibration requirements for the
GC/MS methods for volatiles (624, 1624, 8240,
etc.) are summarized below.
FWPCA. Under the FWPCA, the "600
Series" has two GC/MS methods for volatile
organics (624 and 1624). Instrument tuning is
required with bromofluorobenzene (BFB) prior
to calibration and analysis of samples. Method
1624 requires a five-point calibration curve for
each analyte while 624 requires only a three-
point calibration. Both methods require the
response factors (RF) used for quantitation to be
constant at all concentrations with percent
relative standard deviations (RSD's) ranging
from less than 10% to less than 35% in order to
use the mean RF for calculation. In 624, ongoing
calibration and BFB tuning verification is
required at least daily, while in 1624 it is
required every eight hours when the systems are
in use. Tables with specific acceptance criteria
for each compound are provided in the 600
methods.
SDWA. Under the SDWA, the "500 Series"
includes two similar GC/MS methods for volatile
organics, Methods 524.1 (packed column) and
524.2 (capillary column). The instruments must
be tuned with BFB prior to calibration and
analysis, same as with the 600 Series for VOA's.
The criteria for key ion abundances are also
6-11
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Table VI-4
Studies
AnaTytes
Clean Water Act
Water &
Wastewater
Samples
GC Purgeables
GC "600" Series
GC/MS
Purgeables
(VGA)
GC/MS
Semivolatiles
AAS Metals
ICP Metals
Safe Drinking
Water Act
Finished
Drinking Water
and Raw Source
Water
Organic "500"
Series
Metals - Same as
CWA
CERCLA-
Superfund(CLP)
Water, soil,
waste samples
GC-Pest.&
PCB's
Diox!n(2378)
GC/MS
Purgeables
(VOA)
GC/MS
Semivolatiles
Metals-AA
ICP
Approved EPA Methods in 40 CFR 136 Supported by Formal EMSL-Cincinnati Method Validation
., .. , Method Field Field Dup. Spike Matrix _La.b . Sur-
Methods Blank Blank Dup Sample Dup Sp±e^ Control rogateg g
jr Act
601-602
603-619
624
625
200.0
200.7
Daily
ESS
Daily
ESS
ESS
ESS
NS
NS
NS
NS
NS
NS
10%
10%
5%
5%
Daily
Daily
Req
Req
Opt., 10%
Yearly
502.1-
531
Daily
ESS
10%
10%
Qtrly.
608-CLP
613-CLP
624-CLP
625-CLP
200.0-
CLP
200.7-
CLP
5%, ESS
ESS
Daily,ES
S
5%, ESS
5%, ESS
5%, ESS
Rec
Rec
Rec
Rec
Rec
Recom.
5%
5%
5%, ESS 5%,
5%, ESS 5%, ESS
5%, ESS 5%,
5%, ESS 5%,
5%, ESS
5%, ESS
Req.
ACC
ACC
ACC
ESS
ESS
Qtrly.
ESS
Qtrly.
Qtrly.
Qtrly.
Qtrly.
RCRA
Soil, waste
samples
GC "8000" Series
GC/MS VOA
GC/MS Semi-
Vol.
Dioxin & Furans
HPLC(PAH)
Metals -Acid
Dig.
AA
ICP
8010-
8150
8240
8250,827
0
8280
8310
3000
7000
8010
ESS
Daily
ESS
ESS
ESS
ESS
ESS
ESS
NS
NS
NS
NS
NS
NS
NS
NS
-
-
-
NS
-
NS
NS
NS
ESS
ESS
ESS
ESS
ESS
20%
5%
5%
ESS
ESS
ESS
-
-
.
5%, 10%
20%
ESS
ESS
ESS
ESS
ESS
ESS
20%
5%
100%
CLP
CLP
CLP
-
ESS
-
-
-
-
-
NS
-
_
.
-
ESS - Each samples set NS-Not Specified Opt-Optional Qtrly - Quarterly
Req - Surrogates required, no acceptance criteria CLP - CLP criteria are used
ACC - Surrogate required; acceptance criteria established
Recom - Recommended
6-12
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similar to the 600 Series except for differences in
the requirements for mass 173 in Method 524.1.
Both methods require five-point calibrations
with constant RF's at all concentrations (percent
RSD ranging from less than 10 to less than 35)
for mean RF calculations. Similar to the 600
Series methods, ongoing calibration checks and
BFB tuning are required at least daily. Unlike
the 600 Series methods, however, the 500 Series
require the daily calibration check for every
compound to respond within 20% of the initial
calibration.
CERCLA. The method adopted by the CLP
for VGA's is Method 624-CLP-M which is
basically the same as 624 except that a five-
point calibration is required. In addition, key
compounds, termed system performance check
compounds (SPCC), must meet minimum RF's.
Calibration check compounds (CCC) must have
RF's within 30% RSD. Ongoing calibration
checks and BFB tuning verification are required
for every 12 hours of analyses. The minimum RF
criteria for the SPCC's (0.3) and the CCC's (RF's
- 25% of the initial calibration) must be achieved
every 12 hours.
RCRA. Under RCRA, the SW-846 Manual
has one method (8240) for GC/MS analysis of
volatile organics which operationally contains
requirements virtually identical to the CLP
requirements.
Laboratory Control Samples
Laboratory control (LCS) samples are
samples that are analyzed to verify that the
method performance was within specified
control limits. Laboratory control samples
include method or reagent blanks and check
samples containing known amounts of analyte.
The quality control samples supplied by EMSL-
Cincinnati are frequently used as LCS's. The use
of LCS's does not measure the performance of
the method on the samples analyzed, but does
demonstrate that the method was properly
performed.
FWPCA. For organics, most of the QC
samples required by the 600 Series organic
methods are generated in the laboratory and
include method blanks, sample spikes and
laboratory control samples. For inorganics, the
only QC sample specification contained in the
200.0 AA method is an "optional requirement"
to analyze a reference sample once per quarter.
The results for the reference sample should be
within the control limits established by EPA.
The ICP method (200.7) requires the analysis of
a "quality control sample" obtained from an
outside source to be used for the verification of
the calibration. The quality control sample
"should be prepared" in the same acid matrix as
the calibration standards. This does not
necessarily require that the QC sample is
carried through the entire sample preparation
and analysis methods. The "200" Series metal
methods do not, therefore, require a laboratory
control sample.
SDWA. For organics, the SDWA 500 Series
methods for volatile organic compounds (VOCs)
emphasize detectability at low concentrations
near the MCLs. Laboratory control samples at a
10% frequency or at least 2 samples per month
are required. The SDWA methods have also
specified the analysis of a low level QC check
sample on a weekly basis. The inorganic QC
requirements for SDWA are the same as those
under FWPCA.
CERCLA. The CLP methods under
Superfund require method blanks or preparation
blanks for every sample matrix or every 20
samples, whichever is more frequent, and lab
control samples for inorganics. There are no LCS
requirements for organics.
RCRA. Under the RCRA program, the SW-
846 Manual, 3rd Edition, has quality control
requirements in several sections, which
sometimes have confusing specifications. The
RCRA methods specify the collection of field
duplicate samples, field blanks, and equipment
blanks (rinsates) in the general QA section but
do not specify a frequency. For inorganics the
only QC sample required for AA or ICP is the
preparation blanks. Method 6010 also requires
the preparation of a "quality control sample" in
the same acid matrix as the calibration
standards, similar to Method 200.7. Unlike
Method 200.7, however, the RCRA method does
not indicate when or if that sample should be
6-13
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analyzed. Requirements for the analyses of
LCS's for organics are not specified.
Sample Specific Quality Control
Sample specific QC requirements are
contained in the analytical methods to document
the performance of the method for the samples
analyzed. The QC requirements include matrix
spikes, duplicate matrix spikes, duplicates, and
surrogate spikes. A lab sample duplicate is a
sample that is a split at the laboratory and both
the splits are carried through the entire sample
preparation and analysis procedures as separate
samples. A sample spike is the addition of
standard(s) to a sample before sample
preparation. A sample spike duplicate is a
sample split at the lab with both splits spiked
with the same standard and then carried
through the entire sample preparation and
analysis procedure as separate samples. Most
programs require either duplicate samples and a
spike sample or sample spike and duplicate
sample spikes. Only the RCRA program requires
all three in some cases, a duplicate sample, a
spiked sample and a duplicate spiked sample.
FWPCA. The 600 Series methods for
organics require a laboratory spiked sample at a
frequency of 10%, except for methods 624 and
625 which require a frequency of 5% (one per 20
samples). The GC/MS methods require the
addition of surrogate spikes to each sample.
Neither duplicate samples nor duplicate spike
samples are required in the organic methods.
For inorganics, neither the 200.0 AA method
nor the 200.7 ICP method requires duplicate
samples or spiked samples, although a duplicate
sample is recommended in the AA method
(200.0). An analytical (post-digest) spike is
recommended in method 200.7 (ICP) for new or
unusual sample matrices and is required in the
individual AA methods for every sample matrix
to verify that standard additions are not
required. There are no criteria specified for the
AA spiked sample, while a criteria of 100 ± 10%
recovery is specified for the spike in the ICP
method to indicate possible interferences.
SDWA. The 500 Series methods for organic
compounds do not require laboratory duplicates,
spike samples, or surrogates. The inorganic
methods have the same requirements as those
under FWPCA.
CERCLA. The organic CLP methods
require a spike sample and a spike sample
duplicate at a frequency of 5% or per sample
batch, whichever is more frequent, and
surrogates in each sample. The criteria for the
matrix spike and matrix spike duplicate
recoveries for each compound are contained in
tables in the SOW. The inorganic CLP methods
require a matrix spike sample and a duplicate
sample at a frequency of 5% or per sample set,
whichever is more frequent. The duplicate
samples must be within ± 20% and the matrix
spike recovery must be 100 ± 25%. If the matrix
spike is out of control, an analytical spike (post-
digest) is required to separate the analytical
method performance from the digestion
performance.
RCRA. The sample specific QC procedures
contained in the 3rd Edition of SW-846 is
somewhat confusing since the QC section, the
general sections, and each individual method,
often have different requirements. The QC
chapter, 1.3, requires a detection limit and
quantification limit of all analytes to be
evaluated by determining the noise level of
response for each sample. Method 6010 for ICP
specifies only a duplicate sample at 5%
frequency and a spiked sample duplicate (i.e.,
two separate spiked samples) at a 20% frequency
(every 5 samples). The general AA method
(7000) specifies a duplicate and a spike sample
every twenty samples (5% frequency), while the
individual AA methods often specify a third
requirement. Method 7060 for arsenic, for
example, requires "duplicates, spiked samples,
and check standards should be routinely
analyzed" in 7.8, but the QC Section 8 requires
only a spike duplicate sample every 20 samples
(5% frequency), not a duplicate sample and not
the 20% frequency specified in the ICP method.
Method 7470 for mercury requires a spike
duplicate every 10 samples (a 10% frequency).
Thus, for AA methods, the QC requirements
include 5% and 10% frequencies, sometime a
spike and duplicate and sometimes a spiked
duplicate without a duplicate sample. The ICP
method requires a duplicate spike sample at a
20% frequency. The QC requirements in the
6-14
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digestion methods specify a duplicate sample at
a 20% frequency (every 5th sample) which
contradicts both the AA and the ICP methods.
There is no obvious reason why the QC
requirements should be so dramatically
different between methods and analytes and it
adds significant confusion to the laboratory
attempting to analyze the sample according to
the recommended methods.
For organic analyses, a spiked sample and a
spiked sample duplicate are required at a
frequency of 5% (one every 20 samples) with
surrogates required on all samples. The
surrogate spikes are not identified in the GC
methods. Duplicate samples are not required.
There is some confusing language in the method
however. For example, method 8250, 5.6, states
that the matrix spike standard is injected "into
the GC/MS to determine recovery of surrogate
standards in all blanks, spikes and extracts".
Although most of these problems are probably
due to typographical errors, these
inconsistencies become requirements for the
laboratory community when the methods are
quoted in the regulations.
A summary comparison of the QC
requirements for the various programs is shown
in Table VI-2. Another summary comparison of
the QA/QC requirements including criteria are
given for some methods in the methods
comparisons in Tables V-l, V-2 and V-3.
Computerized Quality Assurance
Because EPA realized that the exponential
increase in the volumes of data generated places
a burden on its ability to monitor the integrity of
analytical results, the Agency is moving toward
computerized evaluation of environmental data
quality.
As an example of this, the Industrial
Technology Division (ITD) in EPA's Office of
Water Regulation and Standards has been
evaluating results of gas chromatography/mass
spectrometry (GC/MS) analyses on EPA's
mainframe computer. The advantages of
computerized evaluations are the removal of
subjectivity of human judgment and drudgery
and the rapid availability of quality-assured
results.
ITD's need for computerized quality
assurance was brought about by the large
volume of data generated in analyses of
wastewaters. In ITD's programs, data generated
by the contract laboratories are placed on
magnetic tape in a raw data format used to
archive data for subsequent testing as a part of
the 1976 Consent Decree paragraph 4(c) and in a
reduced data format for reporting final results.
Magnetic tapes of the raw data are shipped to
EPA's Environmental Research Laboratory in
Athens, Georgia for identification and
quantification of unknown pollutants. The
reduced data are shipped to EPA's National
Computer Center in Research Triangle Park,
North Carolina for computerized data quality
evaluation. After evaluation, reports of final
pollutant concentrations and statements of data
quality are printed out at EPA Headquarters for
ITD use in developing effluent limitations and
guidelines.
Based on the concepts provided by ITD, and
on the commonality of quality assurance in
EPA's GC/MS methods, instrument
manufacturers have begun producing software
packages capable of computerized evaluation of
data quality. In turn, EPA has had to refine the
quality control requirements in its contracts to
make them more definitive. The obvious
advantage of monitoring data quality at the
point of generation is that data, will be of
acceptable quality when received by the user
and rejections and reruns will be reduced.
Data Reporting Requirements
In nearly all of the Agency's environmental
monitoring programs, the reporting
requirements are external to the analytical
methods. This separation permits the method to
be used by organizations external to EPA (e.g.,
industry). One exception to this separation is the
Superfund Contract Laboratory Program (CLP),
in which the reporting requirements are
included in the analytical methods. This
inclusion is desirable for the CLP because the
methods and data are intended almost
exclusively for Agency use, whereas nearly all
6-15
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other Agency methods are intended for use by
EPA and the analytical community at large.
For other methods, each regulatory program
has defined its reporting requirements, leading
to a variety of reporting formats through EPA
and adding to the difficulties in comparing
environmental data between programs. Data
reporting requirements, whether internal or
external to methods, are not always consistent.
Inconsistencies result from varying program
requirements, or changes in method technology.
One example is the problem of reporting
pollutant contaminants at concentrations which
cannot be measured accurately or which cannot
be quantitated. Many of the different and
accepted "codes" for reporting these levels are
contained in RCRA's SW-846 Manual Table 11-
2. Unfortunately, RCRA allows 14 variations to
be used. Other programs have similar reporting
codes as follows: LOD (Limit of Detection), LOQ
(Limit of Quantification), PQL (Practical
Quantitation Limit), MQL (Method
Quantitation Limit), MDL (Method Detection
Limit), IDL (Instrument Detection Limit),
CRDL (Contract Required Detection Limit), LT
(Less Than), BDL (Below Detection Limit), <
(Less Than #), - (i.e., <0.01), "trace" or "t", ND
(Not Detected), "K" (i.e., K0.01), "u" (i.e.,
STORET),- (dash), large numbers (i.e., 99999),
zeros, 0 (i-e., [0.01]), and of course blanks. In
many cases, the symbols are ambiguous because
the meanings could be that the value was at the
limit of detection or the constituent was not
present. This problem is exacerbated when
samples must be diluted.
Once the data are reported, the problem
arises as to how calculations are performed for
the various requirements such as spike
recoveries, duplicate precisions, etc. In some
cases, zero is used and in other cases one of the
many types of detection or quantitation limits
are used. Many methods include general method
detection limits, but provide little guidance for
determining a practical quantitation limit for
real samples. The following section summarizes
the few data reporting requirements specified in
the various EPA programs.
FWPCA. The organic "600" series methods
specify that "all QC data obtained should be
reported with the sample results". Exactly how
or what QC is to be reported is not specified, and
often this requirement is not followed by
laboratories. The methods also specify that the
concentrations should be reported as ug/L
without correction for recovery. The inorganic
"200" series AA methods specify only that
results entered into EPA's STORET database
must be in ug/L. The ICP method (200.7),
however, requires data be reported in mg/L up to
three significant figures as well as corrected for
the reagent blank.
SDWA. The inorganic requirements for
SDWA are the same as in FWPCA methods. The
organic "500" series methods all require
reporting in units of ug/L. The methods also
require that "all QC data obtained should be
reported with the sample results"! Additional
requirements are specified under the National
Primary Drinking Water Regulations
(NPDWR): results of all analytical methods
including negatives (i.e., not detected); the name
and address of the system that supplied the
sample; contaminants; analytical methods used
and the dates of sampling and analysis. The
SDWA set the PQL's for 7 regulated VOCs at 5
ug/L, and at 2 ug/L for vinyl chloride, which was
described as approximately 5 to 10 times the
MDL.
CERCLA. The reporting requirements
under Superfund's Contract Laboratory
Program are very detailed and quite extensive to
permit independent review by other chemists.
Nearly every aspect of the analysis is
documented with rigid format and specified as-a
deliverable. All the QC to be reported and its
format is specified in detail. Specifications are
also given for calculations, units, detection
limits, etc. The most recent CLP requirement for
reporting all the data results on computer
diskette has resulted in exact directions and
formatting for the reports to allow direct reading
into the EPA computers. The organic
deliverables include, but are not limited to:
summary of GC and GC/MS calibrations, GC/MS
tuning results, calibration verifications, sample
and QC samples tabulated results (blanks,
surrogates, spikes, spiked duplicates, etc.), raw
data (i.e., mass spectra and chromatograms) and
results for the tentatively identified compounds.
6-16
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The inorganic deliverables include the summary
of the AA ICP calibrations, the calibration
verifications (initial and continuing), the sample
results and sample description, the QC samples
results (blanks, spikes, spiked duplicates, etc.),
and the raw data (i.e., direct readout from the
instrumentation). Despite the perception that
the CLP requires tremendous amounts of extra
results, the CLP protocols do not require
exceptional amounts of QC, but only that all the
QC have criteria, that these criteria be met, and
that all QC be reported and delivered with the
results.
RCRA. The third edition of SW-846
stipulates that the QC data must be available
from the laboratory upon request and adopted
most of the reporting requirements of
Superfund's CLP, including all the forms.
Unfortunately, some of the QC requirements do
not always fit with the CLP forms and confusion
can arise. Many contract analytical laboratories
assess an additional fee to cover the cost of
providing the cost of the data packages for
RCRA. Both RCRA and CLP require the
reporting of percent moisture or percent solid
content of the samples without blank correction.
The determination of PQL's for organic
compounds in various matrices are specified in
SW-846 and are calculated by multiplying the
MDL by a matrix "factor". The MDL's and the
matrix factors are provided with each method.
For example, in method 8250 (GC/MS for semi-
volatiles), the factors are 10 for groundwater; 70
for low level soil; 10,000 for high level soil; and
100,000 for non-water miscible waste. The PQL's
do not take into account any dilution or pre-
concentration and the matrix "factors" may be a
somewhat simplistic approach to the problem of
reporting limits in different matrices.
In general, most methods do not provide
sufficient information for reporting
requirements. Documentation should be
available to provide information sufficient to
support all claims made from the results
including the QA and QC data. Measurements
should be reported in consistent units only to the
number of significant figures consistent with
their limits of uncertainty. Reports should make
clear which results, if any, were corrected for
blank and recovery measurements. Reports
should be written to include sufficient
information so that the users of the data can
understand the results without having to return
to the raw data to make their own
interpretation. Finally, and most importantly,
data should be reported with enough
information to establish the quality of the
results.
Quality Assurance and Quality
Control for Biological Methods
Quality assurance guidance for the various
biological methods is very diverse in its goals,
requirements, and adherence. A solid QA/QC
program for microbiological methods has been
established by the Agency for the SDWA
Drinking Water Certification Program and can
serve as a standard against which other EPA
programs can be compared. The SDWA QA
program includes analyses of performance
evaluation (PE) samples on an annual basis, on-
site visits, initial certification and
recertification procedures, investigation
methods for problems and rigid inhouse
requirements for precision studies. In response
to the 1986 Amendments to the Safe Drinking
Water Act, this program will need to be
expanded to include samples for viruses,
heterotrophic plate counts and presence/absence
tests for total and fecal coliform bacteria.
A similar program does not yet exist for
FWPCA biological tests. It should be developed
for all biological or bioassay methods
promulgated in 40 CFR 136.
A national program for the certification of
toxicity testing laboratories would be useful in
insuring the quality of test data. At present, two
states (California and New Jersey) have
laboratory certification programs for toxicity
testing laboratories. QC support for a toxicity
laboratory certification program has been
started within the Quality Assurance Branch at
the EPA EMSL-Cincinnati. Standard reference
toxicants (copper sulfate, cadmium chloride, and
sodium dodecylsulfate) are available upon
request. Ampuls are supplied with instructions
and an expected range of LC50 results. While
this reference toxicant program is conceptually
sound, it has been very limited in scope in the
absence of a national certification program for
6-17
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the FWPCA. Sample distribution is limited due
to current funding problems. While temporary,
this may inhibit the development of the QA/QC
practices necessary for the technique-oriented
biological and biomonitoring methods in testing
laboratories. EPA should accelerate the
development of a full QA/QC program for
biology and seek to make the use of QC and PE
samples mandatory for aquatic toxicity.
The QA section of the acute toxicity methods
manual includes a cumulative summary
(cusum) graph or control chart developed from
data for a specific reference toxicant and species
of test organism. This running plot is
maintained by adding new data each time a
standard reference toxicant test is performed.
The LC50 should fall between the upper control
limit (mean plus two standard deviations) and
the lower control limit (mean minus two
standard deviations), the sensitivity of the test
organisms or the credibility of the test system
are suspect. The reference toxicant test should
be repeated with the same organisms or a
different source of test organisms.
The maintenance of a control chart is a
useful concept to ensure quality data and should
be required. In the "Short-Term Methods for
Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms
Manual", a frequency for reference toxicant tests
is specified. This requirement should be
incorporated into all toxicity test methods.
Chapter Six References
1. Taylor, J.K. Principles of Quality Assurance
of Chemical Measurements. U.S.
Department of Commerce, National Bureau
of Standards, Gaithersburg, MD. February,
1985.
2. Principles of Environmental Analysis. The
American Chemical Society. Revision to the
Guidelines for Data Acquisition and Data
Quality Evaluation in Environmental
Chemistry:, Anal. Chem. 1980, 52,2242-
2249.
3. Quality Assurance for Environmental
Measurements. ASTM Special Technical
Publication - J.K. Taylor and T.W. Stanley,
Editors. American Society for Testing and
Materials, 1985.
4. Keith, L.H. Identification & Analysis of
Organic Pollutants in Water. Ann Arbor
Science Publishers, Inc., 1977.
5. Quality Control in ' Remedial Site
Investigation. Perket, C.L. American Society
for Testing and Materials, 1986.
6. EPA, 1983. Interim Guidelines and
Specifications for Preparing Quality
Assurance Project Plans. Office of
Exploratory Research, Washington, DC.
EPA-600/4-83-004. February, 1983.
7. Manual for the Certification of Laboratories
Analyzing Drinking Water. EPA Office of
Drinking Water, EPA-570/9-82-002, 1982
(In re vision).
6-18
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CHAPTER SEVEN
IMMEDIATE AND LONG-TERM TECHNOLOGY AND
TESTING METHODS NEEDS
The regulatory programs directed and
managed by EPA have significantly motivated
the development and commercialization of the
analytical technology required to support
environmental monitoring. In addition, the
Agency has been the principal developer of
testing procedures and methods and provider of
testing methods to perform chemical and
biological monitoring required to support all
environmental programs in the United States.
Although the EPA has made significant strides
in developing the technology and methods in use
today, the recent pace of environmental
regulation has created a demand for testing
technology and methods greater than ever
before. The demands for new technology and
improved methods are based on program needs
attributable to increased emphasis on the
measurement of more analytes in more complex
matrices at lower levels and with better
performance. In order to ensure continued
success to meet these increased demands, EPA
should continue its role as the leader in the
development of methods in a number of areas.
Some of these areas require immediate
attention to meet a specific program need (e.g.,
methods to measure organic chemicals and
metals in POTW sludges). Other areas are
broader based and will require the
implementation of new technology (e.g.,
methods for the measurement of polar water-
soluble organics). In addition, there are needs to
improve the reliability of existing methods and
to develop generic methods that are suitable for
many needs (e.g., multiresidue pesticide
methods). This chapter discusses these
immediate and long-term needs and the process
used, or that should be used, to meet these needs.
Overview and Summary
The ability of laboratories to detect and
measure pollutants in environmental samples
has improved exponentially over the past 25
years. For example, in 1951, the U.S. Public
Health Service first reported the presence of
organic chemicals in drinking water (7-1). The
method required the collection of up to 80,000
gallons of water for each analysis. Extensive,
laborious operations were performed to
demonstrate that the water contained organic
chemicals in the parts per billion (ppb) range at
an analytical cost of several thousand dollars
(today's dollars). The specific chemicals present
could not be identified. By comparison, a routine
analysis for halogenated volatile organic
compounds can now be performed on as little as
5 milliliters (mL) of sample (0.0002% of the
sample required in 1951). Today, reliable
identification and accurate measurements of
these compounds can be performed at the sub
part per billion level for about $100 per analysis.
This improvement in technology has also
been reflected in other ways. At the time of the
Natural Resources Defense Council (NRDC)
Consent Decree in 1976 (7-2), environmental
analyses for toxic chemicals were typically
performed at universities or research centers.
There were few commercial laboratories
operating gas chromatography/mass
spectrometry (GC/MS) instrumentation and
7-1
-------
there were virtually no standardized methods
for the measurement of specific pollutants in
water. In the decade since the Consent Decree,
the improvements in instrumentation, the
quality of the analytical methods and the growth
of laboratories capable of performing these
analyses has been astronomical. It has been
estimated that in 1986 over 500,000
environmental samples were analyzed in the
United States (7-3). Similarly, there have been
dramatic improvements in the sensitivit/ of
short-term toxicity tests and in the development
of new genotoxicity tests.
Despite these improvements, much remains
to be done. Based on the increasing demands
from existing regulations, existing testing
methods will require significant improvement
and new technology must be developed and
standardized to satisfy these demands.
Specifically, new technology, or modifications to
existing methods are required to improve
sensitivity, precision, accuracy, specificity,
applicability and reliability. Many of these
methods require highly skilled analysts and
complex, expensive instrumentation. The
explosive demand for analytical data has
resulted in a proliferation of commercial
analytical laboratories, and a shortage of
trained and experienced personnel. These
factors contribute to the need for significant
improvements in the methods and technology
available today. These factors also contribute to
the need for training of analytical chemists,
continued support in supplying methods,
reference materials, and guidance to the
regulated community. Significant limitations
are inherent in existing technology and will
require development of completely new
technologies to solve some analytical problems.
The combination of needs to improve the
performance of existing methods and to develop
new technology will require a concerted
intensive effort by the Program Offices and
ORD.
As explained in more detail in subsequent
sections, there are a multitude of immediate
needs which need to be addressed. These needs
range from improving an existing method to
developing a new method in response to
legislative mandates. Beyond these immediate
needs, the Agency plans to continue its
investigations into new technologies which will
provide solutions to tomorrow's environmental
problems. The Agency must maintain a
leadership role in analytical methods
development if it is to maintain technical
credibility in this area.
Until the early 1980's, the scientific and
regulated community, as well as technical staff
within the Agency, believed that there was a
good balance between the available technology
and methods and the regulatory requirements.
However, in the last five years, the consensus is
that the monitoring demands have significantly
outstripped the Agency's ability to provide
technology and methods capable of fully
supporting these programs. The Agency with its
current organization and resources cannot
provide the technology and methods required to
fully support the immediate and long-term
monitoring requirements established under
current environmental laws. While the Agency's
resources must be greatly increased to solve
priority problems, federal efforts need to be
more sharply focused on developing technology
and improving existing methods. Novel and
innovative programs need to be implemented to
encourage the commercial sector (e.g.,
instrument manufacturers) to develop the
technology evolving from federal laboratories or
academia. The use of mechanisms contained in
the Technology Transfer Act of 1986 (Public
Law 99-502) needs to be implemented to
enhance the commercial-ization of new
technology. A more organized effort within the
Agency is essential to eliminating the
tremendous duplication of efforts being
expended in solving the same basic problems.
Immediate Methods Needs
Near term methods needs arise principally
from environmental legislation. The Program
Offices typically are faced with demands to
develop regulations that-require either new
methods or improvements in the existing
methods. The development of methods in this
situation requires close coordination between
the Program Offices and ORD. The method
needs are very specific, for example, the
measurement of specific organic compounds in
7-2
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POTW sludges, and the time available to
develop the method is typically very short. Due
to the tremendous and varied needs from the
Program Offices, the researchers are overloaded
and many development programs are not being
done or are being done at contract laboratories.
Furthermore, due to the lack of a focused effort,
each Program Office is developing methods for
its program resulting in inconsistent approaches
to the development process.
The formation of an Environmental Methods
Management Group (EMMG) will resolve many
of these problems. The fact is that many methods
needs cross program lines. For example, an
improved extraction technique for pesticides
will result in better data for all of the Agency
programs which require measurement of
pesticides. For this reason it is important that
all Agency methods development work be
coordinated.
One of the objectives of the EMMG is to
coordinate Agency-wide short term methods
development activities. One of the first activities
of this group should be to review and prioritize
the immediate methods development needs of
the Agency. Based on a review of Program Office
needs, over 200 different short-term needs were
identified which directly impact monitoring
required under the Federal Water Pollution
Control Act (FWPCA).
These needs encompass the technical
disciplines of inorganic chemistry, organic
chemistry, microbiology and aquatic biology.
Some of these needs are well defined and should
be readily achieved, e.g., a capillary method for
volatile organics. Others will require more
intensive efforts, e.g., establishment of
definitive holding times. In some cases, a
generic need (e.g., better cleanup techniques,
better pollutant identification techniques) may
solve both short-term and long-term problems.
For example, it may be possible to develop a
cleanup technique based on existing technology
which improves an existing method. New
technology may in the future provide even better
performance.
Most of the short term methods development
needs are oriented towards improving the
performance (cost, sensitivity, reliability,
accuracy, etc.) of an existing method or
increasing its applicability (new matrices,
additional analytes). Some of these needs are
listed in Table VII-1. It should be noted that this
table is not a complete inventory of immediate
needs, but examples of the types of needs that
require solutions. Virtually all of these needs
are also needs in other programs.
Long-Term Technology Needs
The methods developed by the Agency that
are used today are based on the best
demonstrated technology that is available to the
regulated community. Research efforts are
ongoing to improve these methods. However,
every method has limitations. These limitations
are generally caused by:
• the chemical and/or physical property of
the analyte being measured;
• interferences present in the sample
matrix;
• the adequacy of the method to
unambiguously determine the analyte at
the specificity and sensitivity required; or
• insufficient knowledge of the biology of
commonly used test organisms.
The Agency is conducting research into new
technologies that address these concerns. For
example, liquid chromatography coupled with
mass spectrometry is being investigated as a
technique for the measurement of polar water-
soluble organic compounds.
It should be noted that while some of these
research areas may soon result in improvement
to current methods, it is more likely that it will
be years before these research efforts will have
any real impact. In fact, it is likely that some of
these techniques will never prove useful. This
factor should not deter the ongoing efforts.
As an example of this process, Table VII-2
traces the development of three technical areas
which are related to environmental analyses:
• Gas Chromatography - Fourier
Transformer Infrared Spectrometry
(GC/FT-IR)
• Open Tubular (capillary) Column GC
7-3
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Table VTI-1 E xamples of Immediate FWPCA Methods
Development Requirement Needs
• Effective extraction and digestion methods for
metals and organic analysis of complex matrices,
e.g., sludges, sediments, fish tissue.
• Standardized clean-up methods for metals and
organics in sample extracts from complex and
variable matrices, e.g., sludges, tissues.
• Determination of scientifically valid and legally
defensible sample holding times in all sample
matrices.
• Reliable sampling protocols for all environmental
media.
• Artificial intelligence systems for inferring
substance identity from instrumental analytical
data when the compound does not match any spectra
available in the libraries.
• Computer data processing systems capable of
performing routine QA/QC evaluation of monitoring
data.
• Direct methods (no-preconcentration) for
quantitation of toxic and related organic compounds.
• Methods to measure organics and metals at lower
levels.
• Methods to analyze for longer target lists of
chemicals which also can identify the presence of
other toxic metals and organics.
• Automation of organics sample preparation
techniques.
• Ion chromatographic procedures for anions.
• Development of solid sorbents for water sampling.
• Incorporation of capillary column GC methods.
• Methods for measuring effects of wastewaters on fish
and aquatic life.
• Rapid methods to detect and quantify sublethal
aquatic toxicity in industrial and municipal
discharges.
• Rapid methods to detect pathogens in sludges.
• Ion Chromatography
These three examples illustrate the time
required for a technique available at the
research level to become commercially available
and fully standardized. These three areas are
discussed below.
The GC/FT-IR technique is under
investigation as a technique for environmental
analysis. The technique holds promise as a
technique for rapid screening of samples to
determine compound class assignments. In the
20 years since the technique first appeared in
the literature, instrument costs have decreased
and the sensitivity of the techniques has
increased. However, the technique is still
considered to be under development. GC/FT-IR
is not being used on a routine basis for
environmental analyses.
By comparison, the development of capillary
column GC technology has had a very rapid (10
year) growth with continued improvements. The
glass capillary columns available in the 1970's
were very cumbersome to use and were less
efficient than the fused silica columns available
today. Capillary column technology has
essentially replaced the packed column method
originally developed for Method 625. In addition
to the improvements in column efficiency, the
newer columns have improved the precision and
accuracy of the measurements and now require
less skill in their installation and maintenance.
Ion chromatography was patented in 1975
for measuring anions in water. In essentially a
10-year period, the technique has been refined to
measure both cations and organic ions. Over
Table VH-2 Examples of the Development of Envi-
ronmental Analytical Instrumentation
Limit,ug
Price
Event
1965 N/A First publication
1969 10-5 $200K First commercial
instrument
• Very slow scan
rate
• No library
search
1975 10-7 $ Gold light pipe &
MCT detector
technology became •
commercially
available
1980 $180K Research began on
new sources and FT
technology
1986 10-8 $40K 1980 technology
became
commercially
available as a GC-
only detector; result
was major price
breakthrough
1987 10-8 $70K High sensitivity;
10-10 capillary GC
$150K Matrix isolation
1989? 10-8 <$100K First EPA method
verified and
published
7-4
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(2) Open Tubular (Capillary) Column GC
Date Column Efficiency Event
1977 2000 plates/meter Glass capillary columns and
capillary injectors became'
widely available
commercially
1980 4000 plates/meter Fused silica (physically
rugged) capillary columns
developed.
1980 4000 plates/meter Bonded phase (chemically
rugged) capillary columns
developed.
1984 - First EPA capillary GC
methods finalized.
N/A Megabore™ columns
developed.
1987 10,000 lOOum I.D: capillary
plates/meter columns commercially
available
< 5% of EPA methods using
'capillary GC technology
(3) Ion Chromatography (1C)
D t Incremental pri
Uate Capability Knce
Event
1975 Anions(-) $10K
1980 Cations( + )
1985 Organic Ions
Anions
1986 Reverse phase $10-40K
Patent issued to Dow
Chemical Dionex
Incorporated
Development of
gradient elution;
election; able to elute
organic and inorganic
ions
First EPA method
published (Method
300 - drinking water)
Technique merges
w/HPLC
6000 instruments are used in environmental
laboratories. The time from the development of
the instrumentation until the approval of the
first EPA method was less than ten years, one of
the fastest developments of technology and
methods.
The EMMG should focus its energies on
prioritizing the long-term research goals of the
Agency, in cooperation with instrument
manufacturers, universities and commercial
laboratories. These long-term research needs
should address the major limitations, such as
those listed below, associated with today's
technology.
Table VII-3 lists some examples of new
technologies which are currently being
investigated. These technologies hold promise
not only for superseding the performance of
existing methods (i.e., better sensitivity, lower
cost, more reliable identification) but also in
solving additional needs such as:
• measurement of polar water-soluble
organics,
• speciation of organometallic or inorganic
species,
• providing on-line continuous monitoring,
and
• use of immunoassay and gene probes to
detect pathogens.
These techniques are discussed in more
detail subsequently.
Discussion of Emerging
Technologies and Methods
The previous section discussed generically
both short-term and long-term methods
development needs. This section provides more
detailed discussion of some areas that are
undergoing development, organized into
inorganic chemistry, organic chemistry and
biology.
Inorganic Chemistry
With the increased emphasis on the
measurement of toxic metals to determine
compliance with health based regulations, more
metals will need to be measured simultaneously
in a broader suite of sample matrices. Several
new emerging technical and commercial
developments over the next five years will have
a significant impact on environmental analyses
for inorganic analytes. These new technologies
should decrease the cost of analyses, increase
laboratory productivity and the quality of the
analytical data and lower the effective detection
limits in a wide variety of sample matrices.
Some of these technologies are described below.
7-5
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Table VII-3 Examples of New Technology for Potential
Routine Use
Gradient Ion Chromatography
Continuous Monitoring Electrodes
Enzyme Electrodes
Inductively Coupled Plasma/Mass Spectrometry
Inductively Coupled Plasma - Hydride - Optical Emission
Spcctroscopy
Inductively Coupled Plasma - Fourier Transform - Optical
Emission Spectroscopy
X-Ray Fluorescence
Anodic Stripping Voltametry
High Performance Liquid Chromatography/Electrochemical
Detection
Immuno Assay
High Performance Liquid Chromatography/Mass
Spectrometry
Super Critical Fluid - Mass Spectrometry
High Performance Liquid Chromatography/Fourier
Transform Infrared Spectroscopy
Gas Chromatography/Fourier Transform Infrared
Spectroscopy
Super Critical Fluid/Fourier Transform Infrared
Spcctroscopy
High Resolution Mass Spectrometry
Triple Quadrupole Mass Spectrometry
Robotics
Super Critical Fluid Extraction
Gas Chromatography Atomic EmissionSpectroscopy
Super Critical Fluid Atomic Emission Spectroscopy.
The area of sample preparation is the most
labor intensive segment of environmental
analyses. Unfortunately, EPA and other
government agencies have established digestion
methods for many different metals which are
basically the same except for small differences
(e.g, acid strength, amounts added, etc.). In the
coming years, there should be a consolidation of
digestion methods which would improve the
comparability of data. Microwave digestion
techniques could significantly impact the
sample preparation for inorganics. In this
method, the sample is placed in a pressurized
digestion vessel, acidified, and then heated in a
special microwave oven. Preliminary studies
indicate that this technique may result in a
more complete digestion in less time than
conventional heating on hot plates. More studies
must be done on this and other digestion
methods for various matrices to ensure precision
and accuracy in the digestions and the
comparability of results with existing
techniques. Microwave digestion methods can be
developed for oily wastes to finally resolve the
problems of analyzing metals in very difficult
matrices.
While not a significant problem for water
samples, getting a representative sample of all
other matrices is the most significant factor
controlling the precision of a test. Another
improvement in sample preparation will be in
the development of standardized sample
homogenization methods to permit more
reproducible analyses of soil, sediment and
waste samples. Standard sample preparations
must also be developed for biological tissues as
more and more environmental studies are
addressing bioaccumulation.
For mercury, multiple sample preparations
are presently used within EPA and in other
agencies. Studies should be conducted to
determine the significance of the differences in
the various digestions and develop a
consolidated method to permit better
comparison of the data. Improved sample
preparation techniques must also be developed
for silver and antimony, particularly in soils and
sludges.
In the next decade, the application of
inductively coupled plasma/mass Spectrometry
(ICP/MS) to environmental analyses could result
in the single greatest impact on the analysis of
metals. The ICP/MS technique has all the
advantages of optical ICP/atomic emission
Spectroscopy (AES) in that it can perform rapid,
multielement determination of almost all
elements in the periodic table in a sample, but
ICP/MS also has very low detection limits,
nearly equal to .graphite furnace atomic
absorption Spectroscopy (GFAA). Similar to
GC/MS, ICP/MS is very specific for the
identification and quantification of a specific
target list of elements and can identify and semi-
quantitate other metals that may be present in
the sample by operating in the scanning mode.
ICP/MS also has a much wider linear working
range than GFAA (i.e., 0.001 to 100 ppm).
ICP/MS can also provide isotope measurement
capability, improve the accuracy of
measurements by using isotope dilution
methods, and provide analyses for radionuclides.
7-6
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The ICP/MS could perform many of the
traditional radiochemical methods and perform
the analyses in minutes instead of days.
The ICP/MS can be used in the scan mode, as
mentioned earlier, to provide a quick screen for
metals in environmental samples by the rapid
identification, and semi-quantitative
measurements of most elements. ICP/MS will
also be used in conjunction with liquid
chromatography (LC) to measure organometals
and other metal species.
Improvements in ICP optical systems should
occur with the computerization and automation
of the instrumentation, improved selectivity and
sensitivity, and in the use of the hydride
technique to measure low levels of critical
elements (i.e., arsenic and selenium) in a
simultaneous, multielement mode. Although
presently a difficult method to perform correctly,
recent studies have indicated that improved
hydride methods will be developed for
application to routine production analyses.
Ion chromatography (1C), particularly
gradient ion chromatography, will become more
routine in the future. Currently approved only
for analysis of drinking waters for nitrate, the
technique has not been widely applied for
routine analyses in other matrices. The
advantages of the method are that it is relatively
fast, has good sensitivity and determines several
analytes at once. Further improvements in
column technology and experience with this
technique will aid in the expansion of 1C into
routine chemical analysis for many matrices.
Inorganic analytical instrumentation as a
whole is evolving towards an emphasis in
automated sampling and analysis including
computerization of the quality control decisions
with corresponding action to be taken (i.e.,
reanalysis, respiking, etc.), networks and
electronic communication (instruments to and
from main computers), Laboratory Information
Management Systems (LIMS), and
environmental-specific software. These
developments are being driven by the need to
interface with LIMS systems to allow automated
data acquisition, automated quality assurance/
quality control (QA/QC) review, data archival
and result reporting packages, all of which lag
significantly behind the more computerized
organic analytical instrumentation. The prices
of instrumentation will continue to decrease as
ICP's become as common as atomic absorption
spectrophotometers. ICP/MS will be refined and
used routinely as instrument conditions and
interference corrections are better defined. For
EPA work, on-line communications will be used
to transport and review data results, at least for
the CLP laboratories. AA instrumentation,
particularly, will be computerized and
programmed to make the QC checks and
decisions now performed by the analyst with the
data transmitted to a central computer which
will correlate the incoming data and write the
reports for the laboratories.
Holding times for samples is fast becoming a
critical issue as sample loads increase for
laboratories. Studies will need to be completed to
determine scientifically supportable holding
time requirements for organic and inorganic
compounds in a variety of matrices including
waters, soils, wastes, sludges and biological
tissue. Important inorganic analytes that should
be studied are the unstable elements such as
mercury, cyanide and chromium (particularly
hexavalent Cr). Efforts to develop and improve
analytical methods will continue for a variety of
inorganic analytes such as Total Organic
Halides (TOX) in sediments and soils, cyanide in
the presence of sulfide, fluoride, ammonia, Total
Kjehldahl Nitrogen (TKN), sulfate and phenols.
In addition, requirements for the analysis of
asbestos in air and water will increase the
development of improved, standardized asbestos
analysis, probably by Transmission Electron
Microscopy (TEM) or other optical techniques.
Hopefully, a method will be standardized for the
analysis of hexavalent chromium, Cr (VI), to
meet environmental program requirements to
assess the fate and effects of this important but
very difficult analyte to measure.
Organic Chemistry
A large number of new technical and
commercial developments will evolve during the
next five years. These will be available to
environmental laboratories and should
significantly impact the quality of analytical
7-7
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data, laboratory sample throughput, and/or cost
of analysis.
Some of these techniques are currently
available and used in applications other than of
environmental analysis. It is clear that major
emphasis must be placed on the enhancement of
existing GC/MS techniques and the development
of other multi-analyte technologies such as
LC/MS.
Laboratory Robotics
Benchtop laboratory robotics will begin to
replace labor intensive tasks such as weighing,
diluting, pipetting standards and loading
autosampler vials. The benefit is increased
sample throughput, with decreased labor
content in each sample, and precision equal to or
better than manual operations. For these
reasons, sample analysis done with robotics are
perceived to be more defensible in litigation.
Laboratory robotics systems are not faster
but can work longer hours. They are designed
only for laboratory scale tasks which require
lifting less than 1500 grams. They will therefore
not be capable of manipulating sample
containers or large pieces of laboratory
apparatus (e.g., liquid-liquid extractors).
Overall, use of robotics should result in a
significant savings in the total cost of analysis.
Sample Preparation Techniques
Numerous new methods of sample
preparation are needed to separate and measure
the broad range of organic compounds currently
of concern. These techniques represent a trend
towards increasing the amount of in-situ analyte
extraction and, consequently, require little or no
prior sample preparation. Many of these
techniques will be capable of sample
preconcentration, thereby effectively lowering
the detection limits of the technique. Bar code
readers/writers enhance the chain of custody in
sample tracking from field sampling through
generation of the final report, including error
checking each time the sample is manipulated,
transferred or analyzed. Note that all of the
techniques listed are amenable to automation,
and may be directly coupled on- line to GC's
and/or SFC's.
These techniques are expected to have the
largest single impact on quality, credibility,
sample throughput, and cost of analysis in the
near term. For these reasons, a subcommittee on
Sample Preparation Methods is proposed for the
Environmental Methods Management Group.
Capillary Column Technology
A very wide range of open tubular (capillary)
columns should be incorporated into GC
methods and replace all packed column GC
methods in use today. The benefits of each are
outlined below.
Open Tubular GC Column Analytical Characteristics
I.D.
0.76 mm
0.53 mm
0.32 mm
0.25 mm
0.18mm
0.10mm
Com-
patibility
with
Spectro-
scopic
Detectors
Yes
Yes
Yes
No
No
No
Resolu-
tion
Slow
Inter-
mediate
High
High
High
High
Analysis
Time
Slow
Inter-
mediate
Inter-
mediate
Fast
Fast
Fast
Ease of
Use
Fair
Excellent
Good
Fair
Difficult
Difficult
It is expected that the 0.5 mm ID columns
will become the de-facto standard for
environmental applications. Research problems
and dioxin analyses will require columns of
<0.25 mm because of the very high separation
efficiency capability.
HPLC Technology
HPLC separation methods will be the major
new development in environmental
methodologies. This development will be driven
by potential future monitoring requirements
pertaining to the analysis of polar, ionizable,
and thermally labile compounds. Based on 15
years of GC/MS experience, it is clear that the
method of choice will be HPLC/MS because of
the need for separation, sensitivity, and direct
identification. High resolution columns are now
available for compounds with molecular weights
consistent with environmental regulatory
requirements. They will emerge for both
7-8
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analytical (with MS) and sample
preparation/cleanup applications.
Super-Critical Fluid Chromatography
Super-critical fluid chromatography (SFC)
became commercially available in 19.86 and will
extend the molecular weight limit from
nominally 1000 amu for GC to 30,000 amu. SFC
allows the use of gas phase detectors, including
MS, and therefore is capable of both high
sensitivity detection and high efficiency
separations with open tubular columns. It will,
therefore, compete with HPLC for some
applications and the Agency needs to begin
environmental methods development in this
technique immediately.
Spectroscopic Identifications
Spectroscopic identification of GC and HPLC
effluents will expand because of the
requirements of both positive qualitative
identification and low detection limits.
Secondly, the cost of Spectroscopic identification
has decreased by as much as a factor of four
during the last six years; (e.g., FT/IR).
Environmental analyses in the 1990's will
involve an increasing number of analytes and
complex matrices. Coupled with the fact that
chromatographic separations are now at their
theoretical limit of efficiency, the advent of more
"hyphenated techniques" has the potential to
improve the information content and the
confidence and quality of the final result.
Thus, Fourier Transform infrared detection
(FT/IR) and identification will be used as a
complimentary on-line technique to GC-MS.
New interface technologies will allow HPLC/MS
to give electron impact (El), chemical ionization
(CI), and/or fast atom bombardment (FAB)
spectra which can be matched to standard
library spectra for the first time. It has been
projected that there will be as many HPLC/MS
systems in world-wide use by the turn of the
century as there are GC/MS systems in use
today. Therefore, the Agency has an immediate
need to develop LC/MS methods as discussed in
the Separations Section above.
Atomic emission Spectroscopic detectors
represent a new capability for increasing the
specificity of detection for both GC and SFC
effluents. These will be heteroatom specific
detectors (ex., Cl and/or N-, S-, O- containing
compounds) and may lead to measurements and
calculation of the empirical formula of GC
effluents. This hyphenated technique will
therefore be complimentary to MS (structural
analysis) and FT/IR (function group and
structural analysis) techniques. Data reduction
of one or more of these detectors will require
either high level, experienced organic analytical
chemists or expert (computer-software) systems
for unambiguous qualitative identification.
Thus the information content of each sample
analysis will increase substantially and require
more, faster and advanced computation power in
order to maintain the current level of sample
throughput in the laboratory.
Computer Systems
Computer systems for environmental
laboratories will continue to evolve with
emphasis on networks, communications
(terminal-to-terminal, instrument- to- com-
puter, and computer-to-computer), LIMS, and
environmental specific software. These
developments are driven by the needs for (a)
greater sample and result integrity, (b) QA/QC
and management review of data, (c) need to
archive and retrieve data into and out of data
bases, (d) edit and consolidate result and report
files, and (e) accommodate updates in computer
system hardware and software.
Market specific software packages will begin
to be effective in the 1990's. This development
will increase the quality of data, make it easier
for noncomputer people to manipulate data,
results, and reports by having software which is
designed for specific environmental tasks,
methods, data bases, spectral libraries, etc. This
will make it easier and faster for nonexpert
analysts to produce results without the overhead
of large, general purpose software. The
laboratory-computer developments can be
expected to follow the trends in office
automation, thus standard networks and
communication protocols will converge towards
industry standards.
7-9
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Biology
During the description of the FWPCA
programs, the inventory of required analytes,
and determination of availability and adequacy
of test methods, the following future
development needs were identified. The needs
are grouped for convenience even though several
are interrelated and no specific order of priority
is implied.
Microbiological Needs
• As a result of the amendments to the Safe
Drinking Water Act (SDWA), methods
should be developed for detecting
pathogenic bacteria, protozoa, and
parasites for wastewaters, sludges, and
sediments. Pathogenic candidates include
Salmonella, Shigella, Clostridium
botulinum, Pseudomonas aeruginosa,
Vibrio cholerae, Aeromonas hydrophila,
Leptospira, Crypstosporidium, Giardia
lamblia, Entamoeba histolytica,
nematodes, Ascaris (ova), and Taenia
(ova).
• Improved and new methods for microbial
toxicity and mutagenicity are needed.
Candidate tests include Microtox
(Photobacterium phosphoreum) (7-4),
Microscreen (Escherichia coli), Bacillus,
and Saccharomyces cerevisiae. The degree
of correlation between these tests and
aquatic toxicity tests should be
determined, particularly for toxic organics,
and single lab precision studies should be
performed. Stormwater discharges should
be included in the media tested.
• Methods are needed for the rapid
identification and verification of pathogens
and indicator species when detected in
traditional methods. Candidate methods
include gene probes and immunological
tests (monoclonal and polyclonal
antibodies).
• Integrated microbiological monitoring
systems using analytical instrumentation
to characterize microbial communities and
measure toxicity (sensitivity to pollutants
and toxicants) are needed.
• The EPA Manual of Methods for
Microbiology needs to be updated to
address the program needs for monitoring
pathogens and indicator organisms.
Virology Needs
• The EPA Manual of Methods of Virology
(1984) needs to be updated periodically,
consistent with scientific advances.
Additional research is necessary to further
improve virus sampling, extraction, and
concentration techniques in the manual. A
section should be added on precision and
replication.
• Standardized methods are needed for virus
detection in shellfish- growing waters.
Edible shellfish are known to concentrate
viruses from fecal-contaminated waters
during feeding. Since they are often eaten
raw or insufficiently cooked, subjecting
shellfish-growing waters to human waste
constitutes a public health risk.
Microbiological acceptance of the sanitary
quality of these estuarine and coastal
growing areas is based on coliform
standards. However, growing areas that
have been bacteriologically approved for
shellfish have been a source of viral
disease outbreaks. To effectively establish
an acceptable and practical program for
virological monitoring of shellfish and
shellfish growing waters, new techniques
that rely on a virological index need to be
made available.
• Aerosolized sewage due to the production
of aerosols from domestic sewage
treatment plants and wastewater spray
from irrigation and land disposal systems
are known to contain enteric viruses, but
only the most rudimentary technology
exists for their detection in air. The
potential for virus disease dispersed
through aerosolized sewage spotlights the
need for development of methods for their
detection.
• Better detection and identification
techniques are needed for waterborne
viruses. The existing gene probe
technology entails development of nucleic
7-10
-------
acid hybridization probes. If applicable, it
would be a much more rapid and cost-
effective technique than current enteric
virus methods.
• More suitable indicators of the presence of
viruses in water, wastewater, sludges and
soils are needed.
Aquatic Toxicity Methods
• EPA should develop methods to assess
toxicity persistence in receiving waters,
sediment toxicity, and bioaccumulation,
teratogenic, mutagenic, or carcinogenic
potential or waste.
• EPA should also standardize procedures
for conducting toxicity tests in
combination with low dissolved oxygen or
high temperature since these are common
additional stresses. EPA should seek to
standardize the format and requirements
of all toxicity test procedures.
• EPA should develop methods for
monitoring the toxicity of municipal and
industrial sludges. Emphasis should be
placed on microbial toxicity and on
methods for toxicity tests with suspended
solids.
• EPA should finalize criteria and required
testing requirements for sediment disposal
to support the §404 program.
• At the request of several EPA Regional
offices and State agencies, EPA should
consider the development of methods for
determining toxicity to tropical organisms.
These methods would support NPDES
permits programs in Hawaii, California,
and Puerto Rico.
• EPA should continue its developmental
work on the duckweed toxicity test
including the production of a manual and
demonstration of single lab precision.
» EPA should initiate research into the basic
biology of the principal aquatic toxicity
tests organisms that are the basis for
effluent monitoring. Inadequate
information is available on many of the
test species. This research should be
directed at a better understanding of the
basis for the responses of the organisms
during testing and for developing better
culture techniques for producing
consistently healthy test organisms in the
quantities needed.
• Methods are needed to relate toxic
substances detected in fish tissues with the
health of fish. Standardized methods for
detection and quantification of toxic
material in target tissue of fish and
shellfish should be a future requirement.
This will include developing a relationship
between (acute and chronic) toxicity and
the distribution of toxics in cellular
proteins (cytosol).
• EPA should also develop a method for
determining the amount of biomass
inhibition at treatment plants due to toxic
effluents.
• Cost effective methods are also needed for
multispecies test procedures using
standardized microcosms.
Field Surveys and Damage Assessment
• The EPA SAB recommends that EPA update
existing guidelines and develop methods for
field studies for monitoring the biological
integrity of aquatic communities in
receiving waters. This will include methods
needed to evaluate. and define ecosystem
stability and resilience which is necessary to
better define the acceptable degree of
biological effects and the frequency of
exposures under the water quality based
approach for controlling toxic discharges.
• The ecoregion methods of defining regional
patterns in water chemistry and aquatic
biota can be a valuable tool to help states
define attainable goals in water quality and
aquatic community improvements. The EPA
SAB recommends that EPA continue to
refine these methods so that they can be
used in state regulatory programs.
Quality Assurance/Quality Control
• Due to continued requests from States and
EPA Regional offices administering the
NPDES permits program and to requests
7-11
-------
from the regulated industries, the EPA
should develop a certification program for
labs that perform aquatic toxicity testing
and related biological tests. These data are
subject to legal review and challenge in
enforcement efforts and must be legally
defensible. This program would parallel or
be a part of the existing SDWA lab
certification program for drinking water
analyses.
• The EPA should increase its technology
transfer program for training commercial
testing laboratories, state laboratories, and
EPA regional laboratories in the major
testing methods to ensure consistency
between laboratories in data quality.
Emphasis should be placed on implementing
the QA/QC recommendations associated
with the various test methods. This effort
would include further reliance on the EPA
Quality Assurance Branch of EMSL-
Cincinnati and the availability of reference
standards.
Chapter Seven References
1. Braus, H., F.M. Middleton, and G. Walton.
Organic Chemcial Compounds in Raw and
Filtered Surface Waters. Analytical
Chemistry, Vol. 23, No. 8, August, 1951.
2. National Resources Defense Council v. Train
(8 ERG 2120, D.D.C. 1976).
3. Worthy, W. Contract Labs Respond to
Growing Demand for Analytical
Testing.C&EN, September 7,1987.
4. Ulitzer, A., 1986. Bioluminescence test for
genotoxic agents. In: M. DeLuca and W.D.
McElroy (eds.), Bioluminescence and
Chemiluminescence, Part B. Methods in
Enzymology, Vol. 133, pp 264-274.
5. EPA Scientific Advisory Board, 1986.
Review of EPA Water Quality Based
Approach Research Programs. EPA
Scientific Advisory Board, Washington D.C.
December 11,1986 SAB-EC-87-011. 53 pp.
7-12
-------
APPENDIX
Approximate Ranges of Concentration for Quality Control (QC) Samples-Water Quality Analyses
QC Samples Series Analytes
DEMAND ANALYSES (1-
200 mg/L)
EPA/API STANDARD
REFERENCE OILS (Neat
Oils)
LINEAR ALKYLATE
SULFONATE (5-6%)
MINERAL/PHYSICAL
ANALYSES (1-100 mg/L)
NONIONIC
SURFACTANT (CTAS
TEST) STANDARD (Neat
Compound)
NUTRIENTS (0.5-5 mg/L)
OIL AND GREASE (20
mg/L)
PESTICIDES IN FISH
(0.01-3 mg/Kg)
PHENOLS, TOTAL
(4AAP Method) (45 ug/L)
POLYCHLORINATED
BIPHENYLS(PCBs)IN
OILS (10-500 ug/L)
PCBS IN SEDIMENTS (5-
10 mg/Kg)
SUSPENDED SOLIDS (0-
500 mg/L)
TRACE METALS - WPI
(1-500 ug/L)
TRACE METALS - WP II
(10-20 ug/L)
TRACE METALS - WP III
(0.1-10 ug/L)
TRACE METALS IN FISH
(0.1-50 mg/Kg)
BOD, COD, and TOC in water
Arabian Light Crude Oil, Prudhoe Bay Crude Oil, South Louisiana Crude Oil, No. 2 Fuel Oil
(high aromatics), and No. 6 Fuel Oil (high viscosity) Bunker C (laboratory must request specific
oil)
LAS, the anionic surfactant standard for the MB AS in water
sodium, potassium, calcium, magnesium, pH, chloride, fluoride, alkalinity/acidity, total
hardness, total dissolved solids, and specific conductance in water
Reference Nonionic Surfactant, C12-18 Ell. Standard Methods Method 512 C
nitrate-N, ammonia-N, Kjeldahl-N, orthophosphate, and total P in water
analyzable by IR and gravimetrically in propanol
alpha-BHC, endrin, DDD, DDE, and DDT
total phenols in water
Aroclor 1016,1242,1254, and 1260 in transformer, hydraulic, and capacitor oils, (specify
Aroclor and oil)
Aroclor 1242 and 1254
non-filterable, volatile and total filterable residue
aluminum, arsenic, beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese,
mercury, nickel, selenium, vanadium, and zinc in 0.5% nitric acid solution
antimony, silver, and thallium in 0.5% nitric acid solution
barium, calcium, potassium, sodium, magnesium, and molybdenum in 0.5% nitric acid solution
arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc
A-l
-------
Approximate Ranges of Concentration for QC Samples-Priority Pollutants/Hazardous Wastes/Toxic Chemicals
QC Samples Series . Analytes
n-ALKANES (0.05-2 ug/L)
CHLORINATED
HYDROCARBONS
(Method 612) (10-100 ug/L)
CHLORINATED
HYDROCARBON
PESTICIDES-WPI
(Method 608) (2-10 ug/L)
CHLORINATED
HYDROCARBON
PESTICIDES-WP II
(Method 608) (50 ug/L)
CHLORINATED
HYDROCARBON
PESTICIDES-WP III
(Method 608) (2-10 ug/L)
CYANIDE, TOTAL (500
ug/L)
EP METALS (1-100 mg/L)
EP PESTICIDES &
HERBICIDES (10-5,000
ug/L)
GC/MS ACIDS (Method
625) (100 ug/L)
GC/MS BASE
NEUTRALS -1 (Method
625) (100 ug/L)
GC/MS BASE
NEUTRALS - II (Method
625) (100 ug/L)
GC/MS BASE
NEUTRALS - III (Method
625) (100 ug/L)
GC/MS PESTICIDES -1
(Method 625) (100 ug/L)
GC/MS PESTICIDES -II
(Method 625) (100 ug/L)
HALOETHERS (Method
611) (10-150 ug/L)
ICAP-19(1 mg/L)
ICAP- 7 (0.5-10 mg/L)
NITROAROMATICS AND
ISOPHORONE (Method
609) (1-150 ug/L)
dodecane, eicosane, heptadecane, hexacosane, tetradecane, tricosane in acetone
hexachloroethane, hexachlorobenzene, 1,2,4-trichloro-benzene, o-dichlorobenzene, p-
dichlorobenzene, m-dichlorobenzene, hexachlorobutadiene, 2-chloro-naphthalene in acetone
aldrin, dieldrin, DDT, DDE, DDD, and heptachlor in acetone
chlordane in acetone
alpha-BHC, beta-BHC, heptachlor epoxide, endrin, aldehyde, and alpha and beta endosulfan in
acetone
in water, pH greater than 9.0
arsenic, barium, cadmium, chromium, lead, mercury, selenium, silver in acetic acid
lindane, endrin, methoxychlor, 2,4-D, and Silvex in acetone
2-chlorophenol, 2-nitrophenol, phenol, 2,4-dimethyl-phenol, 2,4-dichlorophenol, 2,4,6-
trichlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, and 4-nitrophenol in methanol
bis-2-chloroethyl ether, 1,3-dichlorobenzene, 1,2-dichlorobenzene, nitrosodipropylamine, bis-2-
chloroethoxy methane, 1,2,4-trichlorobenzene, hexachlorobutadiene, 2-chloronaphthalene, 2,6-
dinitro-toluene, 2,4-dinitrotoluene, diethyl phthalate, hexachlorobenzene, phenanthrene,
dibutyl phthalate, pyrene, benzo(a)anthracene, dioctyl phthalate, benzo(k)fluoranthene in
methanol
1,4-dichlorobenzene, bis-2-chloroisopropyl ether, hexachloroethane, nitrobenzene,
naphthalene, dimethyl phthalate, acenaphthene, fluorene, 4-chlorophenyl phenyl ether, 4-
bromophenyl phenyl ether, anthracene, fluoranthene, butyl benzyl phthalate, benzo(a)pyrene,
benzo(b)fluoranthene, benzo(a,h)anthracene, benzo(g,h,i) perylene, chrysene, and bis (2-ethyl-
hexyl phthalate) in methanol
4-chlorobenzotrifluoride, m-chlorotoluene, 2,4-dichloro-toluene, 1,3,5-trichlorobenzene, 1,2,4,5-
tetrachloro-benzene, 1,2,3,4-tetrachlorobenzene, 2,4,6-trichloro-aniline, 1,2,3-trichlorobenzehe,
and pentachlorobenzene in acetone
heptachlor, heptachlor epoxide, dieldrin, endrin, DDD, alpha BHC and gamma BHC in acetone
beta-BHC, aldrin, alpha and beta Endosulfan, 4,4'-DDE, and 4,4'-DDT in acetone
bis (2-chloroisopropyl) ether, bis (2-chloroethoxy) methane, bis (2-chloroethyl) ether, 4-
chlorophenyl phenyl ether, 4-bromophenyl phenyl ether in acetone
As, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Se, Ti, Tl, V and Zn in dilute nitric acid
Ag, Al, B, Ba, K, Na, and Si in dilute nitric acid
isophorone, nitrobenzene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene in acetone
A-2
-------
Approximate Ranges of Concentration for QC Samples-Priority Pollutants/Hazardous Wastes/Toxic Chemicals
QC Samples Series Analytes
n-ALKANES (0.05-2 ug/L)
PHENOLS (GO (Method
604) (2-275 ug/L)
PHTHALATE ESTERS
(Method 606) (10-50 ug/L)
POLYCHLORINATED
BIPHENYLS (Method
608) (50 ug/L)
POLYNUCLEAR
AROMATICS -1 (Method
610) (5-100 ug/L)
POLYNUCLEAR
AROMATICS - II (Method
610) (10-100 ug/L)
dodecane, eicosane, heptadecane, hexacosane, tetradecane, tricosane in acetone
phenol, 2,4-dimethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, 2,4-dichlorophenol,
2,4,6-trichloro-phenol, pentachlorophenol, 2-nitrophenol, 4-nitrophenol, and 2,4-dinitrophenol
in acetone
dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butyl benzl phthalate, diethyl
hexyl and dioctyl phthalate in acetone
separate samples available for Aroclor 1016,1221,1232,1242,1248,1254, and 1260 in acetone
(laboratory must request specific Aroclor needed)
acenaphthene, anthracene, benzo(k)fluoranthene, naphthalene, and pyrene in acetone
acenaphthylene, benzo(a)anthracene, benzo(g,h,i)perylene, benzo(a)pyrene, dibenzo(a,h)
anthracene, fluoranthene, and phenanthrene in acetone
Approximate Ranges of Concentration for QC Samples-Biology/Microbiology
QC Samples Series Analytes
ALGAE FOR
IDENTIFICATION
BACTERIA INDICATOR
STRAINS (108-109
organisms/vial)
CHLOROPHYLL (3-80
ug/L) CHLOROPHYLL
(0.20-80 mg/L)
CHLOROPHYLL (0.20-80
mg/L)
REFERENCE
TOXICANTS
SIMULATED
PLANKTON
Samples contain algae preserved in 5% formalin for microscopic identification:
Sample No. 1 contains: 1 green, 1 bluegreen
Sample No. 2 contains 3 bluegreens
Sample No. 3 contains: 1 green, 1 bluegreen
Sample No. 4 contains: 1 diatom (Hydrax mounted slide)
(Laboratory must specify sample needed.)
Enterobacter aerogenes, Escherichia coli, pneumoniae, Pseudomonas aeruginosa and
Streptococcus faecalis, lyophilized (laboratory must request specific organisms needed). Also
available are sterile lyophilized blanks for evaluation of aseptic technique.
fluorometric analyses, 1 calibration sample approximately 80 ug/L pure chlorophyll; 1 check
sample approximately 3 ug/L pure chlorophyll; 1 check sample approximately 20 ug/L mix of
pigments. A 3 ampul set.
spectrophotometric analyses, (#1 is pigment #2 is pure chlorophyll ), two levels in acetone. A
2 ampul set.
sodium lauryl sulfate (30-60 mg/mL) in aqueous solution cadmium chloride (10 mg/mL) in
aqueous solution, copper (4 mg/mL) in aqueous solution (available 9/1/87) (laboratory must
specify toxicant(s) needed)
20 mL aqueous suspension of latex spheres for particle counting, and a permanent, glass slide
mount of latex spheres for particle size distribution determinations.
A-3
-------
Approximate Ranges of Concentration for QC Samples-Drinking Water Analyses
QC Samples Series Analytes
CORROSIVITY/SODIUM
(0.1-15 mg/L)
HERBICIDES (10-100
ug/L)
NITRATE/FLUORIDE
(0.1-10 mg/L)
CHLORINATED
HYDROCARBON
PESTICIDES - WSI (0.20-
20 ug/L)
CHLORINATED
HYDROCARBON
PESTICIDES-WS II (50
ug/L)
RESIDUAL FREE
CHLORINE (1 mg/L)
TRACE METALS-WS
(1.0-500 ug/L)
TRIHALOMETHANES
(20 ug/L)
TURBIDITY (0.5-5 NTU)
VOLATILE ORGANIC
CONTAMINANTS-I
(Methods 503,524,602
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS-II
(Methods 503,524,602
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS-III
(Methods 503,524,602
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS-IV
(Methods 502,524,601
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS-V
(Methods 502,524,601
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS-VI
(Methods 502,524,601
and 624) (20 ug/L)
VOLATILE ORGANIC
CONTAMINANTS - VII
(Methods 502,524,601
and 624) (20 ug/L)
Langlier's Index Value and Sodium in water
2,4-D, 2,4,5-TP (Silvex) in methanol
nitrate-N and flouride in water
lindane, endrin, and methoxychlor in acetone
toxaphene in acetone
solvent is water
arsenic, barium, cadmium, chromium, lead, mercury, selenium, and silver in 0.3% nitric acid
solution
chloroform, bromoform, dichlorobromomethane, and chlorodibromomethane in methanol
in water
benzene, ethylbenzene, m-xylene, n-propylbenzene, p-chlorotoluene, 1,3,5-trimethylbenzene
and p-dichlorobenzene in methanol
trichloroethene, p-xylene, o-xylene, t-butylbenzene, p-cymene and m-dichlorobenzene in
methanol
toluene, chlorobenzene, isopropylbenzene, sec-butylbenzene, 1,2,4-trimethylbenzene, n-
butylbenzene, and o-dichlorobenzene in methanol
1,1-dichloroethylene, cis-l,2-dichloroethylene, 1,1,1-trichloroethane, 1,1-dichloropropene,
1,1,2-tri-chloroethane, 1,1,2,2-tetrachloroethylene, bromoform, and bis(2-chloroethyl) ether in
methanol
bromochloromethane, chloroform, carbon tetrachloride, 1,1,2-trichloroethylene, 1,2-
dibromoethane, 1,1,1,2-tetrachloroethane, pentachloroethane, l,2-dibromo-3-chloropropane
and m-dichlorobenzene in methanol
dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, bromodichloromethane, 1,3-
dichloropropane, 2-chloroethyl ethyl ether, 1,2,3-trichloropropane, chlorobenzene,
bromobenzene and o-dichlorobenzene in methanol
trichlorofluoromethane, trans 1,2-dichloroethene, dibromomethane, 1,2-dichloropropane,
chlorodibromo-methane, 1,1,2,2-tetrachloroethane, chlorohexane, o-chlorotoluene, and p-
dichlorobenzene in methanol
A-4
-------
Concentrations are 5,000 ng of QAS-Pure Compound per mL of Met Hanoi Solvent
Unless Otherwise Noted
E001 Acenaphthene ~~
E002 Acrolein**
E003 Acrylonitrile (10,000 ug/mL)
E004 Benzene
E005 Benzidine
E006 Chlorobenzene
E007 1,2,4-Trichlorobenzene
E008 Hexachlorobenzene (1000 ug/mL)*
E009 1,2-Dichloroethane
E010 1,1,1-Triehloroethane (10,000 ug/mL)(QAR)
EO11 Hexachloroethane
E012 1,1-Dichloroethane (5,500 ug/mL)
E013 l,l,2-Trichloroethane(QAR)
E014 1,1,2,2-Tetracfaloroethane (10,000 ug/mL)(QAR)
E015 Chloroethane (11,000 ug/mL)***
E016 bis(2-Chloroethyl) ether
EO 17 2-Chloroethyl vinyl ether (QAR)
E018 2-Chloronaphthalene
E019 2,4,6-Trichlorophenol
E020 p-Chloro-m-cresol
E021 Chloroform
E022 2-Chlorophenol
E023 1,2-Dichlprobenzene
E025 1,4-Dichlorobenzene
E026 3,3'-Dichlorobenzidine
E027 1,1-Dichloroethylene (1,000 ug/mL)
E028 trans-l,2-Dichloroethylene (11,500 ug/mL)
E029 2,4-Dichlorophenol
E030 1,2-Dichloropropane (10,000 ug/mL)
E033 2,4-Dinitrotoluene
E034 2,6-Dinitrotoluene
E036 Ethylbenzene (10,000 ug/mL)
E037 Fluoranthene
E038 4-Chlorophenyl phenyl ether
E039 4-Bromophenyl phenyl ether
E040 bis(2-Chloroisopropyl) ether (QAR)
E041 bis(2-Chloroethoxy) methane (QAR)
E042 Methylene chloride (10,000 ug/mL)
E043 Methyl chloride***
E044 Methyl bromide (9940 ug/mL)***
E046 Dichlorobromomethane
E047 Fluorotrichloromethane
E050 Hexachlorobutadiene (QAR)
E051 Hexachlorocyclopentadiene
E052 Isophorone
E053 Naphthalene -
E054 Nitrobenzene
E055 2-Nitrophenol _^
"In Acetone "In para-Dioxane ""In 2-Propano! """Acetonitrile
+ ln Methylene Chloride + +lri Isooctane + + +ln Cyclohexanone
A-5
-------
Concentrations are 5,000 yg of QAS-Pure Compound per mL of Methanol Solvent
Unless Otherwise Noted
E056 4-Nitrophenol
E057 2,4-DinitrophenoKQAR)
E058 4,6-Dinitro-o-cresol
E059 N-Nitrosodimethylamine
E060 N-Nitrosodiphenylamine
E061 N-Nitrosodi-n-propylamine
E062 Pentacchlorophenol
E063 Phenol
E064 bis(2-Ethylhexyl) phthalate
E065 Butyl benzyl phthalate
E066 Di-n-butyl phthalate
E067 Di-n-octyl phthalate
E068 Diethyl phthalate
E069 Dimethyl phthalate
E070 Benzo(a)anthracene (1,000 ug/mL)
E071 Benzo(a)pyrene (1,000 ug/mLXQAR)*
E072 Benzo(b)fluoranthene (2,500 ug/mL)*
E073 Benzo{k)fluoranthene (1,000 ug/mL)*
E074 Chrysene (1,000 ug/mL)*
E075 Acenaphthylene (QAR)
E076 Anthracene (1,000 ug/mL)*
E077 Benzo(g,h,i)perylene (1,000 ug/mL)**
E078 Fluorene(QAR)
E079 Phenanthrene
E081 Indeno(l,2,3-c,d)pyrene (500 ug/mL)*
E082 Pyrene (1,000 ug/mL)
E083 Tetrachloroethylene
E084 Toluene (10,000
E085 Trichloroethylene (10,000 ug/mL)
E088 Dieldrin (1,000 ug/mL)
E089 Chlordane (QAT)
E091 4,4'-DDE
E092 4,4'-DDD
E093 alpha-Endosulfan (1,000 ug/mL)**
E094 beta-Endosulfan (1,000 ug/mL)**
E095 Endosulfansulfate (1,000 ug/mL)(QAR)**
E096 Endrin(QAR)
E097 Endrin aldehyde (2,500 ug/mL)
E098 Heptachlor
E099 Heptachlor epoxide (2,500 ug/mL)
E100 alpha-BHC (2,500 ug/mL)
E101 beta-BHC (2,500 ug/mL)*
E102 gamma-BHC (Lindane)
E103 delta-BHC (1000 ug/mL)
E104 PCB-Aroclor 1242 (QAT)
E105 PCB-Aroclor 1254 (QAT)
E107 PCB-Aroclor 1232 (QAT)
BIOS PCB-Aroclor 1248 (QAT) ; '
*In Acetone **In para-Dioxane ***In 2-Propanol ****Acetonitrile
+In Methylene Chloride + +In Isooctane + + +In Cyclohexanone
A-6
-------
Concentrations are 5,000 ug of QAS-Pure Compound per mL of Methanol Solvent
Unless Otherwise Noted
E110
Bill
E124
E125
E126
E129
E129
E129
E130
E131
E132
E132
E132
E135
E135
E135
E136
E149
E150
E151
E152
E153
E156
E168
E169
E170
E171
E173
E175
E176
E177
E179
E180
E182
E183
E200
E201
E202
E203
E212
E214
E218
E219
E220
E222
E224
E225
E231
PCB-Aroclor 1016 (QAT)
Toxaphene (QAT)
4,4'-DDT(QAR)
PCB-Aroclor 1016 (1,000 pg/mL)(QAT)+ +
PCB-Aroclor 1221 (QAT)+ +
PCB-Aroclor 1260 (500 p.g/mL,)(QAT) + +
PCB-Aroclor 1260 (1,000 ng/mL)(QAT)+ +
PCB-Aroclor 1260 (3,000 p.g/mL)(QAT) + +
PCB-Aroclor 1262 (QAT)+ +
PCB-Aroclor 1268 (2,500 ng/mL)* (QAT)
PCB-Aroclor 1242 (500 ng/mL)(QAT)+ +
PCB-Aroclor 1242 (1,000 p.g/mL)(QAT) + +
PCB-Aroclor 1424(3,000 p.g/mL)(QAT) + +
PCB-Aroclor 1254(500 ng/mL)(QAT)+ +
PCB-Aroclor 1254 (1,000 ug/mL)(QAT) + +
PCB-Aroclor 1254 (3,000 iig/mL)(QAT)+ +
Bromochloromethane (10,000 ng/mL)
2,4-Dichlorotoluene
2-Chlorotoluene
3-Chlorotoluene
4-Chlorotoluene (QAE)
4-Chlorobenzotrifluoride
Pentachloronitrobenzene
alpha,alpfaa,2,6-Tetrachlorotoluene
Benzyl chloride (QAR)****
2,3-Dichloro-l-propylene (10,000 jig/mL)
1,2-Dibromoethane (EDB) (10,000 pg/mL)
cis-1,2-Dichloroethylene (10,000 ng/mL)(QAR)
1,2,3-Trichlorobenzene
1,3,5-Trichlorobenzene
1,2,4,5-Tetrachlorobenzene (2,500 p.g/mL)(QAR)****
2,4,5-Trichlorophenol (QAR)
2,4,6-Trichloroaniline
3-Chlorophenol
4-Chlorophenol
Chlorodibromomethane (10,000 pg/mLXQAR)
ortho-Xylene
meta-Xylene
para-Xylene
Bromoform
1,3-Dichlorobenzene
cis & trans 1,3-Dichloropropylene (QAR)
Mirex(l,OOOp,g/mD*
Aldrin
2,3,5-Trichlorophenol (QAR)
2,4-Dimethylphenol
1,2,3,4-Tetrachlorofaenzene (2,500 y,g/mL)
Dibenzo(a,h)anthracene (1,0
*In Acetone **In para-Dioxane ***In 2-Propanol ****Acetonitrile
+In Methylene Chloride + +In Isooctane + + + In Cyclohexanone
A-7
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Concentrations are 5,000 pg of QAS-Pure Compound per mL of Methanol Solvent
Unless Otherwise Noted
E236
E237
E238
E239
E240
E241
E242
E244
E250
E251
E252
E255
E257
E258
E260
E261
E262
E263
E270
E271
E282
E284
E285
E286
E295
E298
E299
E300
E305
E306
E311
E322
E324
E325
E327
E329
E330
E334
E335
E337
E338
E342
E349
E360
E363
E364
E366
E368
n-Decane
n-Undecane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Heptadecane (2,500 ng/mL)
n-Nonadecane (1,000 ng/mL)
ortho-Cresol(QAR)
meta-Cresol (QAR)
para-Cresol
Dibutyl ether
Styrene
Epichlorohydrin****
Pentachlorobenzene (2,500 ug/mL)
Dibenzofurane
Diphenyl ether
Diphenylamine
Acrylamide (10,000 ng/mL)
Pyridine (10,000 ug/mD
Diisodecyl phthalate
Acetone
Diethyl ether (4,500 ug/mL)
1,2-Epoxybutane****
Phenacetin
N-Nitrosopyrrolidine
2-Fluoroacetamide
Pentachloroethane
4-Chloroaniline
Urethane (Ethyl carbamate)
Methyl ethyl ketone
Methylene bis (o-chloroaniline)
o-Nitroaniline
m-Nitroaniline
Vinyl acetate****
Ethylenethiourea
2,4-Dichlorophenoxyacetic acid (2,4-D)****
N-Nitrosodiethylamine
1,1,1,2-Tetrachloroethane (QAR)
Malononitrile
Propionitrile
p-Nitroaniline
4-Methyl-2-pentanone
Carbon tetrachloride (10,000 ng/mL)
Carbon disulfide
Hexachloropropylene (1,000 ug/mL)
Safrole
1,2,3-Trichloropropane
*In Acetone **In para-Dioxane ***In 2-Propanol ****Acetonitrile
+In Methylene Chloride + + In Isooctane + + +In Cyclohexanone
A-8
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Concentrations are 5,000 ug of QAS-Pure Compound per mL of Methanol Solvent
Unless Otherwise Noted
E369 Saccharin (2,000 ug/mL)
E375 3-Chloropropionitrile (1,000 ug/mL)
E406 Bromobenzene
E411 Acetophenone
E439 Methyl methacrylate (1,000 ug/mL)
E455 Dinoseb****
E458 1-Nitrosopiperidine
E470 PCN Halowax 1099 (QAT)
E471 PCN Halowax 1001 (QAT)
E472 PCN Halowax 1000 (QAT)
E473 Acetonitrile***
E475 Allyl alcohol (1,000 ug/mL)
E480 para-Dioxane (10,000 ug/mL)
E536 Vinyl chloride***
E541 Benzoicacid****
E542 Aniline
E543 Propargyl alcohol (1,000 ng/mL)+ + +
E548 N,N-Dimethylformamide
E552 2,4,5-TP(Silvex)(QAR)****
E560 Ethyl parathion (1,000 ug/mL)****
E565 2-Naphthylamine (1,000 ug/mL)
E567 7,12-Dimethylbenz(a)anthracene (1,000 ug/mL) (QAR)
E572 Methyl parathion (1,000 ug/mL)****
E573 Kepone(l,OOOug/mL)(QAR)+ + +
E662 3-Nitrophenol
E669 1-Methyl ethyl benzene (Cumene)
E686 Methacrylonitrile (1,000 ug/mL)
E687 Ethyl methacrylate (1,000 ug/mL)
E688 2-Picoline
E700 Resorcinol
E713 Picloram (1000 ug/mL)****
E715 Carbofuran
E856 Isodrin
E952 p.p'-Methoxychlor
E954 Aldicarb(l,OOOug/mL)****
E993 l,2-Dibromo-3-chloropropane
E995 Aldicarb sulfone (1,000 ug/mL)****
E996 Aldicarb sulfoxide (1,000 ug/mL)****
E1089 Alachlor (1,000 ug/mL)
E1090 Atrazine (1,000 ug/mL)
E1097 Dibromomethane
E1103 l,3,5-Trimethylbenzene(Mesitylene)
El 104 sec-Butylbenzene
E1105 n-Butylbenzene
El 106 tert-Butylbenzene
E1107 l,2,4-Trimethylbenzene(QAR)
E1108 4-Isopropyltoluene (p-Cymene) (QAR)
E1109 • 1,3-Dichloropropane • •
*In Acetone **In para-Dioxane ***In 2-Propanol ****Acetonitrile
+In Methylene Chloride + + In Isooctane + + + In Cyclohexanone
A-9
-------
Concentrations are 5,000 ug of QAS-Pure Compound per mL of Methanol Solvent
Unless Otherwise Noted
E1112 n-Propylbenzene
E1166 1,1-Dichloro-l-propylene (QAB)
E1167 2,2-Dichloropropane
Surrogates and Internal Standard for USEPA GC/MS Methods 624 and
625
E188 Phenanthrene - dlO (150 yg/mL>(QARX100 p.g/mL)*
E189 Phenol-d5 (100 p.g/mL>*
E190 2,4-Dimethylphenol-3,5,6-d3 (QARK100 pg/mL)*
E191 Pentachlorophenol-13C6 (100 p.g/mL)*
E192 Dimethyl phthalate-d6 (150 ng/mL)*
E193 2-Fluorophenol (QAR) (100 ng/mL)*
E194 2-Fluorobiphenyl (100 ng/mU*
E195 1-Fluoronaphthalene (100 ng/mL)*?
E196 l,4-Dichlorobutane-d8 (150 pg/mL)
E197 2-Bromo-l-chloropropane-d6 (150ug/mL)(QAT)
E198 Bromochloromethane-d2 (150 p.g/mL)
E199 Benzo (g,h,i) perylene-13C12 (100 pg/L)
E232 Fluorobenzene (150 ug/L)
E233 4-Bromofluorobenzene (150 pg/L)
E234 4,4-Dibromooctafluorobiphenyl (100 pg/L)*
E776 1.2-Dichlorobenzene-d4 (150 ng/L)
*In Acetone **In para-Dioxane ***In 2-Propanol ****Acetonitrile
•Hn Methylene Chloride ++In Isooctane + + +In Cyclohexanone
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A-10
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