United States
Environmental Protection
Agency
Office of Water
Engineering and Analysis Division (4303)
Washington, DC 20460
EPA-821-D-96-004
December 1996
&EPA Guide to Method Flexibility and
Approval of EPA Water Methods
> Printed on Recycled Paper
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Guide to Method Flexibility and
Approval of EPA Water Methods
Prepared by
Analytical Methods Staff
Engineering and Analysis Division (4303)
Office of Science and Technology
Office of Water
IL S. Environmental Protection Agency
Washington; DG
December 1996
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In Memory Of
This guide is dedicated to Dr. Baldev Bathija, in memory of his commitment to the
improvement of EPA methods, his boundless enthusiasm, arid his unwavering support for
the streamlining initiative described in this document.
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Acknowledgments
This guide was prepared under the direction of William A. Telliard of the Engineering
and Analysis Division within the EPA Office of Water. :It was prepared under EPA
Contract No. 68-G3-0337 by DynCorp Environmental Services Division with assistance
from Interface, Inc.
EPA would like to thank the numerous organizations whose comments on the
streamlining initiative were valuable in preparing this guide.
Disclaimer
This guide does not establish Agency-wide policies or procedures. This guide is not
intended to and cannot be relied upon to create any rights, substantive or procedural,
enforceable by any party in litigation with the United States. EPA reserves the right to act
at variance with the policies and procedures in this guide and to change them at any time
without public notice. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
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Foreword
This draft guidance document describes the principles and procedures for a comprehensive
initiative to expand method flexibility and expedite approval of analytical methods for wastewater and
drinking water at 40 CFR parts 136 and 141. This initiative represents a combined effort of EPA's Office
of Science and Technology and Office of Ground Water and Drinking Water to streamline EPA's water
methods approval programs.
This guide was prepared by the Engineering and Analysis Division of the Office of Science and
Technology within EPA's Office of Water. The guide is for use by EPA Headquarters and Regional
personnel, permittees, state and local regulatory authorities, purveyors of new technology, and analytical
laboratories in implementing the Office of Water's streamlining initiative.
This guide does not duplicate other Agency guidance and should be supplemented with other
guidance for specific topics. Citations for supplemental guidance are included in the guide where
applicable.
Inquiries and comments concerning this guide should be directed to:
W. A. Telliard, Director :
Analytical Methods Staff
Engineering and Analysis Division (4303)
USEPA Office of Water
401 M Street, SW
Washington, DC 20460
Phone:202-260-7120
Fax:202-260-7185
Email: telliard.william@epamail.epa.gov
7 i
Additional copies of this guide may be obtained from the following organizations:
USEPA National Center for Environmental
Publications and Information (NCEPI)
11029 Kenwood Road
Cincinnati, Ohio 45242
Phone: 513-489-8190
Document No: EPA-821-D-96-004
Water Resource Center
Mail Code RC-4100
401 M Street, S.W.
Washington, D.C. 20460
Phone: 202-260-7786 •
Document No: EPA-821-D-96-004
National Technical
Information Service (NTIS)
5285 Port Royal Road
Springfield, Virginia 22161
Phone: 703-487-4650
Document No: PB97-117766
Educational Resources
Information Center (ERIC)
1929 Kenny Road
Columbus, Ohio 43210
Phone: 800-276-0462
Document No: D-A43
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Table of Contents
Chapter 1: Introduction 1
1.1 Background l
1.1.1 Statutory Authority 2
1.1.2 .. Current Office of Water Methods Approval Programs 3
1.2 The Streamlining Initiative 3
1.2.1 Streamlining Objectives : 4
1.2.2 Benefits of Streamlining •. 6
1.2.3 Development of EPA's Streamlining Initiative. 6
1.2.4 Implementation Issues 8
1.3 Purpose of Guide ' 9
1.4 Content and Organization of Guide ,- : 10
Chapter 2: Method Flexibility 13
2.1 Introduction .'..'..:.. '. 13
2.2 Existing Flexibility 13
2.3 Scope of Flexibility Provided by Streamlining .. . 14
2.3.1 Reference Method 14
2.3.2 Modifications to Front-end and Determinative Techniques 17
2.3.3 Method-Defined Analytes... -.., 19
2,3.4 Flexibility to AddNew Target Analytes "... ...... 23
2.3.5 New Methods, Screening Methods, and Modified Methods 24
2.4 Controls on Flexibility 26
Chapter 3: Quality Control Requirements , , 27
3.1 Introduction 27
3.2 Description of Tiers 28
3.3 Standardized Quality Control 28
3.3.1 Calibration Linearity 28
3.3.2 Calibration Verification •. 30
3.3.3 Absolute and Relative Retention Time Precision 31
3.3.4 Initial Precision and Recovery ., 31
3.3.5 Ongoing Precision and Recovery ; '. 31
3.3.6 Analysis of Blanks '. 31
3.3.7 Surrogate or Labeled Compound Recover 32
3.3.8 Matrix Spike and Matrix Spike Duplicate ..,;.. 32
3.3.9 Demonstration of Method Detection Limit -. .... 32
3.3.10 Reference Sample Analysis. 33
3.4 Development of Quality Control Acceptance Criteria 33
3.4.1 Quality Control Acceptance Criteria Development for New Methods at Tier 1 34
3.4.2 Quality Control Acceptance Criteria Development for New Methods at Tier 2 38
3.4.3 Quality Control Acceptance Criteria Development for New Methods at Tier 3..... 44
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Chapter 4: Method Validation Requirements '. 51
4.1 Introduction 51
4.2 Summary of Validation Requirements. 52
4.3 Description of Tier 1, 2, and 3 Validation Studies 55
4.3.1 Tier 1 Validation Studies 56
4.3.2 Tier 2 Validation Studies 58
4.3.3 Tier 3 Validation Studies 59
4.4 Development of a Validation Study Plan 59
4.5 Detailed Procedures for Conducting Tier 1,2, and 3 Validation Studies .: 61
4.5.1 Optional Preliminary Testing 61
4.5.2 Method Compilation 61
4.5.3 Method Detection Limit Study 61
4.5.4 Calibration 62
4.5.5 Initial Precision and Recovery 62
4.5.6 Field Sample Analyses 63
4.5.7 Ongoing Precision and Recovery 65
4.5.8 Calibration Verification 65
4.5.9 Contamination Level in Blanks .....' 66
4.5.10 Surrogate or Labeled Compound Recovery 66
4.5.11 Absolute and Relative Retention Time 66
4.5.12 New Analytes '. 66
4.5.13 Further Validation Studies for New Methods 67
4.6 Validation Study Report 67
4.6.1 Background 68
4.6.2 Study Design and Objectives 68
4.6.3 Study Implementation -. 68
4.6.4 Data Reporting and Validation 69
4.6.5 Results 69
4.6.6 Development of QC Acceptance Criteria ! 70
4.6.7 Data Analysis/Discussion 70
4.6.8 Conclusions 70
4.6.9 Appendix A - The Method , 70
4.6.10 AppendixB - Validation Study Plan '. 70
4.6.11 Appendix C - Supporting Data 71
4.7 Reporting Validation Study Results 72
4.7.1 Reporting Validation Study Results for New Methods 72
4.7.2 Reporting Validation Study Results for Method Modifications 72
Chapter 5: Method Approval Process ; 73
5.1 Introduction 73
5.2 Pre-Submission Procedures 73
5.2.1 Method Development 73
5.2.2 Method Validation 74
5.2.3 Compilation of Information to Support Development of Preamble 74
5.2.4 Method Publication , -.'. 76
5.3 Submission of Method Approval Applications to EPA 76
5.4 EPA Review of Method Approval Applications 76
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5.5 Tier 1/Single-Laboratory Use Methods ..., 77
.5.6 Rulemaking Process , '. 78
5.7 Proprietary Reagents, Instruments, and Methods 79
Chapter 6: Assessing Method Equivalency.... -. 81
6.1 Introduction 81
6.2 Checking Completeness of the Method Validation Study Report Package 82
6.3 Assessing Equivalency Using the Checklists ,..".. 84
6.4 Data Review Guidance „ 84
6.4.1 Standardized Quality Control 84
6.4.2 Details of Data Review , 85
Chapter 7: Biological Methods :... 89
7.1 Introduction ; 89
7.2 New WET Methods . ....' , 89
7.3 Modified WET Methods 90
7.4 Validation Requirements 90
Appendices
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Appendix F
Appendix G
Acronyms and Symbols
Glossary
Current Method Flexibility
Suggested Data Elements
Equivalency Checklists
Inorganic Criteria
Bibliography
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Chapter 1
Introduction
1.1 Background and Overview
Within the U.S. Environmental Protection Agency (EPA), the Office of Water (OW) publishes
test procedures (analytical methods) for analysis of wastewater and drinking water. Listed at parts 136 and
141 of Title 40 of the Code of Federal Regulations (CFR), these methods are authorized for use in data
gathering and environmental monitoring under the Clean Water Act (CWA) and the Safe Drinking Water
Act (SDWA). These methods have been developed by EPA, by consensus standards organizations, and
by others. Many of these methods, especially methods published before 1990, are prescriptive with limited
ability to modify procedures or change technologies to accommodate specific situations. There has been a
- growing awareness within EPA and the analytical community that the requirement to use prescriptive
measurement methods and technologies to comply with Agency regulations has unintentionally imposed a
significant regulatory burden and created a barrier to the use of innovative environmental monitoring
technology.
EPA has demonstrated its commitment to reducing unnecessary regulatory burdens by initiating a
number of programs that respond to the needs of the regulated community, the technology development
community, and the laboratory services community. As part of this new Agency-wide approach, EPA's
Office of Science and Technology (OST) and Office of Ground Water and Drinking Water (OGWDW)
have coordinated with Various Headquarters offices, EPA Regions, States, other governmental agencies,
water and wastewater utilities, industry, environmental laboratories, instrument vendors, consensus
standards organizations, and other interested parties to define a comprehensive program to streamline
OW's water test methods approval program. The streamlining initiative encourages the use 'of1 emerging
and innovative technologies by (1) increasing method flexibility so that approved methods can be
modified without formal EPA approval, (2) providing a mechanism for non-EPA organizations to develop
and submit new methods for approval, and (3) expediting the method approval process. EPA believes that
streamlining also offers the opportunity to improve the quality of environmental monitoring.
The streamlining initiative seeks to allow laboratories and regulated entities to use professional
judgement in modifying and developing alternatives to approved test methods to take advantage of
emerging technologies that reduce costs, overcome analytical difficulties, and enhance data quality. A
necessary condition of method flexibility is the requirement that a modified method produce results
' equivalent or superior to results produced by the approved reference method. EPA believes that increasing
method flexibility and streamlining the method approval process will provide several benefits. Permittees,
permit writers, public water systems, and drinking water laboratories will be allowed the flexibility to
select the analytical method that yields improved performance in specific discharge or drinking water
monitoring situations. The flexibility to select more appropriate methods provides an opportunity to use
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Streamlining Guide
new technologies to overcome matrix interference problems, lower detection limits, improve laboratory
productivity, or reduce the amount of hazardous wastes in the laboratory.
A more flexible method approval program is consistent with President Clinton's Environmental
Technology and Reinventing Government initiatives and Congress' National Technology Transfer and
Advancement Act of 1995 (NTTAA). It will empower stakeholders while decreasing demands on Agency
resources. The streamlined program is intended to accelerate environmental technological innovation as a
means of strengthening America's economy and creating jobs while enhancing environmental protection.
EPA believes that the incentives provided by a more flexible water test methods approval program will
spur the development of new technologies and with it, new jobs. In addition, EPA anticipates that the use
of new technologies may lower the cost of environmental measurements, thereby reducing costs of
environmental compliance for American industries and municipalities.
7,7.7 Statutory Authority
1.1.1.1
Clean Water Act requirements
The CWA requires the EPA Administrator to promulgate effluent limitations guidelines for
specified categories and classes of point sources. Section 301 of the CWA prohibits the discharge of any
pollutant into navigable waters unless the discharge complies with a National Pollutant Discharge
Elimination System (NPDES) permit issued under Section 402 of the Act. Section 307 requires the EPA
Administrator to publish regulations establishing pretreatment standards for introduction of pollutants into
publicly owned treatment works (POTWs). Section 401 requires certification for the construction or
operation of facilities which may result in any discharge into the navigable waters.
CWA Section 304(h) requires the EPA Administrator to promulgate guidelines establishing test
procedures for data gathering and monitoring compliance with published guidelines. EPA's approval of
analytical methods is authorized under this section of CWA, as well as the general rulemaking authority in
CWA Section 501 (a). The Section 304(h) test procedures (analytical methods) are specified at 40 CFR
part 136. They include "Methods for Chemical Analysis of Water and Waste" (MCAWW); the 600- and
1600- series methods; methods published by consensus standards organizations such as ASTM and
AOAC-International, and the publication "Standard Methods for the Examination of Water and
Wastewater" (Standard Methods), which is published jointly by the American Public Health Association
(APHA), the American Water Works Association (AWWA), and the Water Environment Federation
(WEF); methods used by the U.S. Geological Survey; methods developed by the environmental
community; and other methods referenced in CWA regulations. EPA uses these test procedures to support
development of effluent limitations guidelines approved at 40 CFR parts 400 - 499, to establish
compliance with (NPDES) permits issued under CWA Section 402, for implementation of the
pretreatment standards issued under CWA Section 307, and for CWA Section 401 certifications.
1.1.1.2
Safe Drinking Water Act requirements
The SDWA requires the EPA Administrator to promulgate national primary drinking water
regulations (NPDWRs) that specify maximum contaminant levels (MCLs) or treatment techniques for
listed drinking water contaminants (Section 1412). In addition, Section 1445(a) of SDWA authorizes the
Administrator to establish regulations for monitoring to assist in determining whether persons are acting in
compliance with the requirements of SDWA. EPA's approval of analytical test procedures is authorized
under these sections of SDWA, as well as the general rulemaking authority in SDWA Section 1450(a).
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Introduction
SDWA Section 1401(1)(D) specifies that NPDWRs contain criteria and procedures to ensure a
supply of drinking water that dependably complies with MCLs, including quality control (QC) and testing
procedures to ensure compliance with such levels and to ensure proper operation and maintenance of
drinking water supply and distribution systems. These test procedures (analytical methods) are approved
at 40 CFR part 141. They include MCAWW methods; the 200, 300 and 500 series methods; and other
methods referenced in SDWA regulations. EPA uses these test procedures to establish MCLs under
SDWA Section 1412 and to establish monitoring requirements under SDWA Section 1445(a).
7. 7.2 Current Office of Water Methods Approval Programs
Requirements for approval of alternate analytical techniques (methods) are specified at 40 CFR
136.4 and 136.5 for wastewater methods and at 40 CFR 141.27 for drinking water methods. These
requirements are the basis for the Agency's alternate test procedure (ATP) program for water methods.
Under the ATP program, an organization may submit an application for approval of a modified version of
an approved method or for approval of a new method to be used as an alternate to an approved method.
The submitting organization is responsible for validating the new or modified method. The Agency
reviews the ATP validation package and, if required.; promulgates successful applications in the CFR.
Rulemaking is required when a new or revised method is added to the list of approved methods in the
CFR. The ATP and rulemaking processes make heavy demands on stakeholder, contractor, EPA, and
Federal Register resources. These processes can require several months to approve a minor method
modification and a year or more to promulgate a major modification or a new technology. Because
advances in analytical technology continue to outpace the capacity of OW's method approval program, the
program has been under-utilized and slow to respond to emerging technologies. In the streamlining
initiative, which is described below, EPA proposes to amend the procedures at 40 CFR 136.4, 136.5, and
141.27 to specify a more rapid and less resource, intensive process for approval of new technologies. The
current ATP process is depicted in Figure 1.1.
1.2 The Streamlining Initiative
Upon accepting responsibility for the wastewater methods approval program, EPA's EAD
undertook a review of the method needs and available resources of EPA; the regulated community; state,
regional, and local permitting authorities; and the analytical services community. EAD determined that
the methods approval program would best be served by undertaking a streamlining initiative to (1) expand
the flexibility to modify approved methods without a cumbersome review and approval process, in order
to allow timely introduction of emerging technologies; and (2) expedite the approval of new and modified
methods, involving outside organizations in the method development process. During 1995 and 1996,
EAD developed and refined a comprehensive initiative to streamline OW's method approval program.
This streamlining initiative is a combined effort of EPA's Office of Science and Technology and Office of
Ground Water and Drinking Water and applies to approval of wastewater and drinking water methods.
To keep pace with advances in technology, EPA believes that this is an appropriate time to look to
organizations outside of EPA to assist in the development of new methods and to find ways to take
advantage of emerging technologies to reduce costs, overcome interferences, and enhance data quality.
Once the streamlining initiative is in place, EPA expects to increase its reliance on outside organizations to
develop new methods. EPA will focus its methods development efforts on specialized, esoteric, or orphan
methods to support regulation development or compliance monitoring.
EPA recognizes that expanded flexibility must be matched with controls to ensure that program
quality is maintained. These controls include a system for organizations that modify methods to
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Streamlining Guide
Figure 1-1: The Current Alternate Test Procedure Process
EPA Review
EAD - Wastewater
NERL-Ci - Drinking water
EAD proposes in
FR if apptovsd
304(h)
Committee
provides final
approval
Rtgionil
authority
provides final
approval
NERL-Ci reviews
and
recommends
ast
or Drinking
Water?
OGWDW
proposes in FR if
demonstrate and document equivalency of the modified method to the approved reference method. The
requirements for documenting equivalency of modified methods are tiered to reflect the variety of
conditions under which a modification will be applied. The requirements for validating newly developed
methods are similarly tiered.
An overview of the proposed streamlined method approval program described in this Guide is
depicted in Figure 1.2. This streamlined program would replace the current ATP process depicted in
Figure LI.
7.2.7 Streamlining Objectives
The proposed streamlining initiative is designed to improve overall resource use while making the
method development process more efficient and accessible to non-EPA organizations. The goals of the
initiative are to decrease the need for developers of modified methods to use the ATP program and to
speedup the approval (or disapproval) of methods subject to ATP review. EPA has defined several
specific objectives to meet these goals. The objectives of the streamlining initiative are to:
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Introduction
Figure 1-2: Proposed Streamlined Methods Approval Program
(1) ' increase the current flexibility to modify approved chemical and biological test methods without
formal EPA approval; this will allow laboratories to overcome matrix interferences and will
facilitate early introduction of innovative technologies.
(2) Designate a reference method for each combination of analyte and determinative technique and
establish standardized quality control (QC) tests for approved methods, to ensure data quality
while allowing for method flexibility. ,
(3) Develop QC acceptance .criteria for reference methods lacking these criteria, to provide a means
. whereby a laboratory can demonstrate equivalent or superior performance of a modified method.
(4) Provide a standard mechanism for validation and approval of new chemical and biological test
methods, including a standard method format, to expedite method approval and increase
confidence in the validity of the methods and resulting data.
(5) Encourage stakeholder participation in method development, to keep pace with emerging
technologies.
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Streamlining Guide
(6) Prepare to harmonize the wastewater and drinking water methods by setting the stage for
consolidation of the water methods.
(7) Increase standardized data reporting by recommending use of standard data elements for reporting
analytical results for environmental and QC samples.
(8) Identify and propose withdrawal of outdated methods from 40 CFR parts 136 and 141, to
modernize approved test methods.
1.2.2 Benefits of Streamlining
Advantages of streamlining EPA's water methods approval program are expected to be widely
shared by EPA, purveyors of new technology, the regulated community, regulatory authorities, and
analytical laboratories. Flexibility in methods is expected to enhance compliance monitoring programs by
reducing the need for EPA and state, regional, and local permitting authorities to review and provide
formal approval of specific method adaptations. In addition, method flexibility, along with a well-defined
program for developing and approving new methods, will provide research laboratories, instrument
vendors, and equipment manufacturers with incentives for developing new analytical techniques. This, in
turn, will provide the regulated community and their laboratories more flexibility to select analytical
methods that yield improved performance in specific wastewater discharge or drinking water monitoring
situations.
Expanding method flexibility and streamlining the method approval process will yield several
benefits.
(1) Because of increased flexibility to modify methods without formal EPA approval, only new
methods require formal EPA approval. Because ATPs for modified methods will be processed
only upon request, the number of methods that must pass through the rulemaking process will be
significantly reduced. This will reduce demand on Agency resources- at the same time that the use
of new technologies accelerates.
(2) Allowing more extensive modification of existing methods will make laboratory operations more
efficient, reduce analytical costs, reduce the amount of hazardous materials in laboratories,
enhance development of new instrumentation, and improve the quality of environmental data.
(3) Non-EPA organizations, including instrument vendors and laboratories, will have a mechanism
for gaining timely approval of new methods
(4) Use of direct final rulemaking for approval of noncontroversial method revisions will decrease the
time and effort to approve and list a method in the CFR.
* ' /
(5) Detailed guidance on the preparation and submission of requests for approval of new methods will
ensure that new methods are approved as quickly as possible.
(6) Requirements for standard QC tests in all methods will ensure consistency among methods and
enhance program and data quality.
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introduction
(7)
Established method validation requirements will facilitate method development as well as
ensuring that, prior to approval, all methods undergo levels of testing appropriate to their intended
use.
1.2.3 Development of EPA's Streamlining Initiative
Between April and August 1995, EPA developed a "straw man" for streamlining, composed of
several draft documents dealing with issues of method flexibility, standardized QC, method validation, and
method format. This straw man was provided to and discussed with participants at several public »
meetings on streamlining held by EPA. As of the publication date of this draft guide, EPA has conducted
four public meetings on streamlining its water test methods approval program. These meetings were held
in Seattle, Washington on September 28, 1995; Boston, Massachusetts on January 25, 1996; Chicago,
Illinois on February 14, 1996; and Denver, Colorado on July 24, 1996. The purpose of these meetings
was to present and discuss EPA's straw man for streamlining and to obtain stakeholder suggestions for the
purpose of refining the streamlining approach prior to its proposal.
All meetings were announced in the Federal Register in advance. The first meeting, held in
Seattle, was announced on September 12, 1995, in a Federal Register notice titled, "A Public Meeting and
Availability of Documents on Streamlining Approval of Analytical Methods at 40 CFR Part 136 and
Flexibility in Existing Test Methods" (60 FR 47325). That Federal Register notice provided
supplementary information regarding the streamlining effort and made available several supporting
documents. Subsequent public meetings in Boston and Chicago were announced in a Federal Register
notice dated December 18, 1995 (60 FR 65206), and the fourth public meeting in Denver was announced
in & Federal Register notice on July 10, 1996 (61 FR 36328.).
•' ' ' - ' • i - '
Stakeholder comments at the public meetings showed strong support for all of the streamlining
objectives. The straw man and summaries of the public meetings were distributed to meeting participants
and made available to others in response to requests through OST. Following the first three public
meetings, EPA compiled and reviewed preliminary stakeholder advice to assess the initial response to
streamlining and revise the approach accordingly. In response to stakeholder suggestions, EPA added
seven items to the streamlining initiative: • .
• Drinking water methods (40 CFR part 141) were included.
• Flexibility was expanded to include changes to the determinative technique.
• . Flexibility was qualified to clarify that flexibility in front-end techniques does not apply to sample
collection and preservation.
• Tier 1 validation was expanded to allow single-laboratory application of a method modification to
multiple matrix types. •
• An option to have EPA review Tier 2 and Tier 3 method modifications, upon request, was added.
• An option to have EPA propose and promulgate reviewed Tier 2 and Tier 3 method modifications,
upon request, was added.
• An option to submit screening methods for approval as new methods was added.
This Streamlining Guide and the Guidelines and Format for Methods to be Proposed at 40 CFR
Part 136 or Part 141 (Method Guidelines and Format) were developed in July 1996, and replaced the
supplementary information made available through the September 12, 1995, notice. These documents
served as the new straw man discussed at the final public meeting on streamlining held in Denver.
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Streamlining Guide
In addition to the public meetings, EPA solicited support and expertise from each of the consensus
standards organizations and government agencies that have developed methods already approved for use
under the wastewater and drinking water programs. These groups include the American Public Health
Association (APHA), American Water Works Association (AWWA), and Water Environment Federation
(WEF) as publishers of Standard Methods for the Examination of Water and Wastewater (Standard
Methods); ASTM (formerly, American Society for Testing and Materials); AOAC-International (formerly
the Association of Official Analytical Chemists); and the U.S. Geological Survey (USGS). EPA also
provided the opportunity for individuals, the regulated industry, vendors, laboratories, and laboratory
organizations such as the International Association of Environmental Testing Laboratories (IAETL) to
voice opinions at these meetings. These groups offered valuable insight concerning problems with the
current program and recommended areas of improvement. Also, some of these organizations have
developed or are developing standardized procedures for the areas listed above. In these instances, EPA
has built upon the experience and efforts of these organizations. For example, EPA recommends use of
the method validation protocols developed by ASTM and AOAC-International.
Major stakeholder organizations have participated in and provided input at the public meetings.
These organizations include: International Association for Environmental Testing Laboratories American
Association for Laboratory Accreditation, American Chemical Society, American Council of Independent
Laboratories, American Industrial Hygiene Association, American Water Works Association, Chemical
Manufacturers Association, and Water Environment Federation.
To ensure that the streamlining initiative remains current and is responsive to changing policies,
OW has committed to support committees such as the Environmental Monitoring Management Council
(EMMC) and the National Environmental Laboratory Accreditation Committee (NELAC). OW also is
committed to tracking method development efforts by stakeholders such as ASTM, AOAC-International,
and the National Council of the Paper Industry for Air and Stream Improvement (NCASI).
EPA has used informal suggestions received at public meetings and through unsolicited
correspondence in developing its approach to streamlining that is described in this guide. Formal
comments on the streamlining initiative will be requested when streamlining is proposed in the Federal
Register.
1.2,4- Implementation Issues
Through the public meetings and stakeholder discussions, EPA has identified and is addressing
key implementation issues related to streamlining.
1.2.4.1
Legal issues
Stakeholders expressed concern regarding potential conflicts between regulators and regulated
entities when using modified methods. For example, there was 'wide-spread concern over what would
happen if a discharger used a modified method and demonstrated compliance with a regulatory
concentration limit whereas a regulatory authpriry used the unmodified reference method and obtained
results suggesting that the discharger was out of compliance.
Representatives from EPA's OST, Office of Wastewater Management, and Office of Enforcement
and compliance Assurance met to study this question. Through these discussions it became apparent that
the streamlined program would work only if the modified method, once demonstrated to be equivalent to
the reference method, carried the same legal force and effect as the reference method. Therefore, the
8
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Introduction
difference in results produced by the modified and unmodified reference methods would be attributable
not to the modification, but to differences in results produced by two laboratories. This situation is no
different than the situation that currently exists, in that two laboratories can produce different results, one
of which is above and the other below a regulatory compliance limit. The legal resolution would therefore
remain the same as today — a decision would be made based on examination of the data.
1,2.4.2
Resource issues
Drinking water laboratory certification officials and pretreatment coordinators have expressed a
common C9ncern regarding the expertise and resources needed to adequately assess documentation of
method equivalency when modifications are used. To help alleviate this concern, EPA is providing
detailed guidance and checklists for assessing method modifications for equivalency with a reference
method (see Chapter 6). EPA also may provide training 'and other types of assistance in this area. •
1.2.4.3
The alternate test procedure process
OW anticipates that the flexibility allowed under streamlining will greatly reduce the number of
ATPs processed. The ATP process will remain in place as an option to be used for modified methods that
are approved and listed in the CFR. Expedited approval procedures, including use of direct final
rulemaking for noncontroversial actions, will significantly decrease the time required for approval a
method that has received a favorable recommendation from EPA.
1.2.4.4
Pilot testing
OW plans to pilot test the streamlining program prior to implementation. The pilot tests will focus
on (1) method flexibility and (2) development and approval of new methods. EPA anticipates conducting
several case studies in each of these areas during 1997. The pilot test reports will be reviewed and assessed
for changes that should be made to the streamlining program before nationwide implementation.
1.2.4.5
Concerns by consensus standards organizations
Many of the methods approved at 40 CFR parts 136 and 141 are methods developed by consensus
standard organizations such as Standard Methods, ASTM, and AOAC-International. In designating
reference methods for specific combinations of analytes and determinative techniques, it was EPA's intent
to select as the reference method, the method that contained QC acceptance criteria for the standard QC
elements identified in the streamlining initiative, regardless of whether that method was an EPA method or
one developed by another organization. '
As envisioned, the streamlining initiative allows modification to the reference method, provided
that the QC acceptance criteria are met. Consensus standards organizations have expressed concern that
modification of their methods would constitute a legal violation of the method, termed a "standard".
Therefore, Standard Methods, ASTM, and AOAC-International have declined to allow any modifications
to their designated methods that are not expressly permitted in the methods. Hence, their methods cannot
be modified under the procedures outlined hi this document and cannot be specified as reference methods
in 40 CFR part 136 or 141. This restriction will be noted in the specification of these methods in the CFR
tables. ,
This restriction does hot greatly impact the streamlining initiative, because an EPA method exists
that can be used as a reference method for nearly all analytes, and because most methods from consensus
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Streamlining Guide
standards organizations have sufficient explicit internal flexibility to meet the objectives of streamlining
and are frequently updated to reflect recent advances in technology. EPA expects to continue relying on
consensus standards organizations for the development of future methods as required by the NTTAA and
because of limited Agency resources for method development.
1.3 Purpose of Guide
The purpose of this document is to provide detailed guidance to permittees, water utilities,
regulatory authorities, purveyors of new technology, and analytical laboratories on implementation of a
comprehensive program to expand flexibility and streamline approval of methods under EPA's wastewater
and drinking water programs.
1.4 Content and Organization of Guide
The remainder of this document outlines the framework of and provides detailed guidance on
EPA's streamlining initiative. Some chapters are procedural and others are descriptive, as appropriate to
the topic.
Chapter 2 - Method Flexibility
This chapter describes the extent of existing method flexibility and outlines the principal concepts
of the expanded flexibility that EPA proposes to allow in order to implement a performance-based
approach to approving compliance methods in the Office of Water.
• Chapter 3 - Quality Control Requirements
This chapter describes the standard quality control tests that will be required for all methods and
specifies procedures for developing performance (i.e. QC acceptance criteria) for new methods.
» Chapter 4 - Method Validation Requirements
This chapter describes the requirements and procedures for validating and documenting validation
of a new method or method modification., utilizing a tiered system based on the intended
application of the method.
• Chapter 5 - The Method Approval Process
This chapter describes the expedited method approval process that includes a standard method
format and procedures for submitting validated methods to EPA for approval.
» Chapter 6 - Assessing Method Equivalency
This chapter provides guidance for assessing whether a method modification produces results
equivalent to results produced by a reference method.
» Chapter 7 - Biological Method Issues
The final chapter describes possible future plans to extend flexibility to biological methods.
Biological methods include measurement of microbiological parameters as well as methods with
biological indicators of toxicity.
The Guide includes several Appendices that contain useful reference materials.
10
Draft, December 1996
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introduction
Appendix A provides a comprehensive list of acronyms and abbreviations used in the Guide.
Appendix B is. a glossary of terms used in the Guide.
Appendix C contains descriptions of method modifications to 600- and 1600-series EPA methods
that have been determined to be within the currently allowed flexibility described in Chapter 2.
Appendix D comprises a list of suggested data elements for reporting, as discussed in Chapter 4.
Appendix E provides the EMMC checklists and certification statement that serve as the basis for „
proving and evaluating method equivalency, as described in Chapter 6. It also provides an
example of a completed method equivalency checklist.
Appendix F specifies QC acceptance criteria for approved inorganic methods that are proposed as
reference methods and that do not contain QC acceptance criteria.
Appendix G lists the bibliographic references used in the development of the Guide.
Draft, December 1996
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Chapter 2
Method Flexibility
2.1 Introduction
One of the primary goals of the streamlining initiative is to encourage the use of innovative
technologies by increasing method flexibility so that laboratories can modify approved reference methods
without formal EPA review. Under the streamlining program, it will no longer be necessary to apply for
alternate test procedure (ATP) approval of modified methods. Rather, laboratories will be required to
demonstrate and document that the modified method produces results equal or superior to results produced
by the unmodified reference method. To ensure data quality, EPA is building in well-defined controls on
this increased flexibility. These include designation of a reference method that contains quality control
(QC) acceptance criteria for use in demonstrating equivalency, and specific requirements for validating
modified methods and documenting equivalency. The purpose of this chapter is to describe the scope of
the flexibility that will be offered under streamlining.
\ ' . ,
This chapter begins by describing the current flexibility in EPA's wastewater and drinking water
programs, outlines the increased flexibility offered in the streamlining initiative, and defines the controls
that will be used as the foundation for expanded flexibility. The key concepts presented and discussed in
this chapter are: limited flexibility, reference methods, other approved methods, flexibility in front-end and
determinative techniques, new methods, method modifications, screening methods, method-defined
analytes, and new target analytes. '
2.2 Existing Flexibility
Methods currently approved at 40 CFR parts 136 and 141 under EPA's wastewater and drinking
water programs, respectively, allow two types of flexibility: (1) explicit flexibility, which does not require
prior EPA approval, and (2) flexibility that requires prior EPA approval through the ATP process.
Method modifications currently are allowed without prior EPA approval only when the
modification is explicitly allowed in the approved method. Explicit flexibility is termed limited flexibility.
Some approved methods provide limited flexibility to substitute specific apparatus with apparatus
demonstrated to be equivalent. The areas of currently allowed flexibility are indicated with the terms
"should" or the phrase "or equivalent" Substitution of a 500-mL beaker for a 250-mL beaker or use ofjan
"equivalent" chromatographic column are examples of such explicit flexibility. The EPA 600- and 1600-
series wastewater methods approved at 40 CFR part 136, Appendix A provide limited flexibility to
improve separations and reduce the cost of measurements as long as method performance is not sacrificed.
Laboratories that choose to exercise explicit flexibility are required to meet the quality control (QC)
acceptance criteria of the approved method for certain standardized QC tests. In the development of more
recent methods (e.g., Method 1664 and Method 1613), EPA has expanded its definition of allowed
flexibility to further encourage the use of new techniques that provide equal or better performance at lower
Draft, December 1996
13
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Streamlining Guide
costs. However, no approved methods provide unlimited flexibility and few provide the extensive
flexibility that EPA proposes in this initiative.
Currently, all modifications not explicitly allowed by the method require prior EPA approval.
These modifications must be approved through EPA's alternated test procedure (ATP) program.
Historically, the wastewater program has allowed some changes to front-end techniques but not to the
determinative technique. The drinking water program has been somewhat less restrictive on changing the
determinative technique and has allowed other changes to compliance methods, provided the chemistry of
the method is not changed. Some modifications to a front-end technique, such as changing the extraction
solvent, are not currently allowed in drinking water methods.
Procedures for requesting ATP approval are specified at 40 CFR 136.4 and 136.5 of the
wastewater regulations and at 40 CFR 141.27 of the drinking water regulations. ATP approval requires
concurrence by EPA (and sometimes the state) and in some cases, the method must be listed in the CFR
via an Agency rulemaking. The current ATP process is described in Chapter 1, Section 1.1.2.
2.3 Scope of Flexibility Provided by Streamlining
The streamlining initiative will allow flexibility to modify approved reference methods without
submission of ATPs, provided that a laboratory demonstrates and documents that the modified method
produces results equal or superior to those produced by the EPA-designated reference method. Only new
methods (or Tier 2 or Tier 3 modified methods for which developers specifically request EPA review) will
be subject to the streamlined ATP process. The scope of method flexibility that will be allowed under
streamlining is detailed in Sections 2.3.1 - 2.3.5.
It should be noted that the proposed flexibility does not extend to sample collection or
preservation conditions. These conditions include, but are not limited to, containers, holding times,
preservation procedures or reagents, shipping and storage procedures. Modifications to sample collection
and preservation conditions continue to require a variance as specified at 40 CFR 136.3 (c) and 141.27.
2.3.1 Reference Method
The foundation of EPA's flexibility concept is based on the use of a reference method against
which method modifications can be tested for equivalency. A reference method is a method that has been
approved at 40 CFR part 136 or 141, and contains (or is supplemented with) standardized QC procedures
and the required QC acceptance criteria for each of these procedures. Using QC acceptance criteria as the
performance measure makes the reference methods performance-based without extensive method
redevelopment.
Only one reference method will be designated for each combination of regulated analyte and
determinative technique. The purpose of specifying a single reference method for a given combination of
analyte and determinative technique is to avoid the possible confusion that could be created if two or more
reference methods contained differing QC acceptance criteria. The QC acceptance criteria associated with
the reference method will be the performance criteria against which method modifications are tested.
Method equivalency is demonstrated when results produced by a modification meet or exceed the QC
acceptance criteria hi the reference method.
For the streamlining proposal, EPA selected reference methods primarily on the basis of existing
QC acceptance criteria and/or the availability of data from which to develop QC acceptance criteria for
14
Draft, December 1996
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Method flexibility
each of the standardized QC elements described in Chapter 3 of this guide. An important additional
consideration was whether or not the organization that developed the method would allow its methods to
; be subject to the flexibility proposed by the streamlined method approval process. Some external methods
organizations, including Standard Methods/ASTM, and AOAC-International, have declined to allow
unrestricted modifications to their methods. Their collective decision was based on the need to retain their
methods as official "standards," which they have determined cannot be changed. Most of their methods
have sufficient explicit flexibility to meet the objectives of streamlining or can be updated rapidly through
their respective method approval processes. Because these methods cannot be modified, however, they
cannot be designated as reference methods.
A reference method is needed to exercise the increased flexibility offered by the streamlining
initiative. However, there are not reference methods for all listed combinations of analyte and
determinative technique. In some of these cases (e.g,, 40 CFR 136 Table ID), reference methods have not
been cited because EPA has not yet developed QC acceptance criteria for the methods. In other cases,
reference methods are not cited because the data are not yet available, In still others, it is not possible to
cite a reference method since there are only Standard Methods, ASTM, or AOAC-International methods
for that combination of analyte and determinative technique and these organizations do not allow
modification of their methods. EPA has designated most of the reference methods and .specified some of
the QC acceptance criteria (in the Methods and Criteria document) for chemical analytes listed at 40 CFR
parts 136 and 141. In a future rulemaking, EPA plans to designate additional reference methods and
develop QC acceptance criteria for all wastewater and drinking water chemical methods, but EPA has not
delayed proposal of the streamlining initiative while these activities take place.
Upon implementation of the streamlining initiative, EPA will retain all methods that are approved
for use at 40 CFR parts 136 and 141, but will re-categorize each method as either a "Reference Method" or
an "Other Approved Method". Regardless of whether a method has been designated as a "Reference
Method" or as an "Other Approved Method", all approved methods cited at 40 'CFR parts 136 and 141 will
carry equal regulatory status. Reference methods will be cited by adding a column to the tables currently
published at 40 CFR parts 136 and 141. A partial example of one table format is provided in Table 2.1.
Draft, December 7996
J5
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Streamlining Guide
Table 2.1: Example of Proposed 40 CFR part 136 Table IB with Reference Methods.
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Method HexibMty
In the future, it is anticipated that new reference methods will be approved at 40 CFR parts 136
and 141 only if a new analyte becomes of concern to EPA or if a new determinative technique is
developed for an existing analyte of concern. EPA intends to rely on outside organisations to develop
most new methods for approval at 40 CFR parts 136 and 141. To be approved (promulgated) as a
reference method, the method must meet the following requirements:
• , The method submitter must be willing to allow the method to be modified as described in this
streamlining initiative.
• The method must be for a combination of analyte of concern and determinative technique for
which an approved method does not exist. (This requirement precludes non-unique combinations
of analytes and determinative techniques.)
• The combination of analyte and determinative technique must, in EPA's judgement, be useful for
determination of an analyte of concern in a matrix of concern to EPA. (This requirement
precludes useless combinations of analytes and determinative techniques, e.g., use of a flame
ionization detector with EPA Method 508 or 608.)
• The method must pass all criteria set forth in this initiative including requirements for format, QC,
QC acceptance criteria, validation, and submittal of supporting documentation.
• The method must pass peer-review and the Agency ralemaldng process of proposal, public
comment, and final rule.
Based on suggestions and advice received to date, EPA believes that most organizations that
modify methods will choose to document the validity of those modifications without seeking formal
approval. Therefore, the streamlining initiative will eliminate multiple methods for the same combination
of analyte and determinative technique.
After streamlining is implemented, EPA's role in developing methods may be limited to instances
where a method is required for monitoring an unusual analyte and/or for monitoring in a specific sample
matrixand/or on a schedule that cannot be. met by an outside method developer. Regardless of the
organization that develops a new method, all new methods considered for approval under 40 CFR part 136
and 141 would continue to be proposed in the Federal Register and subject to public comment prior to
approval. Additional information concerning the method submission arid approval process is provided in
Chapter 5. '
2.3.2 Modifications to Front-end and Determinative Techniques
Most method modifications allowed under the streamlining initiative fall into one of two
categories: (1) modification of a "front-end" technique or (2) modification of the determinative technique.
A third category, adding additional analytes, is discussed in Section 2.3.4.
A front-end technique is any technique in the analytical process conducted at the laboratory that
precedes the determinative technique (see definition below). Front-end techniques include all procedures,
equipment, solvents, etc., that are used in the preparation and cleanup of a sample for analysis. Under the
streamlining initiative, EPA proposes to allow laboratories the flexibility to modify any and all front-end •
techniques without notifying EPA, provided the modification is not explicitly prohibited in the reference
Draft, December 1996
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Streamlining Guide
method and provided the modification can be demonstrated to produce results equal or superior to results "
produced by the reference method. This flexibility includes the ability to modify the chemistry of the
front-end of the method. For example, changing the extraction solvent and substituting liquid-liquid for
solid-liquid extraction will be allowed. However, if changing the chemistry of the method might affect the
extract holding tunes specified in the reference method, a new extract holding time study must be
performed. For example, extracting the water sample with pentane rather than isooctane is not likely to
affect extract holding times because the chemical properties of the solvents are very similar. However,
replacing ethyl acetate with a chemically dissimilar solvent, acetone, would require a reverification of the
holding times for the target analytes in acetone. The developer of a modified method always has the
option of asking EPA or other regulatory authority for a technical opinion on the acceptability of the
developer's validation data that supports the method modification. As noted in Appendix C (issue 26),
changes in the sorbent trap in the purge-and-trap volatile organic compound (VOC) methods are allowed,
but the methods specifically preclude changes to the purge and desorption times or gas flows. Although
these are front-end procedures, the method explicitly disallows modifications because these conditions are
independent of the sorbent used and have been optimized for full recovery of the target VOCs.
A determinative technique is the physical and/or chemical process by which the measurement of
the identity and concentration of an analyte is made. For most methods, the determinative technique
consists of an instrumental measurement (i.e., a detector). Examples of determinative techniques are
provided in Table 2-2 at the end of this chapter. Under the refined streamlining initiative, EPA proposes
to allow use of an alternate determinative technique that is not explicitly prohibited in the reference
method, provided that equivalency is demonstrated and documented as outlined above, and provided that
four conditions are met: (1) the alternate determinative technique measures a property similar to the
prescribed technique, (2) the alternate technique is demonstrated to be more specific (i.e., identifies the
analyte in the presence of interferences) and/or more sensitive (i.e., produces a lower detection limit) for
the analyte of concern than the determinative technique in the reference method, (3) there is not another
approved method that uses the alternate determinative technique for the determination of that analyte, and
(4) use of the alternate determinative technique will not result in a nonsensical combination of analyte,
front-end technique, and determinative technique.
Examples of allowed changes to a determinative technique are substitution of a photoionization
detector for a flame ionization detector for determination of polynuclear aromatic hydrocarbons,
substitution of a nitrogen-phosphorous detector for an electron capture detector (BCD) for determination
of analytes containing nitrogen or phosphorous, and substitution of a fluorescence detector for an
ultraviolet or visible wavelength detector. Substitution of a mass spectrometer (MS) for an BCD would
not be allowed if there is an approved MS method that measures the analyte of concern. Readers are
referred to the Streamlining Guide for more guidance on this subject.
Substitution of a photoionization detector (PID) for the flame ionization detector (FID) specified
in Method 610 is an excellent example of a useful and allowed modification to the determinative technique
because (1) the PID will provide improved sensitivity and specificity for determination of the polynuclear
aromatic hydrocarbons (PAHs) determined in Method 610, (2) there are no currently approved methods
for PAHs that use the PID as the determinative technique, and (3) use of a PID does not create a
nonsensical combination of analyte, front-end techniques, and determinative technique.
Conversely, substitution of a flame ionization detector (FID) for either an electron capture detector
(BCD) or an electrolytic conductivity detector (ELCD) for determination of chlorinated pesticides in
Method 508 or 608 would not be permitted because the FID is much less sensitive and less selective than
an ECD or ELCD, and would therefore be nearly useless for compliance determinations of pesticides in an
18
Draft, December 1996
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Method F)ex)b))/ty
environmental sample. In contrast, use of a high resolution mass spectrometer (HRMS) in place of an
BCD or ELCD for determination of pesticides would represent a significant improvement in selectivity
(specificity) and/or sensitivity. EPA would accept, and propose for approval, a fully developed method
using HRGC/HRMS for determination of chlorinated pesticides.
EPA chose to limit changes to the determinative technique by the four conditions described above
to preclude nonsensical combinations of analyte and determinative technique, to encourage a net benefit
(increased sensitivity and/or specificity), and to preclude multiple reference methods with the same
determinative technique but with different QC acceptance criteria for the sameanalyte(s) of concern. For
example, if a mass spectrometer were substituted for the conventional detectors in EPA methods 601 -
612, all of these methods would become GC/MS methods, but all would contain different QC acceptance
criteria. ,Further, they would all conflict with approved GC/MS Methods 625 and 1625. The proposed
restriction on detector substitution also is consistent with EPA's decision in the December 5, 1994 drinking
water methods final rule (59 FR 62456) not to allow substitution of MS in methods that specify
conventional GC detectors.. Another reason for limiting changes to the determinative technique is that
there are techniques, such as immunoassay, for which EPA has no reference method and therefore no
history to insure that the standardized QC proposed in today's rule are germane to, or adequate for,
assurance of the quality of data produced by the novel determinative technique. EPA would prefer that a
new method be written and submitted for approval when a novel determinative technique is developed.
EPA invites public comment on the suitability of the conditions EPA proposes to place on the flexibility to
modify determinative techniques in EPA reference methods. EPA would allow limited flexibility to
change the determinative technique. An alternate determinative technique can be used provided that (1)
the.alternate technique is demonstrated to be more specific (i.e., identifies the analyte in the presence of
interferences) and/or more sensitive (i.e., produces a lower detection limit) for the analyte(s) of interest
than the determinative technique in the reference method, (2) there is not another approved method that
uses the alternate determinative technique for determination of that analyte, and (3) use of the alternate
determinative technique will not result in a nonsensical combination of analytes, front-end techniques, and
determinative techniques.
2.3.3 Method-Defined Ana/ytes
In its initial straw man, EPA expressed concern that some techniques may not produce results
equivalent to results produced by techniques employed for "method-defined analytes". A method-defined
analyte is an analyte that does not have a specific, known composition so that the analytical result depends
totally on how the measurement is made. Therefore, a change to either the front-end steps or the
determinative technique for a method-defined analyte has the potential of changing the numerical value of
the result for a given sample. Examples of method-defined analytes include adsorbable organic halides
(AOX), biochemical oxygen demand (BOD), total radioactivity and whole effluent toxicity (WET).
EPA believes that methods for some method-defined analytes will need to have less flexibility
than methods for specific chemical substances. EPA believes, however, that some flexibility can and
should be allowed in these methods. Therefore, EPA intends to restrict the allowable flexibility in methods
for
Draft, December 1996
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Streamlining Guide
Table 2-2,
Examples of Determinative Techniques
Tliefollowing is a partial list of determinative techniques. This list is not all-inclusive; it is merely
intended to provide examples of the types of procedures that may be considered subject to modification
as determinative techniques under the streamlining initiative.
Alkali Flame Detector (AFD)
Alpha Gas Proportional Counter
Alpha Scintillation Detection
Alpha Spectrometry
Amperometric Detection
Anodic Stripping Voltametry
Atomic Absorption Spectroscopy (AA)
Autoradiaography
Beta Gas Proportional Counter
Beta Scintillation Detection
Bioassay
Capillary Gas Chromatography/Electron Capture Detection (Capillary GC/ECD)
Capillary Gas Chromatography/Electrolytic Conductivity Detection (Capillary GC/ELCD)
Capillary Gas Chromatography/FIame lonization Detection (Capillary GGTTD)
Capillary Gas Chromatography/FIame Photometric Detection (Capillary GC/FPD)
Capillary Gas Chromatography/High Resolution Mass Spectrometry (Capillary GC/HRMS).
Capillary Gas Chromatography/Low Resolution Mass Spectrometry (Capillary GC/LRMS)
Capillary Gas Chromatography/Nitrogen-Phosphorus Detection (Capillary GC/NPD)
Capillary Gas Chromatography/Photoionization Detection (Capillary GC/PID)
Cold Vapor Atomic Absorption (CVAA)
Cold Vapor Atomic Fluorescence (CVAF)
Conductivity Bridge (a.k.a. "Wheatstone Bridge")
Current Meter
Electret lonization Chamber
Electrochemical Detector .
Electrochemical Sensor
Electron Capture Detection (ECD)
Electrolytic Conductivity Detection (ELCD)
Electromagnetic Current Meter
Emission Spectroscopy
Filter Photometer
Flame Atomic Absorption (FLAA)
Flame lonization Detection (FID)
Flame Photometric Detection (FPD)
Fluorometry
Fourier Transform Infrared Spectrometer (FTIR)
Gamma Ray Counter
20
Draft, December 1998
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Method flexibility
Table 2-2 (Continued)
Examples of Determinative Techniques
, Gamma Spectrometry
Gas Chromatography (GC)
GC/Alkali Flame Detector (GC/AFD)
GC/ECD
GC/ELCD
GC/FID
•GC/FPD
GC/FTIR .
GC/Halogen Specific Detector (HSD)
GC/Mass Spectrometry (GC/MS)
GC/Nitrogen Phosphorus Detector (GC/NPD)
GC/Photoionization Detector (GC/PID)
GC/Thermal Conductivity Detector (GC/TCD)
GC/Thermionic Detector
Graphite Furnace Atomic Absorption (GFAA)
High Resolution Gamma Spectrometry
High Resolution Gas Chromatography (HRGC)
High Resolution Mass Spectrometry (HRMS) •
HPLC/Electrochemical Detector
HPLC/Fluorescence Detector
HPLC/FTIR
HPLC/Thermospray-Mass Spectrometry Detector
HPLC/Refractive Index Detector
HPLC/Ultraviolet Detector (HPLC/UV)
Human eye
Human nose
Human tongue
Hydrometer
Inductively Coupled Plasma/Atomic Emission spectroscopy (ICP/AES) .
Inductively Coupled Plasma/Mass Spectrometry (ICP/MS)
Infrared Spectrophotometer (IR)
Ion-Selective Electrode
Laser Phosphorimeter
Liquid Scintillation Counter
Mass Spectrometer (MS)
Microscopy
Neutron Activation Analysis
Nitrogen-Phosphorus Detector (NPD)
Non-dispersive Infrared (NDIR)
Draft, December 7996
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Streamlining Guide
Table 2-2 (Continued)
Examples of Determinative Techniques
Nephelometer
Particle Beam Mass Spectrometry
pH Meter
Photoacoustic Infrared Detector
Photoionization Detector
Photometer
Polarograph
Potentiometer
Pressure Meter
Quartz Furnace AA '
Spectrophotometer
Stabilized Temperature Graphite Furnace AA (STGFAA)
Thermal Conductivity Detector
Thermal Chromatography/Mass Spectrometry
Transmission Electron Microscopy (TEM)
Tensiometer
Titration
Toxic Gas Vapor Detector Tube
Turbidimeter
X-Ray Diffraction
X-Ray Fluorescence
22
Draft, December 1996
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Method Flexibility
method-defined analytes and establish more stringent requirements for exercising this flexibility and for
demonstrating equivalency. To implement this proposal, EPA would either not designate a reference
method for a method-defined analyte or would footnote the tables in 40 CFR parts 136 and 141 for those
analytes that are method-defined and either update or supplement these methods with explicit guidance
concerning areas of allowed flexibility. .
EPA will accept and review new or modified methods that produce results significantly different
from results produced by approved methods for method-defined analytes. The Agency cannot guarantee,
however, that such methods will ever be used in regulation development or monitoring. For example,
methods currently approved at 40 CFR part 13 6 for determination of oil and grease are based on
sepafatory funnel extraction using CFC-113 or hexane, drying, concentration, and weighing (gravimetry).
.Other methods based on GC, infrared spectroscopy (IR), or immunoassay techniques have been or are
being developed for determination of oil and grease, but it is not expected that any of these other
determinative techniques will produce results equivalent to results produced by gravimetry. EPA will'
accept application for approval of a new method that employs a different determinative technique from
gravimetry, and will propose and attempt to approve such a method on request by the method developer;
however, EPA will need to create a separate category within the tables in 40 CFR part 136 for such
methods. This table will apply only to methods for method-defined analytes that produce results
significantly different from results produced by the approved methods.
Given this limitation and the potential negative connotation that may be associated with methods
in such a table, purveyors of new technology for determination of method-defined analytes may choose to
avoid submitting a new method to EPA for approval and promulgation. Instead, they may find it
preferable to exercise the flexibility provided in this initiative and demonstrate that the new technique
produces results equivalent to the reference method on a matrix-by-matrix basis. EPA will work with
method developers to determine that a combination of analyte and determinative technique is new and to
assess whether a new method for a method-defined analyte is desirable.
2.3.4 Flexibility to Add New Target Analytes
In today's proposed rule, EPA has also given details for modifying the analytical scope of an
approved method by adding additional analytes. This action is in response to public comment on previous
rules (59 FR 62456, December 5, 1194; 58 FR 65622, December 15, 1993) to extend the scope of an
approved method to the determination of other analytes. Method developers seek this approval when they
want to adapt an existing method rather than develop a new one to obtain occurrence data for a new
analyte. EPA believes these requests have merit when there is a potential for new regulatory requirements
and historical monitoring data might be useful in making process, treatment, or regulatory decisions.
Examples of monitoring for a new analyte include industrial or POTW monitoring for ethers in a
discharge, PWS monitoring for unregulated pesticides or pesticide metabolites, and PWS monitoring for
analytes on the drinking water priority list. EPA also believes these requests have merit when
technological advances make the measurement of additional analytes feasible (e.g. adding lead to the
scope of EPA Method 200.7). Under the proposed flexibility procedures for modified and new methods,
developers can obtain approval for adding analytes to an approved method as an allowed method
modification if the conditions below are met. \
Laboratories may add a new target analyte to Approved methods provided (1) it can be
demonstrated that the analyte does not interfere with determination of the analytes of concern in that
method, (2) QC acceptance criteria are developed and employed for determination of the target analyte, (3)
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Streamlining Guide
there is not another approved method that uses the same determinative technique for that analyte and (4)
the that the reason for adding the analyte is not to avoid the sample preservation or sample (or extract)
holding time conditions that are already required for that analyte in another approved method. The third
and fourth criteria preclude method shopping whereby a user might add analytes to a reference method
with less rigid QC acceptance, sample collection or holding time criteria. For example, if an approved
method for an analyte of concern requires acidification of the sample, a user does not have the flexibility
to modify a method that does not require sample acidification to include analysis of the analyte of concern.
Modifications of this type require EPA approval as a new method.
If QC acceptance criteria do not exist for a new analyte, the guidelines contained in Chapter 3
should be followed to develop and obtain approval for these criteria. Alternatively, under conditions
described in Chapters 4 and 5, QC acceptance criteria for the new analyte may be transferred from the
criteria for an analyte with similar chemical characteristics. Other requirements for obtaining approval of
QC acceptance criteria for additional target analytes are described in Chapters 4 and 5.
2.3.5 New Methods, Screening Methods, and Modified Methods
A critical aspect of the streamlining initiative is to provide flexibility to modify an existing
approved method provided that results obtained using the modified method meet the QC acceptance
criteria of the reference method. Following release of its initial straw man, EPA received several requests
to clarify the differences between new and modified methods and the requirements that pertain to each.
Many reviewers also asked EPA if the procedures for developing, proposing and approving methods for
use in the wastewater and drinking water programs would be applicable to screening methods.
Clarifications that address these issues are as follows.
A new method is a set of procedures that:
(1) Is documented in accordance with the requirements detailed in the Guidelines and Format for
Methods to be Proposed at 40 CFR Parts 136 or 141,
(2) Contains the standardized QC elements detailed in Chapter 3,
(3) Contains QC acceptance criteria that have been developed hi accordance with the requirements
described in Chapter 3,
(4) Employs a determinative technique for an analyte of concern that differs from determinative
techniques employed for that analyte in methods previously approved at 40 CFR part 136 or 141,
and
(5) Employs a determinative technique that is more sensitive and/or selective (specific) than the
determinative techniques hi all methods previously approved for the analyte.
A method that meets all five of these characteristics is considered to be a confirmatory method if
the method also is sufficiently selective and quantitative that most positive results do not have to be
verified by analysis with another method. The term "confirmatory" is used to distinguish this type of
method from a screening method (described below). All methods currently approved at 40 CFR parts 136
and 141 are confirmatory methods.
Methods with disparate characteristics have been developed and marketed as screening methods.
Some are inexpensive and easy to use; others require expensive equipment and training to conduct
complex procedures. Some screening methods are designed to be used at the sample collection site; others
require a well-equipped laboratory. In this Guide, a screening method is defined as a method that meets
the first four of the five conditions described above for new methods and that has been demonstrated to
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Method Flexibility
produce a false negative probability of no more than one percent (1%) at the limit(s) of regulatory concern.
Methods can fail the fifth condition for a new method, if they are non-selective or not quantitative for the
target analyte. A non-selective method is a method in which the determinative (or other step) technique in
the method may produce a result for any one of several analytes that share common physical or chemical
characteristics with the target analyte. For example, an atrazine immunoassay might respond to any
triazine (atrazine, simazine, cyanazine) pesticide in the sample.
Screening methods may be quantitative, but are often semi-quantitative or presence-absence. For
example, if the same water sample containing a free chlorine residual of 1.3 mg/L were analyzed with
several methods, a quantitative titrimetric method might provide a result such as 1.2 ± 0.2 mg/L. A semi-
quantitative colorimetric method might indicate that the free chlorine residual concentration was in the
range of 1.0 to 1.5 mg/L. Analysis with a presence-absence method that had a minimum sensitivity of 0.5
mg/L would produce a presence reading indicating that a free chlorine residual was present at 0.5 mg/1 or
more.
••'•:•'.•' • ' • " "
When using a screening method, .all positive results must be verified by re-analysis with a
confirmatory method because screening methods can be less selective and therefore more subject to false
positives than confirmatory methods. Historically, EPA has not considered screening methods for
approval at 40 CFR part 136 or part 141. Under the streamlining initiative, EPA proposes to consider the
approval of these methods for compliance monitoring provided: (1) the method meets all the requirements
described in the Streamlining Guide and in the regulations at 40 CFR 136.5 and 141.27, (2) all positive
sample results obtained with the method are confirmed and reported using an approved confirmatory
method, and (3) the probability of the method producing a false negative result at concentrations of
regulatory interest is no more than one percent (1%). EPA notes that, for part 141 approval, these criteria
may be when the Agency implements the requirements for screening methods that are in the August 2,
1996 amendments to the SDWA. When the streamlining initiative is promulgated, a separate table will be
published at 40 CFR parts 136 and 141 to list screening methods that have been approved for compliance
monitoring. '",.-'.
The definitions of confirmatory and screening methods in this section are deliberately narrow to
preclude them from being considered as method modifications under the concept of method flexibility. A
modified method is an approved method that has been modified to change a front-end technique or the
determinative technique, either using explicit flexibility or expanded flexibility allowed under
streamlining. Under the streamlining initiative, there will be two forms of method modifications:
• Modifications to approved methods may be made as specified within those methods. This explicit
flexibility existed prior to the streamlining initiative and will continue to exist. Explicit flexibility
exists for all approved methods including EPA, Standard Methods, ASTM, AOAC-International,
and other methods approved at 40 CFR parts 136 and 141.
• Modifications to approved methods designated as reference methods. This flexibility does not
exist prior to implementation of the streamlining initiative. After streamlining has been
promulgated, modifications may be made to reference methods provided that the modification
Meets the requirements detailed in 40 CFR 136 or 141, and
Meets the requirements detailed in this Streamlining Guide which is being incorporated
into the CFR by reference as part of the streamlining rule
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Streamlining Guide
These modifications may not be made to Standard Methods, ASTM, and AOAC-International
methods, and none of these methods have been designated as a reference method under this
initiative. ' f
2.4 Controls on Flexibility
EPA has established a number of controls that provide the foundation for the increased flexibility
allowed under streamlining. These controls are:
* A requirement to demonstrate and document equivalency when method modifications are used.
• Designation of a reference method that contains QC acceptance criteria for use in demonstrating
equivalency.
• Standard procedures for validating new methods and demonstrating equivalency of method
modifications, based on the intended use 'of the method.
* A requirement for all new methods to contain standardized QC and specify QC acceptance
criteria.
• Detailed requirements for preparing the method validation package and supporting data when new
or modified methods are validated.
* Guidance for regulatory authorities' use in assessing equivalency of method modifications.
These controls are described in the appropriate chapters of this guide, as described in Chapter 1, Section
1.4.
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Chapter 3
Quality Control Requirements
3.1 Introduction
As the foundation for method flexibility, EPA will designate an approved method as the
"reference method" for each combination of analyte and determinative technique. Any newly developed
method that contains a unique combination of analyte and determinative technique would be considered a
new method and, when approved, could be designated as the reference method for that unique
combination of analyte and determinative technique. Any approved method not designated as a reference
method will be designated as an "other approved method." All methods must contain standardized quality
control (QC) tests. All reference methods must contain standardized QC tests and specify QC acceptance
criteria for each test. The QC acceptance criteria of the reference method must be met when using other
approved methods or method modifications. The QC acceptance criteria in the reference method are the
performance measures for demonstrating equivalency of method modifications.
The person or organization that develops a reference method for a particular combination of
analyte and determinative technique will be responsible for validating the method and for developing the
QC acceptance criteria.. QC acceptance criteria will be based on data generated during the method
validation study. Under the streamlining initiative, EPA is proposing to require a method validation study
that reflects the level of intended use for a method. This three-tiered approach to method validation is
explained in Chapter 4. EPA believes that the tiered approach will minimize the validation requirements
of limited-use methods (single-laboratory and single-industry use) and will focus resources on validation
of methods that are intended for nationwide use. Because QC acceptance criteria will be developed from
validation studies and because the validation requirements vary with each tier, the statistical procedures
used to develop the criteria will vary by tier.
Some methods presently approved at 40 CFR parts 136 and 141 do not contain acceptance criteria
for all standardized QC tests. In the streamlining proposal, EPA has provided supplementary QC
acceptance criteria for methods proposed as reference methods that do not already contain QC acceptance
criteria. QC acceptance criteria must be developed for and specified in all new methods that will be
approved as reference methods.
This chapter describes the three method validation tiers, lists and describes the standardized QC
tests required in all approved methods, and outlines procedures for developing QC acceptance criteria for
new methods at Tiers 1, 2, and 3. The key concepts presented and discussed in this chapter are:
standardized QC tests, calibration linearity, calibration verification, absolute and relative retention time
precision, initial precision and recovery, ongoing precision and recovery, analysis of blanks, surrogate or
labeled compound recovery, matrix spike and matrix spike duplicate, method detection limit.
demonstration, reference sample analysis, and QC acceptance criteria.
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Streamlining Guide
3.2 Description of Tiers
Tier 1 refers to new methods or method modifications that will be used by a single laboratory for
one or more matrix type(s). As used in streamlining, a matrix type is a sample medium (e.g., air, water,
soil) with common characteristics across a given industrial category or subcategory. Validation
requirements for Tier 1 reflect this limited use and correspondingly require single-laboratory testing in the
matrix type(s) in which the method will be used. In response to comments received during public
meetings, EPA has refined requirements for this tier to allow single laboratories to apply new or modified
methods to an unlimited number of matrix types after the method has been validated in nine discrete
matrix types. If results of Tier 1-Multiple Matrix Type validation studies are to be applied to a different
medium, each medium must be represented in the samples tested in the validation study. Procedures for
developing QC acceptance criteria for Tier 1 methods are given in Section 3.4.1.
Tier 2 refers to new methods or method modifications that will be used by multiple laboratories
analyzing samples of one matrix type from a single industrial category or subcategory. Validation at Tier
2 requires a three-laboratory interlaboratory study in the matrix type(s) in which the method will be used.
Procedures for developing QC acceptance criteria for Tier 2 methods are given in Section 3.4.2.
TierS refers to new methods or method modifications that will be used on a nationwide basis by
all laboratories for all matrix types. Validation at Tier 3 requires a nine-laboratory interlaboratory study
on nine matrix types. Validation must be performed on a minimum of nine matrix types in each sample
medium to which the method will be applied. Procedures for developing QC acceptance criteria for Tier 3
methods are given in Section 3.4.3.
3.3 Standardized Quality Control Tests
Under this initiative, standardized QC tests are required for use with currently approved methods
and are a mandatory component of all new methods. The standardized QC tests are as follows:
* calibration linearity .
• calibration verification
• absolute and relative retention time precision (for chromatographic analyses)
• initial precision and recovery
• ongoing precision and recovery
• analysis of blanks
• surrogate or labeled compound recovery
* matrix spike and matrix spike duplicate precision and recovery (for non-isotope dilution analyses)
• method detection limit demonstration
• analysis of a reference sample
These tests are described in Sections 3.3.1 - 3.3.10 below. .
3.3.7 Calibration Linearity
The calibration linearity specification establishes a break point between a straight line through the
origin and a straight line not through the origin or a curved calibration line. This break point is specified
as a maximum relative standard deviation (RSD=100s7% expressed as percent) of the:
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Quality Control Requirements
• relative response (RE.) for isotope dilution calibration, . •
• response factor (RF) for internal standard calibration, or
• calibration factor (CF) for external standard calibration,
below which an averaged RR, RF, or CF may be used. The number of calibration points is dependent on
the error of the measuring technique. Measurement technique error is determined by (1) calibrating the
instrument at the minimum level (ML) of quantitation and a minimum of two additional points, and (2)
determining the RSD of the RR, RF, or CF. For most analyses, such as the determination of semi-volatile
organic compounds by extraction, concentration, and gas chromatography, the measuring instrument is
calibrated, and sample preparation processes are excluded from the calibration process; for others, such as
the determination of purgeable organic compounds by purge-and-trap gas chromatography, calibration
encompasses the entire analytical process. Table 3-1 below gives the number of calibration points
required depending on the calibration linearity.
Table 3-1; Minimum Number of Points Required for Calibration1
Percent RSD2
0-<2
2-<10
'lO-<25
>25
Minimum Number of Calibration Points
3
5
7
1 Based on Rushneck et al. 1987. Effect of number of calibration points on precision and accuracy of GC/MS, in
Proceedings of Tenth Annual Analytical Symposium, USEPA: Washington, DC.
2 Percent RSD shall be determined from the calibration linearity test.
3 Assumes linearity through the origin (0,0). For analytes for which there is no origin (such as pHQ, a two-point
calibration shall be performed. •
The ideal calibration is a straight line that intersects the origin (zeroth order). In practice, too
calibration line constructed from three or more calibration points will intersect the exact origin (0.000 ...,
0.000 ,..). If, however, an error band is constructed around the calibration line, the error band will include
the origin for most calibrations. The use of an averaged RR, RF, or CF is an attempt to represent the
calibration with a single value that includes all of the points, including the origin, within the error
represented by the RSD.
' -' I
The maximum RSD specification is applicable to calibration with three or more calibration points.
For some methods, a least-squares regression and correlation coefficient have been used. However, an
unweighted least-squares regression that covers a large range will inappropriately weight the highest
calibration point(s). Equally weighing each point in a least-squares regression produces the same result as
an averaged RR, RF, or CF. Therefore, unless the method specifies use of a least-squares regression
and/or correlation coefficient, the RSD of the RR, RF, or CF must be used to establish calibration
linearity.
Calibrations higher than zeroth order calibration (straight line through the origin) are required
when the linearity criterion cannot be met. For most instruments and analytical systems, these calibrations
are first order (linear not through the origin; y = mx + b) and second order (y = ax+ bx + c). A second or
higher order calibration may be justified when an analyte can only be determined with a method that uses
Draft, December 1996
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Streamlining Guide
a determinative technique with a nonlinear response over the calibration range. A second order or higher
order calibration may be used, provided that the calibration increases monotonically. Monotonically
means that the response is successively greater at successively higher concentrations. For example, an
immunoassay typically requires a third (y = ax1 + bx2 + ex + d) or fourth (y = ax4 + bx3 + ex2 + dx + e)
order calibration, although not all of the terms in these equations may be needed.
EPA believes that most instruments and analytical systems are linear over a range large enough to
preclude the need for second order or higher calibration. If the linear range of any of these systems is
limited, sample dilution and reanalysis should be performed to bring the concentration within the linear
range, rather than extend the calibration into a nonlinear region of the instrument response. EPA
discourages use of higher than first-order calibration because responses in the nonlinear region of the
instrument response can mask curvature in the response that may be attributable to preparation of an
inaccurate standard. EPA requires that all calculations of concentrations of analytes in blanks, field
samples, QC samples, and samples prepared for other purposes be based on an averaged RR, RF, or CF, or
on a calibration curve.
3.3.2 Calibration Verification
This test is used to periodically verify that instrument performance has not changed significantly
from calibration. Verification is based on time (e.g., working day; 12-hour shift) or on the number of
samples analyzed in a batch (e.g., after every 10th sample). The terms "shift" and "batch" should be
specified in the method. If not, the general rule has been that calibration verification is performed every
12-hour shift on instruments used for determination of organic analytes and every 10th sample on
• instruments used for determination of metals. However, the over-riding rule should be that verification is
performed frequently enough to assure that the response of the instrument or analytical system has not
drifted significantly from calibration.
Calibration verification tests are typically performed by analyzing a single standard in the
concentration range of interest for the target analyte(s). In most methods, mis standard is in the range of 1
- 5 times the minimum level (ML) of quantitation and is at the same level as one of the standards used for
calibration. The calibration verification standard concentration should be within 1-5 times the ML rather
than at a "midpoint" concentration because specifying the midpoint can be interpreted as one-half (Vz) the-
highest calibration point. Using a concentration this high when the calibration covers orders of magnitude
may lead to erroneous results, because this midpoint standard may be far removed from the range where
most measurements will be made.
If the calibration is linear through the origin (as defined by linearity criteria in Table 3-1),
specifications for calibration verification are developed to define the allowable deviation of the RR, RF, or
CF of the calibration verification standard from the averaged RR, RF, or CF of the calibration. If linearity
criteria for calibration are not met, specifications for calibration verification are developed to define the
allowable deviation of the RR, RF, or CF of the calibration verification standard from a specific point on
the calibration curve.
For calculation of analyte concentrations, the averaged RR, RF, or CF, or the calibration curve is
always used; i.e., the calibration is not updated to the RR, RF, CF or the single point verification.
Updating the calibration to a single point after establishing an averaged RR, RF, or CF, or a calibration
curve is equivalent to performing a single-point calibration. This updating procedure, which is sometimes
termed "continuing calibration," is unacceptable and shall not be used because it nullifies the statistical
power of the full calibration.
30
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Quality Control Requirements
3.3.3 Absolute and Relative Retention Time Precision
Absolute retention time (RT) and relative retention time (RRT) are the QG criteria used in
chromatographic analyses to aid in the identification of each detected analyte and to confirm that sufficient
time was allowed for the chromatographic separation of the analytes in complex mixtures. These, criteria
also prevent laboratories from accelerating the analysis in an effort to reduce costs, only to find that
complex mixtures cannot be adequately resolved.
A minimum RT specification is developed for those methods in which a minimum analysis time
must be established to ensure separation of the analytes in complex mixtures including known or expected
interferences. An RT precision specification is developed for identification of an analyte by external
standard measurements, and an RRT precision specification is developed for (1) each analyte relative to its
labeled analog by isotope dilution measurements,.(2) each labeled compound relative to its internal
standard for isotope dilution measurements, and (3) each analyte relative to an internal standard for
internal standard measurements.
3.3.4 Initial Precision and Recovery , •
The initial precision and recovery (IPR) test, also termed a "startup test," is used for initial
demonstration of a laboratory's capability to produce results that are at least as precise and accurate as
results from practice of the method by other laboratories. The IPR test also is used to demonstrate that a
method modification will produce results that are as precise and accurate as results produced by the
reference method. The IPR test consists of analyzing at least four replicate aliquots of a reference matrix
spiked with the analytes of interest and with either surrogate compounds or, for isotope dilution analysis,
labeled compounds. The concentration of the target analytes in the spike solution may vary between one
and five times the concentration used to establish the lowest calibration point (e.g., one to five times the
ML). The spiked aliquots are carried through the entire analytical process. The IPR test is performed by
the laboratory before it utilizes a method or a method modification for analysis of actual field samples.
Specifications are developed for the permissible range of recovery for each analyte and for an upper limit
on the standard deviation or RSD of recovery.
3.3.5 Ongoing Precision and Recovery
The ongoing precision and recovery (OPR) test, sometimes termed a "laboratory control sample,"
"quality control check sample," or "laboratory-fortified blank," is used to ensure that the laboratory
remains in control during the period that samples are analyzed, and it separates laboratory performance
from method performance in the sample matrix. The test consists of a single aliquot of reference matrix
spiked with the analyte(s) of interest and carried through the entire analytical process with each batch of
samples. Typically, the concentration of the target analyte(s) in the same as the concentration used in the
IPR test. Specifications are developed for the permissible range of recovery for each analyte.
3.3.6 Analysis of Blanks
Blanks are analyzed either periodically or with each sample batch to demonstrate that no
contamination is present that would affect the analysis of standards and samples for the analytes of
interest.. The period or batch size is defined in each method. Typical periods and batch sizes are one per
shift or one for.every 10 or 20 samples, but more or fewer may be required, depending upon the likelihood
of contamination. , .
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Streamlining Guide
For most methods, QC acceptance criteria for blanks are given in each method and are specified as
the concentration or amount of the analyte allowed in each type of blank. The source of contamination in
a blank must be identified and eliminated before the analysis of standards and samples may begin.
Samples analyzed with an associated contaminated blank must be reanalyzed. Methods for which blank
contamination cannot be eliminated should specify blank-subtraction procedures.
3.3.7 Surrogate or Labeled Compound Recovery
The surrogate or labeled compound recovery is used to assess the performance of the method on
each sample. For this test, surrogates or stable, isotopically labeled analogs of the analytes of interest are
spiked into the sample and the recovery is calculated. Specifications are developed for the permissible
range of recovery for each surrogate and/or labeled compound from each sample.
3.3.8 Matrix Spike and Matrix Spike Duplicate
The matrix spike and matrix spike duplicate (MS/MSD) test is used in non-isotope dilution
methods to assess method performance in the sample matrix. In most cases, analytes of interest are added
to a field sample aliquot that is then thoroughly homogenized and split into two spiked replicate aliquots.1
One of these replicates is identified as the matrix spike sample and the other is identified as the matrix
spike duplicate sample. The recoveries of the analytes, relative to the spike, are determined in each
sample. The precision of the determinations also is assessed by measuring the relative percent difference
(RPD) between the analyte concentrations measured in the MS and MSD. The MS and MSD samples
should each be spiked at a level that results in the concentration of the target analyte(s) being
• At the regulatory compliance limit or
• One to five times the background concentration of unspiked field sample, or
• At the level specified in the method, whichever is greater.
If the background concentration in the field sample is so high that the spike will cause the calibration
range of the analytical system to be exceeded, the sample is spiked after the field sample is diluted by the
minimal amount necessary for this exceedance not to occur. This dilution of the sample to stay within the
calibration range of the analytical system for the target analyte is necessary to verify that the sample matrix
has not prevented reliable determination of the analyte. Specifications are developed for the permissible
range of recovery and RPD for each analyte.
3.3.9 Demonstration of Method Detection Limit
Nearly all of the 40 CFR part 136, Appendix A methods contain method detection limits (MDLs),
although few of the methods explicitly require laboratories to demonstrate their ability to achieve these
MDLs. Under the streamlining initiative, EPA will develop MDLs for each analyte in each existing
reference method, and organizations developing new reference methods will be required to develop
analyte-specific MDLs applicable to those methods. The MDLs published for each reference method will
be used as an indicator of method performance. Each laboratory that intends to practice a method will be
required to demonstrate achievement of an MDL that meets the criteria specified in the reference method.
1 For analytes, such as oil and grease, that adhere to container walls and cannot be adequately
homogenized, it is not possible to divide a spiked aliquot into two replicate aliquots. In these cases, two •
field samples are collected and each field sample is spiked with identical concentrations of the analytes of
interest to produce an MS and MSD sample. . .
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Quality Control Requirements
The MDL must be determined according to the procedures specified at 40 CFR part 136, Appendix B.
The Appendix B MDL calculation and analytical procedure is described in Section 3.4.1.1.
3.3.10
Reference Sample Analysis
The most common reference sample is a Standard Reference Material (SRM) from the National
Institute of Standards and Technology (NIST). The reference sample and the period for its use are
specified in each method. EPA is considering setting acceptance criteria for standard reference materials
to be within some percentage of the stated value based on the variability of measurement for that analyte.
One possible indicator of that variability is the relative standard deviation calculation for the initial
precision and recovery samples. Corrective action to be taken when the acceptance criteria are not met
should involve identifying the samples affected, determining the amount of the effect, and if the effect is
significant, determining the impact of the effect on the environmental samples analyzed.
3.4 Development of Quality Control Acceptance Criteria
The procedures for developing QC acceptance criteria at Tier 1, Tier 2, and Tier 3 methods are
described in Sections 3.4.1, 3.4.2, and 3.4.3, respectively. Under the streamlining initiative,
interlaboratory study data are required to develop QC acceptance criteria for Tier 2 and Tier 3 methods.
Although these studies are not necessary for Tier 1 methods, interlaboratory study data may be available.
If interlaboratory data are available for a Tier 1 method, these data should be used to develop QC
acceptance criteria for Tier 1 methods by following the Tier 2 or Tier 3 procedures described in Section
3.4.2 or 3.4.3, respectively. Where possible, interlaboratory study data used for development of QC
acceptance criteria should be derived from study designs that follow the basic principles outlined in
Guidelines for Collaborative Study Procedures to Validate Characteristics of a Method ofAnalysis,-
JAOAC 72 No. 4, 1989, Use of Statistics to Develop and Evaluate Analytical Methods (published by
AOAC-International), ASTM Standard D-2777 (published by ASTM), or other well-established and
documented principles.
The statistical procedures described in Sections 3.4.1 and 3.4.2 for Tier 1 and Tier 2 are based on
the use of interlaboratory multipliers. These multipliers were derived from a comparison of
intralaboratory versus interlaboratory variability in the development of EPA Method 1625. The variation
in the interlaboratory multiplier used is directly related to the number of laboratories used at each of the
two tiers. The general relationship follows the concept'that an increase in the number of laboratories used
results in a decrease in the interlaboratory multiplier.
If the method being developed is applicable to a large number of compounds, the organization
responsible for developing QC acceptance criteria for the method may wish to consider the use of
statistical allowances for simultaneous compound testing. Procedures associated with simultaneous
compound, testing and the develoment of applicable QC acceptance criteria can be found at 49 FR 43242
and in the Method 1625 validation study report.3 .
2 Appendix I, "Estimation of Variance Components", of the Interlaboratory Validation of U.S. ,
Environmental Protection Agency Method 1625A, available from the EPA Sample Control Center
operated by DynCorp, Alexandria, VA 22314, 703/519-1140.
3Interlaboratory Validation of U.S. Environmental Protection Agency Method 1625A. See above.
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Streamlining Guide
3,4.1 Quality Control Acceptance Criteria Development for New Methods at Tier 1
Method validation at Tier 1 consists of (1) using the new method to perform an MDL study in
accordance with the MDL procedure described at 40 CFR part 136, Appendix B, (2) using the results of
this MDL study to establish an ML, and (3) running, in a single laboratory, a test of four spiked reference
matrix samples and four spiked samples of the sample matrix (or matrices) to which the method is to be
applied. The spike level of these reference matrix and real-world matrix IPR samples must be in the range
of one to five times the ML, or at the regulatory compliance level, whichever is higher.
3.4.1.1 Method detection limit and minimum level
An MDL must be determined for each target analyte using the procedure detailed at 40 CFR part
136, Appendix B. This procedure involves spiking seven replicate aliquots of reference matrix or the
sample matrix with the analytes of interest at a concentration within one to five times the estimated MDL.
The seven aliquots are then carried through the entire analytical process, and the standard deviation of the
seven replicate determinations is calculated. The standard deviation is multiplied by 3.14 (the Student's t
value at 6 degrees of freedom) to form the MDL. If the spike level is greater than five times the
determined MDL, the spike level must be reduced and the test repeated until the MDL is within a factor of
five of the spike level. The precautions concerning blanks and the effect of the matrix, and the detailed
steps in 40 CFR part 136, Appendix B must be observed to arrive at a reliable MDL. In addition, if the
analytical system or instrument fails to produce a positive response for any of the seven replicates (i.e.,
produces a zero or negative result), the MDL procedure must be repeated at a higher spike level.
The ML is established by multiplying the MDL by 3.18 and rounding to the number nearest to
(1,2, or 5) x 10", where n is positive or negative integer. The purpose of rounding is to allow instrument
calibration at a concentration equivalent to the ML without the use of unwieldy numbers. The use of 3.18
results in an overall standard deviation multiplier of 10, which is consistent with the American Chemical
Society's (ACS) limit of quantitation (LOQ) (P. S. Porter et al., Environ. Sci. Technol, 22, 1988),
Once established, the ML is used as the lowest calibration point. The instrument or analytical
system is then calibrated at the ML and a minimum of two additional points to assess calibration linearity
(Section 3.4.1.2) and to determine the number of calibration points required and how these points are
spaced (Section 3.3.1).
3.4.1.2 Calibration linearity
Establish the RSD of the response factors (RFs), calibration factors (CFs), or relative responses
(RRs) based on the precision of the determinative technique, as described in Section 3.3.1, and as
determined in Section 3.4.1.1. If the RSD is < 2%, a one- or two-point calibration is employed (see
Section 3.1.1) and it is unnecessary to establish a limit for calibration linearity.
If three or more calibration points are required, the RSD for the RFs, CFs, or RRs is determined as
follows:
(1) Determine the average response factor (&F ), calibration factor (CF), or relative response (RF )
for each analyte from the initial calibration:
RF = (RFj + RF2 + ... + RFn)/n
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Quality Control Requirements
where n is the number of calibration points. ,
(2) Determine the RSD using RF , CF ,or RF and the standard deviation (s) of the RF ,CF, or RR
for each analyte from the initial calibration. The RSD is determined by:
RSD=100s/(RF)
(3) Develop a maximum RSD as follows:
where k is the. square root of the 95th percentile of an F distribution with degrees of freedom
corresponding to the number of points in the initial calibration minus 1 in both numerator and
denominator. For a three point calibration, the value of k is 4.4, and for a five-point calibration,
the value of k is 2.5.
t " , . " , •
Note:. In the above equations, the RF and RF terms should be replaced by CF and CF or RR and RR
terms where appropriate.
3.4.1 .3 Calibration verification . '''•-.
Using the average response factor (RF ), calibration factor (cF), or relative response (RR) from.
the initial calibration, calculate the upper and lower QC acceptance criteria for the calibration verification
as follows: -
(1) Calculate a multiplier, k, as the 97.5th percentile of a Student's / distribution with n - 1 degrees of
freedom times the square root of (1 + 1/n), where there are n points in the calibration. For a three
point calibration, the n - 1 Student's t value is 4.3, and for a five point calibration, the Student's /
value is 2.8, resulting in values for k of 5.0 for a three point and 3.0 for a five point calibration.
(2) Calculate the upper and lower QC acceptance criteria for the, response or calibration factors for
each analyte by developing a window around the average response factor found in the initial
calibration by:
Lower limit =RF - ks
Upper limit = RF + ks
where k is the multiplier determined in Step 1 and s is the standard deviation determined in
3. 4. 1.2, Step 2.
Note: In the above equations, theRF terms should be replaced by CF or Rll terms where appropriate.
3.4.1.4 Initial and ongoing precision and recovery
For Tier 1 methods, an IPR test must be performed in both a reference matrix (usually, reagent
water) and the sample matrix of interest. Results of the reference matrix IPR tests are used to generate QC
acceptance criteria for IPR and OPR tests as described in this subsection. Results of the sample matrix
IPR test are used to develop QC acceptance criteria for the MS/MSD tests (see Section 3.4.1 .5 below).
The reference matrix IPR test is performed by analyzing four aliquots of the reference matrix spiked with
the target analyte(s) at the concentration determined in Section 3.3.4.
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Streamlining Guide
Calculate the QC acceptance criteria for the IPR and OPR tests using results of the test of the
reference matrix per the following steps:
(1) Calculate the average percent recovery (X), the standard deviation of recovery (s), and the relative
standard deviation (RSD=1 OOs/X) of the four IPR results.
(2) IPR QC acceptance criterion for precision - To approximate a 95% confidence interval for
precision, the RSD is multiplied by the square root of the 95th percentile of an F distribution with
3 degrees of freedom in the numerator and denominator. The resulting multiplier on the RSD will
then be 3.0. The QC acceptance criterion for precision in the IPR test (RSQ^) is calculated as
follows:
RSDmax =3.0RSD.
(3) IPR QC acceptance criteria for recovery - Calculate the QC acceptance criteria for recovery in the
IPR test by constructing a ± 5.3s window around the average percent recovery (2£. This factor
comes from the 97.5th t percentile for 3 degrees of freedom, multiplied by
\Jl. 15(1+1) +(1/4 +1/4) to account for interlaboratory variability and the estimation of the mean:
Lower limit (%) =1L- 5.3s
Upper limit (%) ='X-t: 5.3s
(Based on EPA's interlaboratory validation study of Method 1625, the additional variance due to
interlaboratory variability is estimated as 1.15i.)
(4) OPR QC acceptance criteria for recovery - A similar miltiplier is used as for the IPR test but the
second factor is ^1-15(1+1) + (1 + 1/4), so the multiplier is 6.0. Calculate the QC acceptance
criteria forrecovery in the OPR test by constructing a ± 6.0s window around the average percent
recovery X:
Lower limit (%) =]X- 6.0s
Upper limit (%) =X+6.0s
Note: For highly variable methods, it is possible that the lower limit for recovery for both the IPR
and OPR analyses will be a negative number. In these instances, the data should either be log-
transformed and the recovery window recalculated, or the lower limit established as "detected," as
was done with some of the 40 CFR part 136, Appendix A methods (49 FR 43234).
3.4. J.5 Matrix spike and matrix spike duplicate
As noted above, an IPR test must be performed in both an appropriate reference matrix and the
sample matrix of interest for Tier 1 new methods. The results of the sample matrix IPR test are used to
develop acceptance criteria MS/MSD analyses. Sample matrix IPR tests are performed by: (1)
determining the background concentration of the sample matrix, (2) spiking four replicate aliquots of the
sample matrix at a concentration equal to the regulatory compliance limit, one to five times the ML
determined in Section 3.4.1.1, or one to five times the background concentration of the sample, whichever
is greater, and (3) analyzing each of these spiked replicate samples.
Calculate the QC acceptance criteria for the recovery of MS and MSD samples as follows:
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Qualify Control Requirements
(1) Calculate the average percent recovery Q§ and the standard deviation of recovery (s) of each
.target analyte in the sample matrix IPR aliquots.
(2) Calculate the QC acceptance criteria for recovery in the MS and MSD tests by constructing a ±
6,0s window around the average percent recovery (X) (derived the same as for the OPR test
above):
Lower limit (%) =X- 6.0s •
Upper limit (%) =X+6.0s
Note: For highly variable methods, it is possible that the lower limit for recovery for both IPR
and OPR analysis will be a negative number. In these instances, the data should either be log-
transformed and the recovery window recalculated, or the lower limit established as "detected," as
was done with some of the 40 CFR part 136, Appendix A methods (49 FR 43234).
Calculate the QC acceptance criteria for the relative percent difference between the MS and MSD
as follows:
(1) Calculate the relative standard deviation (RSD) of the recoveries of each target analyte in the
sample matrix IPR aliquots as follows:
(2)
Calculate the relative percent difference (RPD) criterion as follows:
, RPDmax = 4.5RSD
This multiplier is calculated asv/2 times the square root of the 95th percentile of an F distribution
with 1 and 3 degrees of freedom.
3.4.1.6 Absolute and relative retention time
Determine the average retention time,RT (and/or average relative retention time,RRT), and the
standard deviation (s) for each analyte and standard. Determine the upper and lower retention time (or
relative retention time) limits using the following: . .
Lower limit =RT^ts
Upper limit =RT +ts
The relative retention time upper and lower limits are determined by replacing.T with RRT in
the equations above. The t value is the 97.5th percentile of a t distribution with n - 1 degrees of freedom,
where n is the number of retention time or relative retention time values used.
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Streamlining Guide
3.4.1.7 Blanks
Establish the QC acceptance criteria for blanks. The usual requirement is that the concentration of
an analyte in a blank must be below the ML or below one-third (1/3) the regulatory compliance lev.el,
whichever is higher. In instances where the level of the blank is close to the regulatory compliance level
or the level at which measurements are to be made, it may be necessary to require multiple blank
measurements and establish the QC acceptance criteria based on the average of the blank measurements
plus two standard deviations of the blank measurements.
3.4.1.8 Reference sample
Establish the QC acceptance criteria for the reference sample based on the error provided with the
reference sample.
3.4.2 Quality Control Acceptance Criteria Development for New Methods at Tier 2
Method validation at Tier 2 consists of running tests on a single matrix type collected from three
different facilities in the same industrial subcategory, with the sample being analyzed in three separate
laboratories (see 40 CFR parts 405 - 503 for industrial categories and subcategories). If the matrix type
being validated is drinking water, then tests shall be run on a drinking water matrix collected from three
different sources or on three drinking water samples that each have different characteristics (see Section
4.4.2). . '
Each of the three laboratories will need to run a full suite of tests, beginning with an MDL study
to determine the appropriate ML, followed by calibration, IPR, OPR, and blank analyses, along with a pair
of MS/MSD analyses for each sample matrix. Results from each laboratory will be submitted to the
organization responsible for developing the method. That organization will use the laboratory results to
develop QC acceptance criteria as described in the following subsections.
3.4.2.1 Method detection limit and minimum level
Each laboratory participating in the MDL study must perform an MDL test as described in
Sections 3.4.1.1 and 6.3.2.9. The organization responsible for developing the new method must establish
an MDL for the method, using a pooled MDL from the three laboratories. The precautions concerning
blanks and the effect of the matrix, and the detailed steps in 40 CFR part 136, Appendix B must be
observed to arrive at a reliable MDL.
A pooled MDL is calculated from m individual laboratory MDLs by comparing the square root of
the mean of the squares of the individual MDLs and multiplying the result by a ratio of t-values to adjust
for the increased degrees of freedom.
MDL
pooled
'S
MDL- ... , MDL- .,. „
' (Labl)s2 + ^ f . (Lab2) .2 .
(0.99^,)
(0.99,d2)
d.+d,+...dm
12 m
U(0.99,d,+d2+...dm)
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Quality Control Requirements
where m = the number of laboratories, and 4= the number of replicates used by lab i to derive the MDL.
In the case of 3 laboratories with 7 replicates per laboratory, the equation simplifies to:
MDL
pooled
MDL^j+K
lDL^a
3
b2)+MDL(Lb3) 2.55
3.14
The organization responsible for developing the method also must use this pooled MDL to
develop an ML. Procedures for determining the ML are given in Section 3.4.1.1. Once established, the
ML is used as the lowest calibration point. The instrument or analytical system is then calibrated at the
ML and a minimum of two additional points to assess calibration linearity (Section 3.4.1.2) and to
determine the future number of calibration points required and how these points are spaced (Section
3.3.1). . ,
3.4.2.2 Calibration linearity
.. Establish the-RSD of the response factors (RFs), calibration factors (CFs),or relative responses
(RR s) based on the precision of the determinative technique, as described in Section 3.3.1 and as
determined in Section 3.4.2.1. If the RSD is < 2%, a one- or two-point calibration is employed (see
Section 3.1.1) and it is unnecessary to establish a limit for calibration linearity.
If three or more calibration points are required, the upper limit on the RSD of the RFs or CFs is
determined as follows:
(1) Calculate the overall average RF (RF ), overall average CF (CF ), or overall average RR (RR ) for
each analyte using the individual results from all three laboratories. For example, for a 3-point
calibration using RFs:
(RF
K,ab
2) +RF3(Iab 2)
(2) Calculate the pooled within-laboratory standard deviation ($) of the-RF, CF, or RR for each
analyte from all three laboratories. The pooled within-laboratory standard deviation is calculated
as the square root of the mean of the squares of the sample standard deviations of the calibration
results at each individual laboratory. , ,
Sw A
222
S(lab 1) * S(lab 2) + s(lab 3)
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Streamlining Guide
(3) Calculate the relative standard deviation of the RF, CF, or RR for each analyte as:
RSD =•-
100sT
RF
(4) Calculate the maximum RSD of the RF, CF, or RR for each analyte as follows:
RSDmax = kRSD
where k is the square root of the 95th percentile of an F distribution with n - 1 degrees of freedom
in the numerator and m(n - 1) degrees of freedom in the denominator, where m is the number of
laboratories and n is the number of calibration points. For three laboratories using a three point
calibration, (m=3, n = 3), the value of k is 2.3, and for three laboratories using a five point
calibration (m=3, n = 5), the value of k is 1.8.
ftjfote: In the above equations, the RF and RF terms should be replaced by CF and CF or RR and RR
terms where appropriate.
3.4.2.3 Calibration verification
Using the average response factor, calibration factor, or relative response from the initial
calibration, calculate the upper and lower QC acceptance criteria for calibration verification as follows:
(1) Determine "k" by multiplying the 97.5th percentile of a Student's ( distribution with m(n-l)
degrees of freedom times the square root of (1 + 1/mn), where there are n points in the calibration
and m laboratories:
k=s
n+ l i
mn
(2)
For a three point calibration with three laboratories, the m(n - 1) Student's / value is 2.4, and for a
five point calibration, the Student's /value is 2.2, resulting in combined multipliers of 2.5 for a
three point calibration, and 2.3 for a five point calibration.
Multiply k by the pooled standard deviation, %, ,found in Section 3.4.2.2.
Calculate the upper and lower QC acceptance criteria for the response factors, calibration factors,
or relative responses for each analyte by developing a window around the average response factor,
calibration factor, or relative response by:
Lower limit = RF-ksw
Upper limit = RF + ks
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Quality Control Requirements
Note: In the above equations, the RF terms should be replaced by CF or RR terms where appropriate.
3.4.2.4 Initial and ongoing precision and recovery
For the IPR and OPR tests, QC acceptance criteria are calculated using the average percent
recovery and the standard deviation of recovery from the IPR tests on four aliquots of the reference matrix
and the OPR test of one aliquot of the reference matrix (for a total of five samples) in the three
laboratories, as follows:
(1) ' Calculate the average percent recovery (X) for each analyte based.on all data points from all
laboratories, the between-laboratory standard deviation_(§) of the mean£esults for each of the three
laboratories (standard deviation of the three lab meansX(lab 1); X(Iab 2), X(Iab 3)), and the pooled
' within-laboratory standard deviation (sj of the 5 samples calculated as in 3.4.2.2. Note: the
organization responsible for developing the method must ensure that all laboratories are spiking
IPR and OPR samples at the same concentration.
(2) IPR QC acceptance criterion for precision - To calculate a 95% confidence interval for precision,
the RSD (computed as s^ divided by X ) is multiplied by the square root of a 95th percentile F
value with 3 degrees of freedom in the numerator and 4m degrees of freedom in the denominator,
where m -the number of laboratories. The resulting multiplier on the RSD for three laboratories
will then be 1.9. The QC acceptance criterion for precision in the IPR test (RSQ^ is calculated as
follows: •
(3) IPR QC acceptance criteria for recovery -Calculate the combined standard deviation for
interlaboratory variability and estimation of the mean (§) as:
s =
\
m
4 n
where m = the number of laboratories, and n = the number of data points per laboratory. For 3
laboratories and 5 data points per laboratory,
Sc=>
4 2
— s2
20. w
(4) Calculate the QC acceptance criteria for recovery in the IPR test by constructing a ± 3.2 ^window
around the average percent recovery (X, where 3.2 is the 9715th percentile Student's t value for 3
degrees of freedom (an estimated degrees of freedom based on the variance ratios observed with
EPA Method 1625):
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Streamlining Guide
Lower limit(%) =X-3.2sc
Upper limit(%)=X+3.2s
If more than 3 laboratories are used, the degrees of freedom for t will increase, but a complete
calculation is beyond the scope of this document. An approximation of degrees of freedom equal
to the number of laboratories will serve for most situations.
(5) OPR QC acceptance criteria for recovery - Calculate the combined standard deviation for
interlaboratory variability and estimation of the mean (s) as:
—
m
n
where m = the number of laboratories, and n = the number of data points per laboratory. For 3
laboratories and 5 data points per laboratory,
(6) Calculate the QC acceptance criteria for recovery in the OPR test by constructing a ± 2.6 sc
window around the average percent recovery (X, where 2.6 is the 97.5th percentile Student's t
value for 5 degrees of freedom (an estimated degrees of freedom based on the variance ratios
observed with EPA Method 1625):
Lower limit(%) =X-2.6sc
Upper limit(%)=X+2.6sc
If more than 3 laboratories are used, the degrees of freedom for t will increase, but a complete
calculation is beyond the scope of this document. An approximation of degrees of freedom equal
to twice the number of laboratories will serve for most situations.
3.4.2.5 Matrix spike and matrix spike duplicate
Results of the MS/MSD analyses performed in the validation study are used to develop the
MS/MSD QC acceptance criteria for Tier 2. Each laboratory will measure MS and MSD in each of the
three samples. Calculate the MS and MSD performance criteria as follows.
(1) Calculate the mean and sample standard deviation of the recoveries of each MS/MSD pair, and
then compute the overall mean recovery (X ), the between-laboratory/matrix standard deviation of
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Quality Control Requirements
(2)
the 9 pairwise means (%), and the pooled within-laboratory/matrix standard deviation ($, as
calculated in 3.4.2.2) for each target analyte.
In order to allow for interlaboratory variability, calculate the combined standard deviation 0 for
interlaboratory variability and estimation of the mean. For 3 laboratories and 3 matrices,
-s2
3SB
-s2
6 w
Derivation of the formula for other than 3 laboratories and 3 matrices is beyond the scope of this
text. .'••'• ' „ -
(3) MS/MSD QC acceptance criteria for recovery - Calculate the QC acceptance criteria for recovery
in the MS/MSD test by constructing a ± 2.2% window around the average percent recovery (X )
using the combined standard deviation. This factor comes from a / value for an estimated 7
degrees of freedom (based on this experimental design and variance ratios observed in Method
1625): • ,
Eower
=X -2.2s
Upper limit(%)=X+2.2s
Note: For highly variable methods, it is possible that the lower limit for recovery will be a
negative number. In these instances, the data should either be log-transformed and the recovery
window recalculated, or the lower limit established as "detected," as was done with some of the 40
CFR part 136, Appendix A methods. , .
(4) MS/MSD QC acceptance criteria for relative percent difference (RPD) - To evaluate a 95%
confidence interval for precision, the RSD (competed using the pooled within laboratory standard
deviation &„ of the MS/MSD samples divided by X ) is multiplied by the square root of the 95th
percentile F value with 1 degrees of freedom in the numerator and 3m degrees of freedom in the
denominator multiplied by
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Streamlining Guide
developing the method specify to the participating laboratories the chromatographic conditions and
columns to be used. Any future laboratories operating under different conditions will need to develop new
acceptance criteria for RT and RRT precision. ,
Determine the average retention timeJRT, (or average relative retention timeJRRT ), and the
corresponding standard deviation (s) for each analyte and standard. Determine the upper and lower
retention time (or relative retention time) limits using the following:
Lower limit =RT -ts
'&\
n
Upper limit =RT+ts
avgA
n
where the t value is the 97.5th percentile of at distribution with n - 1 degrees of freedom and where n is
the number of retention time or relative retention time data values to be used:
3.4.2.7 Blanks
Establish the QC acceptance criteria for blanks. The usual requirement is that the concentration of
an analyte in a blank must be below the ML or below one-third (1/3) the regulatory compliance level,
whichever is higher. In instances where the level of the blank is close to the regulatory compliance level
or the level at which measurements are to be made, it may be necessary to require multiple blank
measurements and establish the QC acceptance criteria based on the average of the blank measurements
plus two standard deviations of the blank measurements.
3.4.2.8 Reference sample
Establish the QC acceptance criteria for the reference sample based on the error provided with the
reference sample.
3.4.3 Qualify Control Acceptance Criteria Development for New Methods at Tier 3
In Tier 3, a single sample collected from each of a minimum of nine industrial categories is
analyzed in nine separate laboratories (one sample analyzed by each laboratory). Details for the
characteristics and definitions of these samples are given in Chapter 4 of this guide. Because data gathered
from nine laboratories lends itself to the statistical procedures used for interlaboratory method validation
studies, the procedures suggested by ASTM and AOAC-International are particularly applicable and those
procedures are preferred for development of QC acceptance criteria. However, QC acceptance criteria
may also be developed for the Tier 3 methods in ways that are analogous to development of these criteria
at Tiers 1 and 2, with minor modifications described below.
3.4.3.1
Method detection limits and minimum levels
Each laboratory participating in the validation must perform an MDL study as described in Section
3.4.1.1. The organization responsible for developing the new method mustestablish an MDL for the
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Quality Control Requirements
method, using a pooled MDL from the nine laboratories. A pooled MDL is calculated from m individual
laboratory MDLs by computing the square root of the mean of the squares of the individual MDLs and
multiplying the result by a ratio of f-values to adjust for the increased degrees of freedom.
MDL
pooled
d (MDL
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Streamlining Guide
RSD = 100-
RF
(3) Calculate the maximum RSD for each analyte by the following:
RSDmax = kRSD,
where k is the square root of the 95th percentile of an F distribution with n - 1 degrees of freedom
in the numerator and m(n - 1) degrees of freedom in the denominator, where m is the number of
laboratories and n is the number of calibration points. For nine laboratories using a three-point '
calibration (n = 3), the value of k is 1.9, and for nine laboratories using a five-point calibration (n ::
5), the value of k is 1.6.
Hote; In the above equations, the RFand RF terms should be replaced by CF and CF or RR and RR
terms where appropriate.
3.4.3.3 Calibration verification
Using the average response factor or calibration factor from the initial calibration, calculate the
upper and lower QC acceptance criteria for the calibration verification as follows:
(1) Determine "k" by multiplying the 97.5th percentile of a Student's t distribution with m(n-l)
degrees of freedom times the square root of (1 + 1/mn), where there are n points in the calibration
and m laboratories:
:=t
mn
For a three-point calibration with nine laboratories, the m(n - 1) Student's t value is 2.1 and for a
five-point calibration, the Student's t value is 2.0, resulting in combined multipliers of 2.1 for both
a three-point calibration and a five-point calibration.
Multiply k by the pooled standard deviation s^ found in Section 3.4.3.2.
(2) Calculate the upper and lower QC acceptance criteria for the response factors, calibration factors,
or relative responses for each analyte by developing a window around the average response factor,
calibration factor, or relative response by:
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Quality Control Requirements
Lower limit-RF-ksv
Upper limit =RF fks
Note: In the above equations, the RF terms should be replaced by CF or RR terms where appropriate.
3. 4. 3. 4 Initial and ongoing precision and reco very
For the IPR and OPR tests, QC acceptance criteria are calculated using the average percent
recovery and the standard deviation of recovery from the IPR tests of four aliquots of the reference matrix
and the OPR test of one aliquot of the reference matrix (for a total of five samples) in nine laboratories.
The QC acceptance criteria are developed using the following steps:
(1)
(2)
Calculate the average percent recovery (50 for each ahalyte based on all data points from all
laboratories, the between-laboratory standard deviation (§) of the mean results for each of the m
laboratories (the standard deviation of them laboratory averagesXlabl, Xlab2, ..... XIabm), and the
pooled within-laboratory standard deviation (%) of the five samples calculated as in 3.4.3.2. .Note:
the organization responsible for developing the method must ensure that all laboratories are spiking
IPR and OPR samples at the same concentration.
IPR QC acceptance criteria for precision - To calculate a 95% confidence interval for precision, the
RSD (computed as s^, divided byX ) is multiplied by the square root of the 95th percentile F value
with 3 degrees of freedom in the numerator and 4m degrees of freedom in the denominator. The
resulting multiplier for nine laboratories will be 1.7. The QC acceptance criterion for precision in
the IPR test (RSDmax) for 9 laboratories is calculated as follows:
(3) IPR QC acceptance criteria for recovery -Calculate the combined standard deviation for
interlaboratory variability and estimation of the mean (§) as:
1.2.1 1.2
h—)sb+(---)sw ,.
m 4 n
where m = the number of laboratories, and n = the number of data points per laboratory. For 9
laboratories and 5 data points per laboratory, .
Sc='
10 2
20
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Streamlining Guide
(4) Calculate the QC acceptance criteria for recovery in the IPR test by constructing a ± 2.3 ^window
around the average percent recovery (X, where 2.3 is the 97.5th percentile Student's t value for 10
degrees of freedom (an estimated degrees of freedom based on the variance ratios observed with
EPA Method 1625):
Lower limit(%) =X -2.3sc
Upper limit(%)=X+2.3sc
If more than 9 laboratories are used, the degrees of freedom for t will increase, but a complete
calculation is beyond the scope of this document. An approximation of degrees of freedom equal
to the number of laboratories will serve for most situations.
(5) OPR QC acceptance criteria for recovery - Calculate the combined standard deviation for
interlaboratory variability and estimation of the mean (s) as:
—
m
n
where m = the number of laboratories, and n = the number of data points per laboratory. For 9
laboratories and 5 data points per laboratory,
10 2
9
sb +Ts
(6) Calculate the QC acceptance criteria for recovery in the OPR test by constructing a ± 2.1 sc
window around the average percent recovery (X, where 2.1 is the 97.5th percentile Student's t
value for 19 degrees of freedom (an estimated degrees of freedom based on the variance ratios
observed with EPA Method 1625):
Lower limit(%)=X-2.1 sc
Upper limit(%)=X+2.1sc
If more than 9 laboratories are used, the degrees of freedom for t will increase, but a complete
calculation is beyond the scope of this document. An approximation of degrees of freedom equal
to twice the number of laboratories will serve for most situations.
3.4.3.5 Matrix spike and matrix spike duplicate
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Quality Control Requirements
Results of the MS/MSD analyses performed in the Tier 3 validation study are used to develop the
MS/MSD QC acceptance criteria for Tier 3. Calculate the MS and MSD performance criteria as follows.
(!)• Calculate the percent recovery (X) and the between-laboratory standard deviation (sj of the mean
results for each of the nine laboratories and also the pooled within-laboratory standard deviation (sw
as calculated as in 3.4.3.2) for each target analyte.using the MS and MSD analyses.
(2) In order to allow for interlaboratory variability, calculate the combined standard deviation ($ for
interlaboratory variability and estimation of the mean as:
m
where m = the number of laboratories. For nine labs.
10 2. 1 2
(3) MS/MSD QC acceptance criteria for recovery - Calculate the QC acceptance criteria for recovery
in the MS/MSD test by constructing a ± 2.2 § window around the average percent recovery X
using the combined standard deviation. This factor comes from a t value for an estimated 11 •
degrees of freedom (based on this experimental design and variance ratios observed in Method
1625):
Lower limit(%) =X ~2.2sc
Upper limit(%)-X+2.2s
Note: For highly variable methods, it is possible that the lower limit for recovery will be a negative,
number. In these instances, the data should either be log-transformed and the recovery window
recalculated, or the lower limit established as "detected," as was done with some of the 40 CFR
part 136, Appendix A methods.
(4) MS/MSD QC acceptance criterion for relative percent difference (RPD) - To calculate a 95%
confidence interval for precision, the RSD (computed using the pooled within-laboratory standard
deviation, s^,, of the MS/MSD samples divided by X ) is multiplied by the square root of the 95%
percentile F value with 1 degree of freedom in the numerator and m degrees of freedom in the
denominator multiplied by \[2. The resulting multiplier on the RSD for nine laboratories will be
3.2. The QC acceptance criterion for precision in the MS/MSD test (RPQax) is calculated as
"follows:
RPDmax = 3.2RSD. *
3.4.3.6 Absolute and relative retention time
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Streamlining Guide
Establishing QC acceptance criteria for RT and RRT precision is problematic when multiple
laboratories are involved because laboratories have a tendency to establish the chromatographic conditions
that suit their needs. Calculating average RTs and RRTs based on different operating conditions will
result in the establishment of erroneously wide windows. It is advised, therefore, that the organization
developing the method specify to the participating laboratories the chromatagraphic conditions and
columns to be used. Any future laboratories operating under different conditions will need to develop new
acceptance criteria for RT and RRT precision.
(1)
(2)
Using replicate RT and/or RRT data, calculate the upper and lower QC acceptance criteria for each
analyte using the procedures in the calibration verification test in Section 3.4.1.3.
Determine the average retention time£T (or average relative retention time,RRT )., and the
corresponding standard deviation (s) for each analyte and standard. Determine the upper and lower
retention time (or relative retention time) limits using the following:
Lower limit =RT-ts.
Upper limit =RT +ts
n
n
where the t value is the 97.5th percentile of a t distribution with n - 1 degrees of freedom, where n
is the number of retention time or relative retention time data values to be used.
3.4.3.7 Blanks .
Establish the QC acceptance criteria for blanks. The usual requirement is that the concentration of
an analyte in a blank must be below the ML or below one-third (1/3) the regulatory compliance level,
whichever is higher. In instances where the level of the blank is close to the regulatory compliance level
or the level at which measurements are to be made, it may be necessary to require multiple blank
measurements and establish the QC acceptance criteria based on the average of the blank measurements
plus two standard deviations of the blank measurements.
3.4.3.8 Reference sample ' • <
Establish the QC acceptance criteria for the reference sample based on the error provided with the
reference sample.
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Chapter 4
Method Validation Requirements
4.1 Introduction
Method validation is the process by which a laboratory or vendor establishes the performance of a
new method or substantiates the performance of a method modification. New and modified methods must
be validated to prove that they accurately measure the concentration of an analyte in an environmental
sample. In keeping with the intent of streamlining and flexibility, EPA proposes to establish validation
requirements that reflect the level of intended use of the method. This is accomplished through a three-
tiered approach, as shown in Table 4-1.
Table 4-1: Application of Method Tiers
Tier Level
Laboratory Use
Applicable to
Tier 1 Single Laboratory One or more matrix types from any industry; or one or more
, ' PWSs
Tier 2
TierS
All Laboratories
All Laboratories
One or more matrix types within one industrial category or
subcategory; or all PWSs
All matrix types from all industrial categories and subcategories
Under Tier 1, single laboratories will be allowed to validate and use modified methods without the
burden of conducting an interlabbratory method validation study. Modified methods intended for multi-
laboratory use in a given industrial category or subcategory (Tier 2) or nationwide use (Tier 3) require
interlaboratory testing. '-,.-.
All new and modified methods must be validated to demonstrate that the method is capable of
yielding reliable data for compliance monitoring purposes under the Clean Water Act or Safe Drinking
Water Act. The same tests are performed to validate new and modified methods; however, the^esults are
used differently. Test results from validation of a new method are used to develop quality control (QC)
acceptance criteria for that method, .whereas test results from validation of a modified method are used to
demonstrate that the modified method produces results equivalent or superior to results produced by the
reference method. :
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Method modifications are considered to be approved by EPA and may be used after successful
validation and documentation at the appropriate tier. For new methods, the validation study must be
submitted to EPA and the new method must be approved by EPA before the method can be used for
compliance monitoring. Requirements for submitting validation documentation and seeking method
approval are provided in Chapter 5.„
Although many compliance monitoring analyses are performed by contract laboratories on behalf
of a regulated entity, the responsibility for maintaining validation documentation for new and modified
methods rests with the regulated entity. Regulated entities, therefore, must inform their contract
laboratories about the requirements for detailed documentation of method modifications that are specified
in this chapter.
The key concepts presented and discussed in this chapter are: method validation, Tiers 1-3,
industrial category, industrial subcategory, matrix type, matrix effect, sample matrix effect validation,
facility, public water system, sample medium, and sample matrix.
4.2 Summary of Validation Requirements
Requirements for validation depend on the tier to which the new or modified method will be
applied. Validation requirements are summarized in Table 4-2. Table 4-2 specifies the numbers of matrix
types and facilities or PWSs that must be tested and the numbers and types of analyses required to validate
a new or modified method at each tier. To clarify the use of the term "matrix type," as compared to the
terms "sample medium" and "sample matrix," a sample medium is the common name for the physical
phase of a sample matrix. Air, water, soil, and sludge are sample media. A matrix type is a sample
medium with common characteristics across a given industrial category or subcategory. For example, C-
stage effluents from chlorine bleach mills, effluent from the continuous casting subcategory of the iron and
steel industrial category, POTW sludge, and in-process streams in the Atlantic and Gulf Coast Hand-
shucked Oyster Processing subcategory are each a matrix type. For the purposes of this initiative, all
drinking waters constitute a single matrix type. A sample matrix is the component or substrate that
contains the analytes of interest. For purposes of sample collection, "sample matrix" is synonymous with
"sample".
As used in Table 4-2, a facility is a plant or group of plants within a single location that is
regulated under a single National Pollutant Discharge Elimination System (NPDES) permit and/or
SDWA. A single facility may have multiple water supplies, discharges, waste streams, or other
environmental media that are subject to compliance monitoring. For example, a single facility within the
Pulp, Paper, and Paperboard industrial category may have a direct discharge, an indirect discharge, and an
in-process waste stream that are all subject to compliance monitoring.
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Method Validation Requirements
Table 4-2. Summary of Validation Requirements for New Methods and,Method
Modifications^
!
Method Application
Number of
Matrix Facilities/
Labs types PWSs
Number of Analyses Required
IPR- IPR-
" reagent sample
water*2' matrix (3) MS/MSD MDL(4)
Tier 1-Single-lab
WW/DW- First matrix type 1 1
or first PWS
WW- Each addt'l matrix 1 1
type (8 max:) from any .
industrial category
DW- Each addt'l PWS ,1 1
(2 max.)
Tier 2-Multi-lab, single
matrix type 3 1
WW/DW- Each matrix type
in a single industrial
category •
Tier 3-Multi-Iab, multiple
matrix types 9(8) 9
WW only- All matrix types,
all industrial categories
1 4 4 2<5> 7
1 0(6) 0(6) 2(5) 0(6)
1 0(6) 0(6) 2(5) 0(6)
3 12 0 6(7) '21
9 36 0 IS*7* 63
(1) Numbers of analyses in this table do not include background analyses or additional QC tests such
as calibration, blanks, etc. Validation requirements are based on the intended application of the
method. Method application would be designated by tier for wastewater (WW) and drinking water
(DW) programs. Three would be the maximum number of public water systems (PWSs) that
would be required to validate a new or modified drinking water method at Tier 1 or 2. Nine would
be the maximum number of matrix types (or facilities) that would be required to validate a new or
modified wastewater method at Tier 1 or 3; at Tier 2 the number would be three matrix types,
(2) IPR reagent water analyses would be used to validate a method modification and to establish QC
acceptance criteria for initial precision and recovery (IPR) and ongoing precision and recovery
(OPR) for a new method. The required number of IPR analyses, except as noted under footnote 7,
would be four times the number of laboratories required to validate a method modification or new
method because each laboratory would perform a 4-replicate IPR test.
(3) IPR sample matrix analyses would be used to establish QC acceptance criteria for matrix
spike/matrix spike duplicate (MS/MSD) recovery and precision for a Tier 1 new method only. .
Would not be required for validation of Tier 2 or 3 new methods because this variability data
would be obtained from MS/MSD tests. Would not be required for validation of a method
modification because MS/MSD data from the reference method would be used.
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Table 4-2. Summary of Validation Requirements for New Methods and Method
Modifications^ (cont'd)
(4) A method detection limit (MDL) test would be performed in each laboratory using the new or
modified method. 40 CFR part 136 Appendix B requires a minimum of seven analyses per
laboratory to determine an MDL. Each lab involved in validation of a wastewater modification
would demonstrate that the modified method would achieve the detection limits specified in the
regulations at 40 CFR parts 136 and 141 and/or in chapter 6 of the Streamlining Guide (EPA
1996a).
(5) MS/MSD" analyses would be required only for a method modification because, for new methods,
the MS/MSD QC acceptance criteria would be established by the 4-replicate sample matrix IPR
test. For modified methods, the MS/MSD test would demonstrate that the reference method
MS/MSD QC acceptance criteria have been met
(6) The MDL, reagent water IPR, and sample matrix IPR tests would not have to be repeated after the
first matrix type, facility, or PWS was validated.
(7) For validation of a new method, the MS/MSD analyses would establish QC acceptance criteria for
MS/MSD recovery and precision. For validation of a method modification, the MS/MSD analyses •
would demonstrate that reference method MS/MSD recovery and precision have been met. The
required number of MS/MSD analyses would be two times the number of facilities, PWSs or
matrix types tested. '
(8) The number of laboratories and samples would vary if a conventional interlaboratory study is used.
The tiered approach to validating new and modified methods, presented in Table 4-2,
accommodates variability in the analytical performance of a method that can be attributed to the type of
sample analyzed. This variability is termed a matrix effect and can be observed in samples taken at
different locations in matrices of the same type (intramatrix) or in samples from different locations and in
different matrix types (intermatrix). Under the streamlining initiative, each successive tier addresses
matrix effects to a greater degree through increasing levels of sample matrix effect validation, broadly
defined as a test of the extent to which differences, if any, in method performance could be attributed to
variability between samples obtained from different industrial matrices, facilities, or PWSs. Matrix effects
need to be tested by the IPR sample matrix and MS/MSD analyses listed in Table 4-2. Intramatrix effects
need to be tested in water samples taken from different PWSs or from different waste streams. Intermatrix
effects need to be validated on a group of samples taken from discharge samples collected from several
different industrial categories. In all cases, the laboratory must try to determine if the measurement result
for the target analyte using a new or modified method differs from the result obtained in a reagent water
matrix or in a previously validated matrix type or PWS sample.
As shown in Table 4-2, a Tier 1 new or modified method is validated in a single laboratory on one
or more matrix types obtained from one or more facilities, or on samples obtained from one or more
PWSs. Validation of additional facilities or PWSs requires analysis of MS/MSD samples for each
additional facility or PWS. However, in response to stakeholder requests that there should be some
maximum number of single-laboratory validations after which further validation would be unnecessary
because sample matrix effects would have been sufficiently addressed, EPA has included a provision for a
maximum number of matrix type, facility, or PWS analyses for Tier 1 methods. For a wastewater method,
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Method Validation Requirements
the maximum number of matrix types or facilities tested under Tier 1 is nine, each from a different
industrial category or subcategory. For a drinking water method, the maximum number of PWS samples
tested under Tier 1 is three, samples, each,from a PWS with different water quality characteristics.
Validation in three PWSs, rather than nine, is required because three is consistent with the validation data
in many EPA drinking water methods and because the variability in drinking water samples (and therefore
the probability of matrix effects) is usually less in drinking water samples than in wastewater samples.
Tier 2 validation is applicable to one or more matrix types within a single industrial category or
subcategory. Because Tier 2 new and modified methods apply to each matrix across all laboratories, EPA
developed Tier 2 validation requirements to incorporate intramatrix variability. Tier 2 requires validation
of the method in drinking water samples obtained from three PWSs, or wastewater samples of one or more
matrix types obtained from three or more facilities within a single industrial category or subcategory.
Because the drinking water program regulates only one matrix type, drinking (potable) water, Tier 2
results in nationwide approval for a drinking water method.
Tier 3 validation is applicable to the wastewater program and applies to all matrix types in all
industrial categories. Consequently, Tier 3 validation requirements include provisions to account for both
intramatrix and intermatrix variability. Tier 3 requires validation of the method in wastewater samples of
up to nine matrix types obtained from nine different facilities. Tier 3 validation applies to the wastewater
program which regulates several industrial categories, each of which may contain more than one matrix
type. Tier 3 does not apply to the drinking water program because the drinking water program regulates
only one matrix type.
For all multi-matrix tiers? it is extremely important to select suitable samples and matrix types for
validation. The matrix types, facilities, or PWSs selected for validation need to have sufficiently different
water quality characteristics so that the matrix effects, if any, can be observed. Proposed criteria for
selecting matrix types, facilities, or PWSs from which to obtain samples for validation are specified in
section 4.4.1.
\ ' ' .
4.3 Description of Tier 1, 2, and 3 Validation Studies
Ideally, a method modification or a new method should be validated through a classical
interlaboratory method validation study of the type used historically by EPA, ASTM, AOAC-
International, and other organizations. EPA recognizes, however, that a formal interlaboratory method
validation may be prohibitively costly to implement, especially for small laboratories and regulated
entities. Therefore, EPA has developed a three-tiered, cost-effective approach to method validation. The
tiered approach to validation encourages laboratories to take advantage of new technologies, overcome
matrix interference problems, lower detection limits, improve the reliability of results, lower the costs of
measurements, and improve overall laboratory productivity without undertaking costly and time-
consuming interlaboratory studies. ,
Tier 1 is expected to be used by commercial laboratories, dischargers, and state and municipal
laboratories repetitively testing samples from the same site(s) on a routine basis. Tier 2 is expected to be
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Streamlining Guide
used by water supply laboratories, dischargers, and state and municipal laboratories repetitively testing
samples from multiple sites within the same industrial category on a routine basis. Tier 3 is expected to
be used by vendors, commercial laboratories, dischargers, and state and municipal laboratories testing a
wide variety of sample matrices from diverse sites. Vendors seeking approval of a new technology would
also be expected to use Tier 3.
4.3,1 Tier 1 Validation Studies
The primary intent of Tier 1 is to allow use of a new or modified method by a single laboratory.
Tier 1 can be applied to a single matrix type or, for drinking water, a single PWS. It also can be applied to
multiple matrix types or multiple PWSs.
Tier 1 - Single matrix type/single PWS
Tier 1-Single matrix type/single PWS validation studies are performed in a single laboratory on a
single matrix type or on a sample matrix from a single PWS. Results of the validation study and the
method modification are applicable in this laboratory to this matrix type or PWS only and cannot be used
by another laboratory or for another matrix type or PWS.
Tier 1 - Multiple matrix types
For wastewater, if a laboratory intends to apply the method to more than one matrix type, the
laboratory must validate the method on each matrix type, to a limit of nine matrix types. Table 4-2'
specifies the specific requirements for the first matrix type and those for each additional matrix type.
Some laboratories may be testing multiple matrix types for the same analytes using the same modified
method. This raises the question of the number of matrix types to which the modification must be applied
to demonstrate that it will likely be successful for all other matrix types. In responding to this question,
EPA believes that the number certainly cannot be greater than the number required for validation of a
method for nationwide use (nine) and has, therefore, established nine different matrix types as the number
after which a test on each subsequent matrix type is not required. The matrices that must be tested for
validation of a method for wastewater are given in Table 4-3.
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Method Validation Requirements
Table 4-3
Wastewater Matrices Required for Multiple-Matrix Validation Studies
1. Effluent from a publicly owned treatment works (POTW)
2. ASTMD5905- 96, Standard Specification for Substitute Wastewater
3. Sewage sludge, if sludge will be in the permit
4. ASTM D 1141 - 90 (Reapproved 1992), Standard Specification for Substitute Ocean Water, if
ocean water will be in the permit
5. Drinking water, if the method will be applied to drinking water samples
6. Untreated and treated wastewaters to a total of nine matrix types
At least one of the above wastewater matrix types must have at least one of the following
characteristics:
• Total suspended solids (TSS) greater than 40 mg/L
• Total dissolved solids (TDS) greater than 100 mg/L
• Oil and grease greater than 20 mg/L
• NaCl greater than 120 mg/L
• CaCO3 greater than 140 mg/L
Tier 1 - Multiple PWSs
For drinking water, if a laboratory intends to apply the method to more than one PWS, the
laboratory must validate the method on each PWS, to a limit of three PWSs. Table 4-2 specifies the
specific validation requirements for the first PWS and those for each additional PWS. EPA proposes to
require validation in three rather than nine PWSs, because three is consistent with the validation data in
many EPA drinking water methods and because the variability in drinking water samples (and therefore
the probability of matrix effects) is usually less in drinking water samples than in wastewater samples.
As with a Tier 1-Single matrix type/PWS validation study, Tier 1 - Multiple PWS validation
studies are performed in a single laboratory and, therefore, cannot be transferred to another laboratory. If
a method is validated by a single laboratory in one or two PWSs, the validation is applicable to those
PWSs only. However, once a laboratory has validated the method in three PWSs and those PWSs possess
different water quality characteristics, as described below, the validation is applicable to all other PWSs.
To test the modified method for potential matrix effects, the three PWS samples must be collected
from PWSs with water quality characteristics that are sufficiently different that sample matrix effects, if
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Streamlining Guide
any, can be observed. In all cases, the laboratory must try to determine if the measurement result for the
target analyte using a new or modified method differ from the result obtained in a reagent water matrix or
in a previously validated matrix type or PWS sample. Selection of suitable PWSs requires a knowledge of
the chemistry of the method. Analysts may review an applicable approved or published method for
indications of matrix effects that are unique to the analyte separation and measurement technologies used
in the new or modified method. Water quality characteristics that can affect analysis of drinking water
samples include,'but are not limited to, pH, total organic carbon content, turbidity, total organic halogen
content, ionic strength, sulfate contamination, metal contamination, and trihalomethane contamination of
the drinking water sample.
4.3.2 Tier 2 Validation Studies
The primary intent of Tier 2 is to allow all regulated entities and laboratories to apply a new or
modified method to a single sample matrix type in a single industry. Since drinking water is considered a
single matrix type and PWSs represent a single industry, Tier 2 facilitates nationwide use of a new or
modified drinking water method.
EPA believes that implementation of Tier 2 will encourage the development and application of
techniques that overcome matrix interference problems, lower detection limits, improve the reliability of
results, lower the costs of measurements, and improve overall laboratory productivity when analyzing
samples from a given industry. For example, the National Council of the American Paper, Industry for Air
and Stream Improvement, Inc. (NCASI) has suggested a large number of improvements to EPA's
proposed and approved methods, with the specific objective of improving method performance in samples
from the Pulp, Paper, and Paperboard industrial category. EPA believes that NCASI's suggestions have
merit and result in improvements in the reference methods. Through Tier 2, EPA is codifying the ability
of NCASI and other industry organizations and associations to improve the approved methods within their
respective industries.
Significant industries within Tier 2 are: PWSs, publicly-owned treatment works (POTWs), and
individual industrial categories and subcategories that are defined in the regulations at 40 CFR parts 405 -
503. At present, there are approximately 42 industrial categories and 650 industrial subcategories defined
in the Part 405 - 503 regulations, eafch of which constitutes an individual industry under the streamlining
initiative.
Tier 2 validation studies are performed in a minimum of three laboratories. Samples of the same
matrix type (e.g., drinking water, final effluent, extraction-stage effluent,) are collected from a minimum
of three separate facilities in the same industrial category or subcategory. A sample from each facility will
be sent to each of the laboratories, for a total of nine sample analyses.
For POTWs, if a new or modified method is validated on final effluent only, that method is
applicable to final effluent only, and the title of the method must reflect that the method is applicable to
final effluent only. If influent to treatment, primary effluent, and sludges will be monitored, the method
must be validated separately on these sample matrix types.
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Method Validation Requirements
In contrast to Tier 1, once a new or modified method has been validated, the validation study
results can be transferred to other laboratories, and the other laboratories may freely use the method, as
long as the method is applied to analysis of samples of matrix types from within the industrial category or
subcategory for which the method has been validated, and as long as the other laboratories meet all of the
method's QC acceptance criteria. If the new or modified method is to be applied to another industrial
category or subcategory, or to other media or matrix types in the same category or subcategory, the
modification must be validated on media/matrix types in each category/subcategory!. '""
4.3.3 Tier 3 Validation Studies
The primary intent of Tier 3 is to allow nationwide use of a new or modified method by all
regulated entities and laboratories. The increased flexibility at Tier 3 should allow vendors to establish
that new devices and reagents produce results that are acceptable for compliance monitoring purposes, and
should allow commercial laboratory chains to apply new technologies or modified techniques throughout
their chain of laboratories to a variety of matrices, matrix types, and media.
Tier 3 validation studies are performed in a minimum of nine laboratories, each with a different
matrix type at minimum, for a total of nine samples. The minimum requirements for sample matrices that
must be used in the validation study are given in Table 4-3. If the method is to be applied to more than
one sample medium (e.g., air; water, soil, sludge), a separate validation must be performed on each
medium. .
When validating a method modification directed at overcoming a matrix interference problem in a
specific matrix type, a minimum of three samples representative of those matrix types must be included in
the matrix types required by item 6 in Table 4-3. For example, if a modification is intended to overcome
matrix interferences associated with effluents containing high concentrations of polymeric materials from
indirect industrial discharges in the Thermoplastic Resins subcategory of the Organic Chemicals, Plastics,
and Synthetic Fibers industrial category, the modification must be tested on a minimum of three such
discharges. Where possible, EPA will assist the purveyor of a method modification in identifying sources
for samples of such discharges.
4.4 Development of a Validation Study Plan
Prior to conducting Tier 1, 2, or 3 validation studies, the organization responsible for conducting
the study should prepare a detailed study plan. For a simple method modification made at Tier 1, a
detailed study plan may be unnecessary if the modification is straightforward and easily understood by the
analyst and regulatory authority. In such a case, a simplified study statement may suffice.
The validation study plan should contain the elements described in sections 4.4.1 through 4.4.6.
4.4.7 Background
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The Background section of the validation study plan must:
• Identify the method as a new method or a modification of a reference method.
• Include a method summary.
• If a modification, cite the organization and method number (given in 40 CFR parts 136, 141, and
405 - 503) for the reference method.
• If a modification, describe the reasons for and extent of the modification, the logic behind the
technical approach to the modification, and the result of the modification.
• If a new method, describe the rationale for developing the method and explain how the method
meets the criteria for a new method specified in section 2 of this guide.
• Identify the matrices, matrix types, and/or media to which the method is believed to be applicable.
• List the analytes measured by the method or modification including corresponding CAS Registry
or EMMI numbers.
• Indicate whether any, some, or all known metabolites, decomposition products, or known
commercial formulations containing the analyte are included in the measurement. (For example, a
method designed to measure acid herbicides should include the ability to measure the acids and
salts of these analytes.)
4.4.2 Objectives
The Objectives section of the validation study plan should describe overall objectives and data
quality objectives of the study.
4.4.3 Study Management
The Study Management section of the validation study plan should: -
• Identify the organization responsible for managing the study.
• Identify laboratories, facilities, and other organizations that will participate in the study.
• Delineate the study schedule.
4.4.4 Technical Approach
The Technical Approach section of the validation study plan should:
*
• Indicate at which Tier level the study will be performed.
• Describe the approach that will be followed by each organization involved in the study.
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Method Validation Requirements
•• . Describe how sample matrices and participating laboratories will be selected.
• Explain how samples will be collected and distributed. -
• Specify the numbers and types of analyses to be performed by the participating laboratories.
• Describe how analyses are to be performed.
4.4.5 Data Reporting and Evaluation
This section of the validation study plan should explain the procedures that will be followed for
reporting and validating study data, and should address statistical analysis of study results.
4.4.6 Limitations
The Limitations section of the validation study plan should explain any limiting factors related to
the scope of the study.
,4.5 Detailed Procedures for Conducting Tier 1, 2, and 3 Validation Studies
When validating new or modified methods, laboratories must adhere to the standardized QC
described in Chapter 3 and detailed in the new or modified method. Laboratories must use a reference
matrix (usually, reagent water) and field samples for the validation study.
4.5.1 Optional Preliminary Testing
Although preliminary testing of the new or modified method is not required, many users may wish
to conduct such studies prior to performing all of the required tests outlined in Sections 4.6.3- 4.6.11
below. Performance of preliminary testing may help organizations identify and correct problems with the
method prior to the more extensive and costly method validation study. Typical preliminary performance
testing may include a determination of the method detection limit (MDL), analysis of initial precision and
recovery (IPR) samples, and fuggedness tests. If such preliminary tests are performed and yield results
that suggest further revision of the method is unnecessary, the preliminary test results may be used to
fulfill the MDL or IPR test requirements described in Sections 4.6.3 and 4.6.5. If, however, changes are
made to the procedures as a result of the preliminary tests, those tests must be repeated as part of the full
validation study described below.
4.5.2 Method Compilation
Prior to conducting a complete validation study, the organization responsible for developing or
modifying the method should detail the full method in accordance with EPA's Guidelines and Format for
Methods to be Proposed at 40 CFR Parts 136 or 141. If the organization that develops a new method is a
consensus standards organization or government organization with a standardized format, that format may
be used. The documented method should be distributed to each laboratory participating in the validation
study to ensure that each laboratory is validating the same set of procedures.
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4.5.3 Method Detect/on Limit Study
Each laboratory participating in the Tier 1, 2, or 3 validation study shall use the procedures
specified in the new or modified method and perform an MDL study in accordance with the procedure
given at 40 CFR part 136, Appendix B. .
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate an MDL that meets the criteria specified in the reference method or in Section 6.3.2.9
of this Guide. For wastewater methods, the MDL must be equal to or less than the MDL of the
reference method or less than 1/10 the regulatory compliance limit, whichever is greater. This
allowance of a higher MDL for a modified wastewater method to support a regulatory compliance
limit recognizes that a method modification that overcomes interferences may not achieve as low
an MDL as the reference method but is potentially more valuable in allowing determination of the
analyte(s) of interest at the regulatory compliance limit in a complex sample matrix.
• If the validation study is of a new wastewater method, the organization responsible for
development of the new method must use the results of the MDL study to determine a minimum
level (ML) of quantitation as described in Chapter 3. Determination of an ML for new drinking
water methods is encouraged but not required, because the regulations at 40 CFR part 141 specify
detection and sometimes quantitation limits for all regulated analytes.
Each laboratory must perform its MDL study on an instrument that is calibrated at a range that will
encompass the ML. -
4.5.4- Calibration
Following completion of the MDL study, each laboratory participating in the study must perform a
multi-point calibration in accordance with the procedures specified in the new or modified method.
However, a single-point calibration is allowed if the < 2% relative standard deviation (RSD) criteria at
Section 3.3.1 of this guide are met. ^ ,
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the linearity criterion and an ML or other quantitation level that is
specified in the reference method or, as may often be the case for drinking water methods, in the
applicable regulations.
• If the validation study is of a new method, the organization responsible for development of the
method must use the results of the validation study to develop a linearity criterion as described in
Chapters.
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Method Validation Requirements
4.5.5 Initial Precision and Recovery
- ] . , ,
After successfully calibrating the instrument, each laboratory participating in the study shall
perform initial precision and recovery (IPR) analyses using the procedures specified in the method to
analyze four spiked reagent water replicates. '
If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the IPR precision and recovery criteria given in the reference method.
• If the validation study is of a new method, the organization responsible for development of the
method must use the results of these IPR analyses to develop precision and recovery criteria as
described in Chapter 3.
For a new method, the concentration of the IPR samples must be stated in the method. As described in
Chapter 3, this concentration should be between one and five times the ML.
4.5.6 Field Sample Analyses
After laboratories participating in the Tier 1,2, or 3 validation study have successfully completed
the IPR analyses, the new method or modification is validated on the matrix type(s) chosen for the
validation study. The numbers of analyses required are described below.
4.5.6.1 Tier 1 - Single Matrix Type/Single PWS Validation Studies
In a Tier 1-Single matrix type/PWS study performed to validate a method modification, the
laboratory must determine the background concentration of an unspiked sample prior to analyzing an
MS/MSD pair for the matrix being tested, for a total of three field sample analyses (background, MS, and
MSD). Each laboratory participating in the study must demonstrate that it can meet the MS/MSD
precision and recovery criteria given in the reference method.
- •
In a Tier 1 - Single matrix type/PWS study performed to validate a new method, the laboratory
must analyze four spiked replicates of the matrix type to which the new or modified method will be
applied. The replicate samples must be spiked with the analyte(s) of interest at either the concentration
specified in the reference method, at a concentration one to five times the background concentration of the
analyte(s) in the sample, or at two to five times the ML, whichever is greater. In other words, the
laboratory will perform an IPR test in the matrix type of interest. Prior to spiking the replicate samples, the
laboratory must determine the background concentration of an unspiked aliquot. In all, Tier 1-Single
matrix type/PWS validation studies of new methods will require analysis of five field samples"(one -
background and four matrix). The organization responsible for developing the method must Use the
results of these sample analyses to develop MS/MSD precision and recovery criteria as described in.
.Chapter, 3. , , •
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4.5.6.2 Tier 1 - Multiple Matrix Type Validation Studies
In Tier 1-Multiple matrix type studies performed fo validate new or modified methods, the
laboratory must determine the background concentration and analyze an MS/MSD pair for each matrix
type being tested, up to a total of nine matrix types. Since three field sample analyses are required for
each matrix type (one background, one MS, and one MSD), and between two and nine matrix types may
be tested, a Tier 1-Multiple matrix type validation study will require analysis of 6 - 27 samples.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the MS/MSD precision and recovery criteria given in the reference
method.
* If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop MS/MSD precision and recovery criteria
as described in Chapter 3.
4.5.6.3 Tier 1 - Multiple PWSs
In Tier 1-Multiple PWSs studies performed to validate new or modified methods, the laboratory
must determine the background concentration and analyze an MS/MSD pair for each PWS sample being
tested, up to a total of three PWS samples. Since three field sample analyses are required for each PWS
sample (one background, one MS, and one MSD), and between two and three PWS samples may be
tested, a Tier 1-Multiple PWSs validation study will require analysis of 6 - 9 samples.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the MS/MSD precision and recovery criteria given in the reference
method. ,
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop MS/MSD precision and recovery criteria
as described in Chapter 3.
4.5.6.4 Tier 2 Validation Studies
In a Tier 2 validation study, each of the three laboratories will determine the background
concentration and analyze an MS/MSD pair for each of the three samples received. Because there are
three laboratories, each of which performs three analyses (one background, one MS, and one MSD) on
each of the three samples received, Tier 2 validation studies will require analysis of 27 samples.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the MS/MSD precision and recovery criteria given in the reference
method.
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• If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop MS/MSD precision and recovery criteria
as described in Chapter 3.
4.5.6.5 Tier 3 Validation Studies
In a Tier 3 validation study, each of the nine laboratories participating in the study will determine
the background concentration and analyze an MS/MSD pair on the sample it receives. Since there, are a
total of nine laboratories, each performing three field sample analyses (one background, one MS, and one
MSD), a Tier 3 validation study will require analysis of 27 samples.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the MS/MSD precision and recovery criteria given in the reference
method.
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop MS/MSD precision and recovery criteria
as described in Chapter 3.
! ,
4.5.7 Ongoing Precision and Recovery
If the field samples discussed in Section 4.6.6 are analyzed as a batch with the IPR samples,
analysis of an OPR sample is unnecessary in the validation study. If; however, field samples are analyzed
in a different batch or batches, then each laboratory participating in the Tier 1,2, or 3 validation study
must analyze an OPR sample with each batch. The concentration of the OPR sample must be as stated in
the method being validated.
• If the validation study is of a modified method, each laboratory participating in the study,
laboratory that analyzes an OPR sample must demonstrate that it can meet the OPR recovery
criteria given in the reference method.
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of the IPR tests described above in Section 4.6.5 to develop OPR recovery
criteria as described in Chapter 3.
4.5.8 Calibration Verification
If the field samples discussed in Section 4.6.6 are analyzed on the same shift or in the same set of
instrumental determinations as the initial calibration sequence, calibration verification is unnecessary.
However, if field samples are analyzed on a different shift or hi a different instrument batch, each
laboratory participating in the Tier 1,2, or 3 validation study must verify calibration as described in the
method.
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• If the validation study is of a modified method, each laboratory participating in the study and
verifying calibration must demonstrate that it can meet the acceptance criteria given in the
reference method for calibration verification.
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of the calibration sequence described above in Section 4.6.4 to develop QC
acceptance criteria for the calibration verification analyses as described in Chapter 3.
4.5.9 Contamination Level in Blanks .
Each laboratory that participates in a Tier 1,2, or 3 validation study must prepare and analyze at
least one method blank with the sample batch during which the matrix samples are prepared and analyzed.
The actual number of blank samples analyzed by each laboratory must meet or exceed the frequency
specified in the method.
• If the validation study is of a modified methodj each laboratory participating in the study must
demonstrate that it can meet the QC acceptance criteria for blanks that are specified in the method.
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop QC acceptance criteria for allowable blank
contamination as described in Chapter 3. i
4.5.1O Surrogate or Labeled Compound Recovery
For methods that use surrogates or labeled compounds, each laboratory participating in the Tier 1,
2, or 3 validation study must spike all field and QC samples with the surrogates/labeled compounds at the
concentrations specified in the method.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the surrogate or labeled compound recovery criteria specified in the
reference method.
• If the validation study is of a new method, the organization responsible for developing the method
must use the results of these sample analyses to develop surrogate or labeled compound recovery
QC acceptance criteria as described in Chapter 3.
4.5.11 Absolute and Relative Retention Time
Each laboratory participating in a Tier 1, 2, or 3 validation study of a chromatographic method
must determine the absolute and relative retention times of the analytes of interest.
• If the validation study is of a modified method, each laboratory participating in the study must
demonstrate that it can meet the absolute and relative retention time criteria that are specified in the
reference method.
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• If the validation study is of a new method, the organization responsible for developing the method
. .must use the results of these sample analyses to develop absolute and relative retention time criteria
as described in Chapter 3.
4.5.72 New Analytes
As described in Chapter 2, EPA proposes to consider the addition of new analytes to approved
methods as acceptable performance-based method modifications under the streamlining initiative.
Because these method modifications are performance-based, laboratories will be required to demonstrate
equivalency in accordance with the requirements summarized above for other Tier 1,2, and 3 method
modifications. In addition, laboratories are required to either develop QC acceptance criteria for the added
analyte, transfer QC acceptance criteria from an analyte with similar chemical characteristics, or transfer
QC acceptance criteria from another method with the same analyte.
4.5.13 Further Validation Studies for New Methods
After completing the Tier 1,2, or 3 validation studies of new methods, the organization responsible
for developing the method must document the study results in accordance with Section 4.7 below and
submit the results and the method to EPA for review and approval, as described in Chapter 5. If, based on
its review of the method, EPA concludes that the method is not sufficiently rugged or reliable for its
intended use, EPA may require further method development and further testing to define the stability and
reliability of the method. The tests and studies that must be performed in this case are dependent upon the
analyte(s) and the analytical system, and will be determined on a case-by-case basis as these situations
arise. .
.4.6 Validation Study Report
Laboratories or other organizations responsible for developing a new or modified method at Tier 1,
2, or 3 must document the results of the validation study in a formal validation study report that is
organized and contains the elements described in this section. There is one exception to this rule. For Tier
1 method modifications, the completed Checklists (Checklist for Initial Demonstration of Method
Performance, Checklist for Continuing Demonstration of Method Performance, and Certification
Statement), along with the raw data and example calculations, are considered adequate to document
method equivalency; a full validation study report is not necessary.
The information and supporting data required in the validation study report are sufficient to enable
EPA to evaluate a new method for adequacy Nor to support a claim of equivalent performance for a method
modification. Some items are required only fora modification; these are clearly identified below. If data
are collected by a contract laboratory, the organization responsible for using the method (i.e. permittee,
POTW, PWS, or other regulated entity) is responsible for ensuring that all method-specified requirements
are met by the contract laboratory and that the validation study report contains all required data.
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Like the validation study plan, the validation study report contains background information and
describes the study design. In addition, the validation study report details the process and results of the
study, provides an analysis and discussion of the results, and presents study conclusions. If a validation
study plan was prepared, it must be appended to and referenced in the validation study report. The
validation study report must identify and discuss any deviations from the study plan that were made in
implementing the study.
The validation study report must contain the elements described in sections 4.6.1 through 4.6.11.
4.6.1 Background
The Background section of the validation study report must describe the method (new method or
method modification) that was validated and identify the organization responsible for developing the
method. This section must:
• Identify the method as a new method or a modification of a reference method.
• Include a method summary.
• If a modification, cite the organization and method number (given in 40 CFR parts 136,141, and
405 - 503) for the reference method.
• If a modification, describe the reasons for and extent of the modification, the logic behind the
technical approach to the modification, and the result of the modification.
• If a new method, describe the rationale for developing the method and explain how the method
meets the criteria for a new method specified in section 2 of this guide.
• Identify the matrices, matrix types, and/or media to which the method is believed to be applicable.
• List the analytes measured by the method or modification including corresponding CAS Registry
or EMMI numbers. (Alternatively, this information may be provided on the data reporting forms
hi the Supporting Data appendix to the validation study report.)
• Indicate whether any, some, or all known metabolites, decomposition products, or known
commercial formulations containing the analyte are included in the measurement. (For example, a
method designed to measure acid herbicides should include the ability to measure the acids and
salts of these analytes.)
• State the purpose of the study. ,.
j , .
4.6.2 Study Design and Objectives
The Study Design and Objectives section of the validation study report must describe the study
design, and identify overall objectives and data quality objectives of the study. Any study limitations must
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be identified. The validation study plan may be appended to the validation study report to provide the
description of the study design. If no validation study plan was prepared, the study design must be
described in this section (see section 4.4 for required elements of the study design).
4.6.3 Study Implementation
The Study Implementation section of the validation study report must describe the methodology
and approach undertaken in the study. This section must:
• Identify the organization that was responsible for managing the study.
• Identify the laboratories, facilities, and other organizations that participated in the study; describe
how participating laboratories were selected; and explain the role of each organization involved in
the study.
• Indicate at which Tier level the study was performed.
• Delineate the study schedule that was followed.
• Describe how sample matrices were chosen, including a statement of compliance with Tier
requirements for matrix type selection.
• Explain how samples were collected and distributed. •
• Specify the numbers and types of analyses performed by the participating laboratories.
• Describes how analyses were performed. -
• Identify any problems encountered or deviations from the study plan and their resolution/impact on
study performance and/or results.
4.6.4- Data Reporting and Validation
This section of the validation study report must describe the procedures that were used to report
and validate study data. Although EPA will not establish a standard format for analytical data submission
because of the large variety of formats currently in use, EPA strongly recommends the Department of
Energy Environmental Management Electronic Data Deliverable Master Specification (DEEMS) because
it will expedite processing of the data review. The DEEMS list contains all of the data elements that
laboratories should submit to document method validation. A DEEMS data element dictionary is
provided in Appendix D of this guide.
4.6.5 Results
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This section of the validation study report presents the study results. Results must be presented on
the Checklists (Checklistfor Initial Demonstration of Method Performance, Checklist for Continuing
Demonstration of Method Performance, and Certification Statement), or if space does not allow, results
may be submitted in a tabular format attached to the Checklists. Raw data and example calculations are
required as part of the results and shall be included in an appendix to the validation study report (see
section 4.6.10).
The Checklists, instructions for their completion, and an example set of completed Checklists are
provided in Appendix E to this guide. For method modifications, the first two Checklists document the
technical details required to establish equivalency; the Certification Statement commits the persons
involved in the method modification and their management to the statements made in the Checklists and
the supporting information provided. The Checklist performance categories, developed with input from
EPA's various programs, were designed to apply to as many of these programs as possible. These
Checklists apply equally well to screening and field techniques and state-of-the-art laboratory procedures.
The completed Checklists verify that all QC requirements of the method were met. For modified
methods, the Checklists verify that the modified method met all QC acceptance criteria of the reference
method, for purposes of assessing method equivalency.
4.6.6 Development of QC Acceptance Criteria
For new methods, the validation study report must contain a section that describes the basis for
development of QC acceptance criteria for all of the required QC tests. The requirements for developing
QC acceptance criteria are detailed in Chapter 3.
4.6.7 Data Analysis/Discussion
This section of the validation study report must provide a statistical analysis and discussion of the
study results. For validation of modified methods, the discussion must address any discrepancies between
the results and the QC acceptance criteria of the reference method.
4.6.8 Conclusions
The Conclusions section of the validation study report must describe the conclusions drawn from
the study based on the data analysis discussion. The Conclusions section must contain a statement(s)
regarding achievement of the study objective(s).
4.6.9 Appendix A - The Method
For new methods, the method, prepared in EPA format (i.e., in accordance with EPA's Guidelines
and Format for Methods to be Proposed at 40 CFR Parts 136 or 141), must be appended to the Validation
study report. All new methods must contain QC acceptance criteria for all required QC elements (see
Chapters).
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For modified methods, the modified portion of the reference method, prepared in EPA format,
must be appended to the validation study report. ,
4.6.10 Appendix B - Validation Study Plan
If a validation study plan was prepared, it must be appended to the validation study report.
4.6.171 Appendix C - Supporting Data
The validation study report must be accompanied by raw data and example calculations that
support the results presented in the report.
4.6.11.1 Raw Data
The Results section of the validation study report must include raw data that will allow an
independent reviewer to verify each determination and calculation performed by the laboratory. This
verification consists of tracing the instrument output (peak height, area, or other signal intensity) to the
final result reported. The raw data are method specific and may include any of the following:
• Sample numbers or other identifiers used by the both the regulated entity and the laboratory
• Sample preparation (extraction/digestion) dates
• Analysis dates and times
• Sequence of analyses or run logs
• Sample volume
• Extract volume prior to each cleanup step
• Extract volume after each cleanup step
• Final extract volume prior to injection
• Digestion volume
• Titration volume
• Percent solids or percent moisture
• Dilution data, differentiating between dilution of a sample and dilution of an extract-or digestate
• Instruments) and operating conditions
• , GC and/or GC/MS operating conditions, including detailed information on
Columns used for determination and confirmation (column length and diameter, stationary
phase, solid support, film thickness, etc.)
Analysis conditions (temperature programs, flow rates, etc.)
Detectors (type, operating conditions, etc.) ;
• Chromatograms, ion current profiles, bar graph spectra, library search results
• Quantitation reports, data system outputs, and other data to link the raw data to the results
reported. (Where these data are edited manually, explanations of why manual intervention was
necessary must be included)
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• Direct instrument readouts; i.e., strip charts, printer tapes, etc., and other data to support the final
results
• Laboratory bench sheets and copies of all pertinent logbook pages for all sample preparation and
cleanup steps, and for all other parts of the determination
Raw data are required for all samples, calibrations, verifications, blanks, matrix spikes and
duplicates, and other QC analyses required by the reference method. Data must be organized so that an
analytical chemist can clearly understand how the analyses were performed! The names, titles, addresses,
and telephone numbers of the analysts who performed the analyses and of the quality assurance officer
who will verify the analyses must be provided. For instruments involving data systems (e.g., GC/MS),
raw data on magnetic tape or disk must be made available on request.
4.6.11.2 Exafnple Calculations
The validation study report must provide example calculations that will allow the data reviewer to
determine how the laboratory used the raw data to arrive at the final results. Useful examples include both
detected compounds and undetected compounds. If the laboratory or the method employs a standardized
reporting level for undetected compounds, this should be made clear in the example, as should adjustments
for sample volume, dry weight (solids only), etc.
4.7 Reporting Validation Study Results
Only validation study results for new methods are required to be reported to EPA, although
entities can request EPA review of method modification validation study results at Tier 2 and 3. Chapter 5
describes procedures for submitting validation study results for EPA review and approval of new methods
and Tier 2 and 3 method modifications.
4.7.1 Reporting Validation Study Results for New Methods
Validation study results for all new methods, regardless of tier, must be submitted to EPA for
approval. Guidance for submitting validation study results to EPA and a description of the approval
process are provided in Chapter 5. The organization responsible for developing the method also must
maintain on file complete records of all validation study documentation, including the study plan,
validation study report, completed Checklists, and all other information submitted to EPA.
4.7.2 Reporting Validation Study Results for Method Modifications
Validation study results for modified methods, regardless of tier, need not be submitted to EPA for
approval. Rather, the organization responsible for developing the method modification must maintain on
file complete records of all validation study documentation, including the study plan, validation study
report, completed Checklists, supporting data, and other information required in section 4.6. Laboratories
using the modification also should provide a copy of the validation study report with appendixes to all
regulated entities whose samples have been analyzed by the modified method.
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Regulated entities must retain validation study reports on file and make the files available for
review on request by a permitting authority. All records must be available for review by auditors.
Submission of validation study results for Tier 1, 2, and 3 method modifications is not required
because EPA does not intend to formally approve such modifications. Tier 1, 2, and 3 modifications are
considered to be approved by EPA as long as all validation study and documentation requirements have
been met. For entities wishing to seek public recognition that their procedures have been demonstrated to
be acceptable for use, EPA proposes to provide an option for submission of Tier 2 and Tier 3 method
modificationsfpr EPA approval as described in Chapter 5.
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Chapter 5
Method Approval Process
5.1 Introduction
/
Two principal objectives of the streamlining initiative are to encourage organizations external to
EPA to develop and submit for approval new analytical methods and to expedite method approval at 40
CFR parts, 136 and 141. The key to the success of these efforts is to define procedures and provide
guidance to the public on how to develop, validate, and submit a method to EPA for approval. This
guidance is intended to encourage participation of external organizations in method development.
Additionally, it will expedite the method approval process by ensuring that methods submitted to EPA for
approval are in the correct format, have been appropriately validated, and are accompanied by the
necessary supporting documentation.
This chapter details the procedures for preparing and submitting method documentation under the
streamlining initiative, and describes the rulemaking process required to approve a new method or method
modification. By providing increased method flexibility as described in Chapter 2 of this guide, EPA
expects to significantly reduce the number of modified methods that must undergo rulemaking as
alternate test procedures (ATPs), while increasing the number of new methods submitted for approval.
Under the streamlining initiative, all new methods will be subject to EPA review and approval. Modified .
methods at validation Tiers 2 and 3 will be reviewed and approved by EPA only if requested. EPA
approval may take the form of a letter of approval or a rulemaking to propose the method at 40 CFR part
136 or part 141, as described in this chapter.
The key concepts presented and discussed in this chapter are: method development, standard EPA
method format, rulemaking process, direct final rulemaking, proprietary reagents, proprietary
instruments, and proprietary methods. - .
5.2 Pre-Submission Procedures
Under streamlining, EPA must review all new methods, and will review Tier 2 and Tier 3 method
modifications upon request. Prior to submitting a method to EPA for review, a party developing a new or
modified method Will undertake several preparatory activities: method development, method validation,
and, if a rulemaking will occur, compilation of preamble information. Method developers also may wish
to publish their method independently.
5.2.1 Method Development • •
Any party who identifies a new or improved procedure or technique for analyzing an analyte of
interest can develop a new method or method modification. A new method must be a unique combination
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of analyte and determinative technique, as discussed in Chapter 2. Otherwise, it would qualify as a
modification of an existing method. In addition, the determinative technique in a new method must be
more sensitive and/or selective (specific) than the determinative techniques in all methods previously
approved for the analyte. Further, a new method must include the standardized QC elements and specify
QC acceptance criteria for each required QC element. The QC acceptance criteria must be developed from
data gathered in the method validation study, as described in Chapter 3 of this guide.
The method development process will typically include drafting the method, and checking,
modifying, and rechecking testing procedures. If an interlaboratory study is required to validate the
method, generally a single-laboratory study is done during the method development phase to identify
method revisions needed preceding the interlaboratory study. The method should be written in the
standard EPA method format. EPA method format requirements are specified in Guidelines and
Format for Methods to be Proposed at 40 CFR Part 136 or Part 141 (Guidelines and Format). The
Guidelines and Format document incorporates the analytical methods format prescribed by EPA's
Environmental Monitoring Management Council (EMMC). An objective of the EMMC format is to
standardize all Agency analytical methods.
A standardized method format used by a government agency such as the U.S. Geological Survey
or a consensus standards organization such as Standard Methods, ASTM, or AOAC-International can be
used by those organizations, in lieu of the EPA format. However, these formats may be used only by
these organizations to avoid possible confusion over authorship. Other parties are required to use the
standard EPA format. EPA will review and approve standardized formats from governmental authorities
and industrial associations upon request, but will not approve miscellaneous formats written by instrument
manufacturers, individual laboratories, and others, because of the potential proliferation of different
method formats. EPA believes that the format provided in Guidelines and Format is more than adequate
to meet the needs of the analtyical community.
5.2.2 Method Validation
Each new method or method modification must be tested to assess its performance. The process
of establishing or substantiating method performance is called validation. Method validation requirements
are described in Chapter 4.. The method developing organization is responsible for performing the
validation study at the appropriate validation tier, according to the procedures described in Chapters 4. A
validation study plan should be prepared prior to the study; the results of the study must be detailed in a
method validation report. The contents of the method validation report and the supporting Checklists and
data that must accompany the report are specified in Chapter 4.
5.2.3 Compilation of Information to Support Development of Preamble
When methods will undergo the rulemaking process, the method submitter must compile
information on the method that will facilitate EPA preparation of a draft preamble for proposal of the
method at 40 CFR parts 136 or 141. Information that should be provided includes: a detailed summary of
the method, a discussion of QC acceptance criteria development, and a description and discussion of the
interlaboratory method validation study and any other method studies conducted during method
development and validation.
When preparing method information, the method submitter must:
• Define the purpose and intended use of the method.
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• State what the method is based upon, noting any relationship of the method to other existing
analytical methods. Indicate whether the method is associated with a sampling method.
• List analytes that can be measured by the method, including each analyte's Chemical Abstracts
Service Registry Number (CASRN). If regulations cite other than the most commonly used
analyte name, refer to the regulation. For pesticides, use "acceptable common names." The use of
registered trade names is permitted.
Identify the matrix(ces) for which the method has been found satisfactory.
f i •
• Indicate the statistically determined method detection limit (MDL) and the analyte concentration
range over which the method is applicable. State the matrix(ces) in which MDL was determined.
If the MDL is not available, report an instrumental detection limit and define how it was derived.
Indicate the minimum level (ML) and water quality criteria if appropriate to the analyte and •
method.
Describe method limitations, such as "This method is not applicable to saline water," or "This
method is not intended for determination of metals at concentrations normally found in treated and
untreated discharges from industrial facilities."' Indicate any means of recognizing cases where the
method may-not be applicable to the sample under test.
• Outline, specifying amounts of sample and reagent, the procedure that is followed to determine
the presence or absence of the listed analytes. Include any sample pretreatment, such as filtration
or digestion. In this description, identify the basic steps involved in performing the method, but
omit the details that are a necessary part of the complete statement of procedure.
• State the type of procedure (colorimetric, electrometric, volumetric, etc.) and describe the source
of color, major chemical reaction, including pertinent chemical equations, etc. For instrumental
methods, state the technique.
• Identify the determinative step in the method. . , .
• List options to the method, if applicable.
• Discuss in a summary fashion how quality is assured in the method. For new methods, describe
and discuss the development of QC acceptance criteria for all of the standard QC elements. For
modified methods, include a discussion that compares the method results to the QC acceptance
1 criteria of the reference method. , ,
• Describe and discuss the method validation study and the study results, including study design and
objectives, study limitations, study management, technical approach, data reporting and
validation, results, data analysis discussion, and conclusions.
• Describe and discuss any MDL studies or other method studies that were conducted during
method development and validation
Looking at previous method rules provides an idea of the type of method information and the
appropriate level of detail for submitting method information to EPA. Examples of preambles for method
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rules include: 49 FR 43234, October 26, 1984; 56 FR 5090, February 7, 1991; 60 FR 53988, October 18,
1995; and 61 FR 1730, January 23,1996.
5.2.4 Method Publication
An objective of the streamlining initiative is to incorporate methods by reference in proposals.
EPA is working with the Office of the Federal Register (OFR) to accomplish this objective. Incorporation
by reference would facilitate method updates, increase the accessibility of the method, and save on
publication-costs. To support incorporation by reference, it would be helpful if the method developing
organization published the method. Method approval requests submitted by.governmental authorities or
industrial associations should meet this requirement without difficulty. Vendors, laboratories and other
small parties may be unable to undertake direct publication. A possible solution for small parties wishing
to incorporate their methods by reference is to have the methods published by the National Technical
Information Service (NTIS) or the Educational Resources Information Center (ERIC). If suitable means
of publication are not available, particularly to small business submitters, EPA may assist in having the
method published by NTIS or ERIC.
5.3 Submission of Method Approval Applications to EPA
When the pre-submission steps are completed, the method submitter must compile and submit to
EPA a method approval application package. The method approval application package will be submitted
to the Analytical Methods Staff (AMS), within EPA's Office of Water. The application package will
contain the method validation study report, including the formatted method and supporting data.
Requirements for the method validation study report and supporting documentation are specified in
section 4.6. If the method will undergo rulemaking, the application package also must include information
to facilitate EPA preparation of a draft preamble as described in section 5.2.3.
5.4 EPA Review of Method Approval Applications
i
EPA will review all new methods, and will review Tier 2 and Tier 3 method modifications if
requested. When a method package is submitted for review, EPA will first check the documentation for
completeness. If all of the documentation is in order, EPA will begin an internal review of the method for
scientific merhX consistency, and appropriateness. If documentation is incomplete, EPA will contact the
submitter and request submission of missing documentation before proceeding with its review.
The internal review at EPA may involve multiple programs and workgroups. Should any
problems or questions arise, EPA will communicate with the submitter to resolve the outstanding issues.
Depending on the circumstances, EPA may return the application to the submitter for revision.
If internal reviewers recommend approval of the new method or method modification, EPA will
issue a letter of acceptance for a Tier 1 new method. For Tier 2 and Tier 3 new methods, EPA will begin
the rulemaking process. For Tier 2 and Tier 3 method modifications, the method submitter has the option
of receiving a letter of approval or proceeding with the rulemaking process.
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Table 5-1: EPA Review and Action for New and Modified Methods
New Method
Modified Method
Tier 1
Single-lab, single matrix
type/single PWS
EPA review required
EPA issues a letter of approval
No EPA review
Tier2
Multi-lab, single matrix
type/all PWSs
EPA review required
Approved through rulemaking
If requested, EPA reviews and
- issues letter of approval, or
- conducts rulemaking
TierS
Multi-lab, all matrix
1 types
EPA review required
Approved through rulemaking
If requested, EPA reviews and
- issues letter of approval, or
- conducts rulemaking
5.5 Tier 1/Single-Laboratory Use Methods
Under the streamlining initiative, EPA proposes to allow use of single-laboratory, limited-use
methods as Tier 1 methods for both wastewater and drinking water. This will provide the means by which
(1) a new technology can be introduced, and (2) specific matrix interference problems can be overcome.
Further, additional single laboratories can use the technology until a sufficient number of devices are
available for interlaboratory validation.
Currently, EPA reviews single-laboratory, limited-use methods only for special applications.
Examples of special circumstances could include procedures to remove sulfate interferences in drinking
water matrices and, as described below, technologies that can eliminate total cyanide false positives in
some wastewater measurements. Under streamlining, EPA will review and issue letters of approval for
Tier 1 new methods. Tier 1 modified methods can be used once they are validated and documented in
accordance with EPA guidelines (see method validation guidelines in Chapter 4). EPA will not review
Tier 1 method modifications.
EPA recognizes that allowing single-laboratory use of a new technology for regulatory
compliance carries with it the risk that results produced with the new technology may not agree with
results produced by'an approved method. However, EPA believes that there can be a net benefit to the
regulated community by allowing new technologies that can overcome matrix interference problems. For
example, it is known that methods that measure total cyanide are susceptible to interferences from
thiosulfates and other substances, and certain members of the regulated industry have pointed out to EPA
that they have been faced with permit violations caused by these interferences. A new technology
involving flow-injection and ligand-exchange has been demonstrated to overcome many of the matrix
interferences in the determination of cyanide. Upon application by a discharger, and provided that the
method could be demonstrated by the discharger to overcome the matrix interference problem, EPA would
grant approval for use of the method on the particular discharge. After a sufficient number of dischargers ,
utilized the new technology, the method employing the technology could be validated in an interlaboratory
study then proposed for listing in Table IB at 40 CFR part 136.3.
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Although method modifications do not require formal approval, Tier 1 new methods must be
submitted to EPA for review. Upon recommendation for approval, a letter of approval will be issued.
Tier 1 modified methods can be used directly upon verification. EPA will not review Tier 1 method
modifications. , • .
5.6 Rulemaking Process
The customary rulemaking process consists of four phases: 1) proposal of the rule, 2) public
comment, 3) response to comments, and 4) publication of the final rule. The proposed rule requests public
comment and allows a specified comment period, for example 30 to 90 days, depending on the magnitude
of the proposed change. At the end of the comment period, EPA will forward any significant comments to
the method submitter. The submitter would then provide technical assistance to EPA in drafting responses
to comments. All comments that have scientific or legal merit, or raise substantive issues with the
proposed rule, must be answered to complete the rulemaking process.
EPA will review the comment responses and complete a response-to-comments document that
must be included in the final rule. EPA will prepare and submit the final rule to the OFR for publication.
The final rule will state the date that the rule becomes effective, typically 30 days after rule publication.
As of this date, the method is approved.
EPA plans to use a direct final rulemaking process to expedite the approval of noncontroversial
updates to methods, such as revisions to currently approved methods published by EPA, other government
agencies, and consensus standards organizations. Direct final rules are warranted when it is not in the
public interest to delay approval of the action and when the action is not expected to elicit public comment
to which the Agency would be required to respond.
The direct final rulemaking process was designed to accelerate the approval of noncontroversial
rules. In this process, the rule is published only once, because the proposed and final rules are considered
to be published simultaneously as a "direct final rule" in the Federal Register. The proposed rule has a
specific comment period (typically 60 days after FR publication) and the final rule has a later effective .
date (typically 120 days after FR publication). If no comments that would normally require an official
Agency response are received during the comment period, the final rule becomes effective.
If comments requiring a response are received during the comment period, the Agency must take
one of two actions before the effective date. The Agency can publish a Federal Register notice
withdrawing all or part of the action, or the Agency can publish another final rule within the 120-day
period. This final rule would include the Agency's response to comments and final action on the proposed
action with a new effective date for updating the CFR. If a second final rule must be prepared, the
submitting party (e.g., consensus standards organization) would be required to provide EPA with technical
assistance in preparing the response to comments before the final rule could be published.
Direct final rulemaking saves time and Agency resources. For example, based on the example
time periods given in this section, if no adverse comments are received, a direct final rule would become
effective within 120 days of publication (i.e., the CFR tables would be updated on the 120-day effective
date).
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5.7 Proprietary Reagents, Instruments, and Methods
EPA separates proprietary components into three categories: proprietary reagents, proprietary
instruments, and proprietary methods. EPA intends to attempt to accommodate the inclusion of
proprietary reagents and proprietary instruments in the approval of analytical methods for compliance
purposes to the extent that such inclusion still provides an adequate opportunity for public review and
comment under the Administrative Procedure Act. EPA does not anticipate, however, that it could
approve the use of proprietary methods for determining compliance with regulatory requirements where
the entire method is claimed as "confidential business information" because the opportunity for public
review and comment might be restricted too severely. If a proprietary method is patented, the method
would be considered for approval as a compliance method because the public would be able to comment
on the patented method. EPA believes the restriction on approval of proprietary methods is not serious
because reagents or instruments, not complete methods, will continue to be the most common proprietary
components used in compliance methods.
Proprietary reagents and instruments are currently included for use in approved methods and
. would continue to be allowed in approved methods. The details of the proprietary elements would need to
be disclosed to EPA, but would be withheld from the public if the person requesting protection for the
confidential business information (CBI) demonstrates that the information is entitled to confidential
treatment under 40 CFR part 2. Examples of proprietary components may include immunoassay reagents
and antibodies and liquid phases in GC columns; e.g., DB-1®, SPB-octyl, Dexsil®, etc. A new or
modified method submitted for EPA approval would need to include language stating that the proprietary,
reagent or instrument could be replaced by an equivalent. Changes made to the method after EPA
approval would require the manufacturer to demonstrate, through supporting documentation, that the new
proprietary equipment, substance, or reagent would produce results equal or superior to results produced
with the material originally tested and oh which the method approval is based. Additionally, EPA would
not propose a method containing a proprietary reagent without accurate, specific instructions for handling
the reagent and for safe disposal of each spent proprietary reagent and/or reaction product. When a
material safety data sheet (MSDS) Would need to accompany the proprietary material, the MSDS would be
the appropriate vehicle to provide these instructions. Submission of a complete MSDS with a new method
would satisfy EPA's need for instructions for safe handling and disposal of the reagent.
EPA recommends that developers of new methods that are proprietary consider Tier 1 validation
because EPA cannot propose or promulgate (i.e.,: list in the CFR) new methods for nationwide use (i.e.,
Tier 2 or 3) in which all or a portion of the procedures used to determine the identity and concentration of
the analyte(s) are considered confidential. EPA cannot approve these proprietary methods for nationwide
use in compliance monitoring because if the entire method is CBI, it is unlikely that the public would have
an adequate opportunity to comment on these procedures. Therefore, proprietary methods will not be
approved through the rulemaking process whether they are Tier 1,2, or 3 new methods, or Tier 2 or Tier 3
method modifications.
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Chapter 6
Assessing Method Equivalency
6.1 Introduction
This chapter provides guidance on reviewing method validation study reports to assess whether a
modified method has been demonstrated to produce results equivalent to results produced by the reference
method. The guidance provided in this chapter is for use by regulatory authorities in assessing method
equivalency when reference methods have been modified. Analytical laboratories may find the
information in this chapter useful when validating a new or modified method.
According to streamlining procedures, validation study results for modified methods, regardless of
tier, need not be submitted to EPA for approval. Rather, the organization responsible for developing the
method modification must maintain on file complete records of all validation study documentation.
Laboratories using the modification should provide a copy of the validation study report to all regulated
entities whose samples are analyzed by the modified method. Regulated entities must retain validation
study reports on file and make the files available for review on request by a regulatory authority or auditor.
Results of the method validations studies are documented on the Checklist for Initial
Demonstration of Method Performance, the Checklist for Continuing Demonstration of Method
Performance, and the Certification Statement (collectively called the "Checklists"). The Checklists are
used by auditors and reviewers to evaluate new methods and method modifications against reference
methods promulgated at Title 40 of the Code of Federal Regulations (CFR) parts 136 and 141. The
process of assessing method equivalency involves (1) checking completeness of the method -validation
study report package, (2) reviewing the Checklists submitted in the validation package to ensure that the
quality control (QC) acceptance criteria of the reference method have been met by the modified method,
and (3) examining the raw data to clarify any questions or inconsistencies identified on the Checklists.
For Tier 1 method modifications, the completed Checklists, along with the raw data and example
calculations, are adequate to document method equivalency, and a full method validation study report is
not required. For all other validation tiers, the data reviewer must ensure that the validation study report is
complete and includes all supporting data. •
< . ,
The key concepts presented and discussed in this chapter are: the Checklists, completness
assessment, -validation study report checksheet, and method equivalency assessment.
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6.2 Checking Completeness of the Method Validation Study Report
Package
A method validation study report must be prepared for every study conducted to validate new or
modified methods. Section 4.6 of this guide details the required contents of the method validation study
report and the supporting data that must accompany the report. The following form can be used to check
completeness of the validation package.
Table 6-1: Validation Study Report Checksheet
Items Required
Background section: Does it-
Identify the method as a new method or a modification of a reference method?
Include a method summary?
If a modification, cite the organization and method number (given in 40 CFR parts 136,141, and 405 -
503) for the reference method?
If a modification, describe the reasons for and extent of the modification, the logic behind the technical
approach to the modification, and the result of the modification?
If a new method, describe the rationale for developing the method and explain how the method meets
the criteria for a new method'specified in the Streamlining Guide?
Identify the matrices, matrix types, and/or media to which the method is believed to be applicable?
List the analytes measured by the method or modification including corresponding CAS Registry or
EMMI numbers? (Alternatively, is this information provided on the data reporting forms in the
Supporting Data appendix to the validation study report? Yes)
Indicate whether any, some, or all known metabolites, decomposition products, or known commercial
formulations containing the analyte are included in the measurement?
State the purpose of the study?
Study Design and Objectives section: Does it...
Describe the study design? [Validation study plan appended? Yes]
Identify overall objectives and data quality objectives of the study?
Identify any study limitations?
Study Implementation section: Does it...
Identify the organization that was responsible for managing the study?
Identify the laboratories, facilities, and other organizations that participated in the study; describe how
participating laboratories were selected; and explain the role of each organization involved in the study?
Indicate at which Tier level the study was performed?
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Table 6-1: Validation Study BLeport Checksheet
Items Required
Delineate the study schedule that was followed?
Describe how sample matrices were chosen, including a statement of compliance with Tier requirements
for matrix type selection?
Explain how samples were collected and distributed?
Specify the numbers and types of analyses performed by the participating laboratories?
Describe how analyses were performed?
Identify any problems encountered or deviations from the study plan and their resolution/impact on
study performance and/or results?
Data Reporting and Validation section: Does it....
Describe the procedures that were used and organizations involved in reporting and validating study
data? - '
Results section: Are results presented on the Checklist for Initial Demonstration of Method
Performance, or in a tabular format attached to the Checklist? '
Are results presented on the Checklist for Continuing Demonstration of Method Performance, or hi a
tabular format attached to the Checklist? •
Is a signed Certification Statement attached to the Checklists? '
Development of QC Acceptance Criteria section (for new methods only):
Does the section adequately describe the basis for development of QC acceptance criteria for all of the
required QC tests? : . .
Data Analysis/Discussion section: Does it...
Provide a statistical analysis and discussion of the study results?
For modified methods, address any discrepancies between the results and the QC acceptance criteria of
the reference method? , . '
Conclusions section: Does it...
Describe the conclusions drawn from the study based on the data analysis discussion?
Contain a statements) regarding achievement of the study objective(s)?
Appendix A - The Method:
Is it prepared in EPA format (i.e., in accordance with EPA's Guidelines and Format for Methods to be
Proposed at 40 CFR Parts 136 or 141)?
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Table 6-1: Validation Study Report Checksheet
Items Required
Appendix B - Validation Study Plan appended? (Optional)
Appendix C - Supporting Data:
Raw Data: Are raw data provided for all samples and QC analyses that will allow an independent
reviewer to verify each determination and calculation performed by the laboratory by tracing the
instrument output to "the final result reported?
Are the raw data organized so that an analytical chemist can clearly understand how the analyses were
performed? • .
Are the names, titles, addresses, and telephone numbers of the analysts who performed the analyses and
of the quality assurance officer who will verify the analyses provided?
Example Calculations: Are example calculations that will allow the data reviewer to determine how
the laboratory used the raw data to arrive at the final results provided?
6.3 Assessing Equivalency Using the Checklists
The method validation results are reported on the Checklists. Copies of the Checklists and an
example of completed Checklists are provided in Appendix E to this guide. The Checklists provide a side-
by-side identification of the performance criteria (reference method QC acceptance criteria) and the results
obtained in the validation study. A checkmark in the final column is used to-indicate that the performance
specifications of the reference method were achieved.
The data reviewer should review each item on the checklist to ensure that the QC acceptance
criteria for each QC element were met. If there are any discrepancies, the reviewer should consult the data
analysis/discussion section of the validation study report for a discussion of results and, if necessary,
examine the raw data.
6.4 Data Review Guidance
This section provides guidance for reviewing data submitted to EPA and state authorities under
CWA and SDWA. This guidance provides a tool for those who want to perform detailed inspection of
data analyzed by methods under 40 CFR parts 136 and 141, to assess equivalency when method
modifications are used or for other purposes. When performing equivalency assessments, any questions or
discrepancies in the Checklists should be resolved by examining the raw data. The material presented in
this section is technically detailed and is intended for data reviewers familiar with analytical methods.
6.4.1 Standardized Quality Control
In developing methods for the determination of pollutants and contaminants in water and in
developing this streamlining initiative, EPA sought scientific and technical advice from many sources,
including EPA's Science Advisory Board; scientists at EPA's environmental research laboratories;
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scientists in industry and academia; scientists, managers, and legal staff at EPA Headquarters and Regions;
States; contractors; contract laboratories; the regulated industry; consensus standards organizations; and
others. The result of discussions held among these groups was the standardized quality control (QC)
approach that is an integral part of the streamlined methods approval program. Standardized QC is
specified for each reference method and contains the following elements:
• Calibration linearity ,
• Calibration verification ,
• Absolute and relative retention time precision (for chromatographic analyses)
. • Initial precision and recovery or "start-up" tests
• Ongoing precision and recovery -
• Analysis of blanks
• Surrogate or labeled compound recovery
• Matrix spike and matrix spike duplicate precision and recovery (for non-isotope dilution analyses)
• Demonstration of method detection limits
• Analysis of reference sample
When reviewing method validation data, the permit writer, PWS, or other individual or organi- ,
zation has the authority and responsibility to ensure that the test data submitted contain the elements listed
above; otherwise, the data can be considered noncompiiant.
6.4.2 Details of Data Review
The details of the data review process depend to a great extent upon the specific analytical
method. Even for data from the same method, there may be many approaches to data review. However,
given the standardized QC requirements of the streamlined methods approval program, a number of basic
concepts apply. The following sections provide the details for reviewing analytical data and discuss EPA's
rationale for the QC tests. Results from the QC tests for all standardized QC elements must be within the
QC acceptance criteria specified in, or associated with, the reference method to validate that results
produced by a method modification are equivalent or superior to results produced by the reference
method.
6.3.2.1 Calibration linearity ,
The relationship between the response of an analytical instrument to the concentration or amount
of an analyte introduced into the instrument typically is represented by an averaged response or calibration
factor, a calibration line, or a calibration curve. An analytical instrument can be said to be calibrated in
any instance in which an instrumental response can be related to a single concentration of an analyte. The
response factor or calibration factor is the ratio of the response of the instrument to the concentration (or
amount) of analyte introduced into the instrument.
Nearly all analytical methods focus on the range over which the response is a linear function of
the concentration of the analyte. This range usually extends from the minimum level of quantitation (ML)
on the low end to the point at which the calibration becomes non-linear on the high end. For regulatory
compliance, it is important that the concentration of regulatory interest (e.g., permit limit; MCL) fall
within this range. Calibration can also be modeled by quadratic or higher order mathematical functions.
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The advantage of a calibration line that passes through the origin is that an averaged response factor or
calibration factor can be used to represent the slope of this line. Use of a single factor simplifies
calculations and the interpretation of the data. Also, it is easier to discern when an inaccurate calibration
standard has been prepared if the calibration function is a straight line.
Many analytical methods, particularly recent methods, specify some criterion for determining the
linearity of the calibration. When this criterion is met, the calibration function is sufficiently close to a
straight line that passes through the origin to permit the laboratory to use an averaged response factor or
calibration factor. Linearity is determined by calculating the relative standard deviation (RSD) of the
response factor or calibration factor for each analyte and comparing this RSD to the limit specified in the
method. If the RSD does not exceed the specification, linearity through the origin is assumed. If the
specification is not met, a calibration curve must be used.
For whatever calibration range is used, a reference method should contain a specification for the
RSD of the response or calibration factor to establish the breakpoint between linear calibration through the
origin and a line not through the origin or a calibration curve. For new methods, the method developer
must provide the RSD results by which one can judge linearity, even in instances where the laboratory is
using a calibration curve. In instances where the laboratory employs a curve rather than an average
response or calibration factor, the data reviewer should review each calibration point to ensure that the
response increases as the concentration increases. If it does not, the instrument is not operating properly,
or the calibration curve is out of the range of that instrument, and data are not considered valid.
6.3.2.2 Calibration verification
Calibration verification involves the analysis of a single standard at the beginning of each
analytical shift or after the analysis of a fixed number of samples (e.g., 10). The concentration of each
analyte in this standard is normally at the same level as in one of the calibration standards, typically at 1 -
5 times the ML. The concentration of each analyte in this standard is calculated using the calibration data.
The calculated concentration is compared to the concentration of the standard. Calibration is verified
when the concentration is within the calibration verification limits specified in the method. If the results
are within the specifications, the laboratory is allowed to proceed with analysis without recalibrating and
allowed to use the calibration data to quantify sample the concentration or amount of each analyte in
samples, blanks, and QC tests.
If calibration cannot be verified, the laboratory may either recalibrate the instrument or prepare a
fresh calibration standard and make a second attempt to verify calibration. If calibration cannot be verified,
with a fresh calibration standard, the instrument must be recalibrated. If calibration is not verified,
subsequent data are considered to be invalid until the instrument is recalibrated.
6.3.2.3 Absolute and relative retention time precision
Retention time specification aid in the identification of analytes in chromatographic analyses. In
some methods, a minimum retention time is specified to ensure adequate separation of analytes in complex
mixtures. If retention time QC criteria cannot be verified, chromatographic identification of analytes is
suspect and reanalysis is necessary.
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6.3.2.4 Initial precision and recovery
This test is required prior to the use of the method by a laboratory. It is sometimes termed the
"start-up test." Performing the startup test "after the fact" or after samples have been analyzed is not
acceptable. The laboratory must demonstrate that it can meet the IPR QC acceptance criteria in the
method. EPA's experience has been that difficulty in passing the start-up test leads to marginal
performance by the laboratory in the routine operation of the method.
The start-up test consists of spiking the analytes of interest into a set of four or more aliquots of a
reference matrix and analyzing these four aliquots. The reference matrix simulates the medium being
tested. A separate IPR test must be performed for each medium. The mean concentration and the standard
deviation of the concentration are calculated for each analyte and compared to QC acceptance criteria in
the method. If the mean and standard deviation are within the limits specified, the analysis system is in
control and the laboratory can use the system for analysis of blanks, field samples, and other QC tests
samples. For some methods (e.g., Methods 625 and 1625), a repeat test is allowed because of the large
number of analytes being tested simultaneously.
If there are no start-up test data, or if these data fail to meet the QC acceptance criteria in the
method, all data produced by that laboratory using that method are not considered valid. It is important to
remember that if a change is made to a method, the start-up test must be repeated with the change as an
integral part of the method. Such changes may involve alternative extraction, concentration, or cleanup
processes; alternative GC columns, GC conditions, or detectors; or other procedures designed to address a
particular matrix problem. If the start-up test is not repeated when a procedure is changed, added, or
deletec, data produced by the modified method are considered invalid.
6.3.2.5 Ongoing precision and recovery
An ongoing precision and recovery (OPR) standard (also termed a "laboratory control sample"
(LCS) or .a "laboratory fortified blank" (LFB)) must be analyzed with each sample batch prior to the
analysis of a blank, sample, or matrix spike or duplicate. The number of samples in the batch is usually 10
or 20, depending on the method, or the OPR is required at the beginning of an analysis shift, regardless of
the number of samples analyzed during that shift. The data reviewer must determine if the OPR standard
has been run with each sample batch or at the beginning of the shift and if all criteria have been met. If the
standard was not run with a given set of samples, or if the criteria are not met, the results for that set of
samples are considered invalid.
6.3.2.6 Analysis of blanks
Blanks must be analyzed either on a periodic basis on with each sample batch, depending on the
method. Blanks may contain contamination at levels no higher than specified in the method. Samples
associated with a contaminated blank must be reanalyzed.
6.3.2.7 Surrogate or labeled compound recovery
\ ,.,...,•_
Surrogate or labeled compounds are used to assess the performance of the method on each sample.
Recoveries of these compounds from each sample must be within QC acceptance criteria to demonstrate
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Assessing Method Equivalency
acceptable method performance on the sample. If the recovery is not within the criteria, the sample is
normally diluted and the dilute sample analyzed to demonstrate that a matrix effect precluded reliable
analysis of the undiluted sample.
6.3.2.8 Matrix spike and matrix spike duplicate
Non-isotope dilution methods require a spike of the analytes of interest into a separate aliquot of
the sample for analysis with the sample. The purpose of the matrix spike (sometimes termed a "laboratory
fortified sample matrix" (LFM)) is to determine if the method is applicable to the sample in question.
While many of the approved methods were tested using effluents from a wide variety of industries,
samples from some sources may not yield acceptable results. It is therefore important to, evaluate method
performance in the sample matrix of interest. If the recovery for the MS/MSD is not within the QC
acceptance criteria, a matrix interference may be the cause. The sample is usually diluted and the diluted
sample spiked and analyzed. If the QC acceptance criteria are met with the diluted MS/MSD, a matrix
problem exists. Cleanup and other processing of the sample are then required to overcome the matrix
interference if analysis of the undiluted sample is required to establish compliance.
6,3.2.9 Demonstration of method detection limits
A laboratory that wishes to use a new or modified wastewater method must demonstrate that the
method detection limit (MDL) specified in the reference method can be achieved. Alternatively, if the
regulatory wastewater compliance limit is above the MDL, laboratories must demonstrate that the
minimum level (ML) determined with the new'or modified wastewater method is at or below 1/3 the
compliance limit. A laboratory that wishes to use a new or modified drinking water method must
demonstrate that the MDL determined with that method meets the detection limits specified at 40 CFR
141.23, 141.24, and 141.89 and/or as published in the table of QC limits in Methods and Criteria. For
both drinking and waste water determinations, demonstration of a valid detection limit requires use of an
MDL study in accordance with the procedure at 40 CFR part 136, Appendix B. If the MDL determined
with the new or modified method is not acceptable, the method may not be used because the laboratory
has not demonstrated an ability to detect the analyte at the level required. EPA notes that the required
detection limits specified in the regulations and/or in the reference method(s) are usually analyte-specific;
and for the same analyte the requirement may differ between the wastewater and the drinking water
reference method.
6.3.2.1O Reference Sample Analysis
EPA is considering setting acceptance criteria for a reference material based on the measurement
error of the method. Ideally, a laboratory should be able to demonstrate the ability to quantitate the
analyte in a reference material to within the acceptance range specified for the reference material.
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Chapter 7
Biological Methods
7.1 Introduction
Although the initial streamlining proposal pertains only to chemical analytical methods, EPA
intends to expand method flexibility to include biological methods in the future. Biological methods
include both the testing of an environmental sample for the presence of microbiological material (e.g.,
bacteria, protozoa, and viruses) and the use of biological organisms in tests for whole effluent toxicity
(WET) of an environmental sample. EPA believes that flexibility in testing for biological material will be
similar to the flexibility allowed in the modification to chemical analytical methods^ Test procedures
should be able to be modified when the modifications produce equivalent or superior results. EPA has
protocols for some microbiological methods that are currently used in the alternate test procedure (ATP)
program (EPA 1996b, 1996c). EPA is developing a protocol for approval of new and modified (alternate)
WET methods that is based on the tiered validation structure provided by streamlining.
Biological methods are considered to be method-defined analytes. As discussed in Chapter 2,
incorporating flexibility into method-defined analytes will likely require more rigorous control than
modifications for specific chemical substances. EPA believes, however, that certain parts of the
procedures can be modified without adversely affecting method performance. At present, this problem has
not been sufficiently addressed to allow proposal of specific flexibility requirements in approved
biological methods. Until EPA can clarify the extent of acceptable flexibility, requests for changes in
biological methods will be reviewed and approved on 'an individual basis.
OW is working with EPA's Biological Advisory Committee (BAG) to identify appropriate
applications of flexibility in WET test methods. As mentioned above, EPA also is developing a protocol
for approval of new and modified (alternate) WET methods that includes procedures for external
organizations to develop, validate, and submit WET methods or method mbdifications for EPA approval.
This protocol will be distributed for comment after it is completed and has undergone internal EPA
review.
EPA anticipates that requests for approval of new or modified (alternate) WET methods will focus-
on one of the following areas: organism; test duration; test procedures; reactor type (e.g., batch, flow
through, or fill and draw); equipment, volume-to-organism ratio, or system monitoring. Factors that will
be considered in reviewing submitted methods include: single- and multi-laboratory precision; the life-
stage, sources, and quality of test organisms; the nature and control of test conditions; test data collection
and reporting requirements; test acceptability criteria; endpoints; methods of data analysis; and test
sensitivity.
7.2 New WET Methods
The following has been suggested as a definition for a new WET test method:
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Biological Methods
A WET test procedure will be considered a "new" procedure if it employs a "new" species or
requires culture conditions, test conditions, endpoints, and/or methods of data analysis that are
substantially different from those used for current Agency-approved species/methods.
7.3 Modified WET Methods
*
The following has been suggested as a definition for a modified (alternate) WET method:
A proposed test procedure will be considered a "modified" procedure if it involves only minor
changes in established test conditions for an approved species/method, or if it employs a "new" species to
be used as a substitute for a related, Agency-approved species, and if:
(1) The proposed test with the "new" species can be performed with essentially the same test
conditions and methods of data analysis used for current Agency-approved species/methods
(i.e., with only minor modifications in one or a few conditions), and
(2) The sensitivity of the proposed test species/method using an approved or "new" species is
demonstrated to be equal to or greater than the sensitivity of current Agency-approved
species/methods, using reference toxicants or effluents, or .
(3) The proposed test results in a significant reduction in the cost or ease of performance of the
test, without an unacceptable loss in sensitivity.
7.4 Validation Requirements
In keeping with method flexibility guidance, laboratories would be required to demonstrate that a
modified (alternate) method produces results equivalent or superior to those produced by the EPA-
approved reference method and would be required to demonstrate that new methods produce data that are
acceptable for use in NPDES compliance monitoring. It has been suggested that this demonstration would
consist of paired side-by-side tests with effluents and a range of reference toxicants (metal, organic, and
salt).
It has been suggested that the following would suffice to document validation of a jiew or
modified (alternate) WET method:
• Summary of Method: For modified methods, including a discussion of how the modified method
differs from the 40 CFR part 136 method and the rationale for requesting the modification
• Toxicity Test Procedure: The method or modified portion of the method prepared in EPA
standard format.
• Data: Data from paired side-by-side tests using both effluents and a range of reference toxicants
(metal, organic, and salt). ".
* References: Including all sources of technical information used in developing the new method or
method modification.
Draft, October 1996
91
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Appendix A
Acronyms and Symbols
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Acronyms and Symbols
Acronyms
ACS American Chemical Society
AOAC AOAC-International; formerly the Association of Official Analytical Chemists
AOX adsorbable organic halides
APHA American Public Health Association
ASTM formerly the American Society for Testing and Materials
ATP alternate test procedure •
AWWA American Water Works Association
BAC
BOD
Biological Advisory Committee
biochemical oxygen demand
CAS Chemical Abstract Services (
CF calibration factor ' '
CFR Code of Federal Regulations
CVAA Cold Vapor Atomic Absorption
CWA Clean Water Act •
DEEMS Department of Energy Environmental Management Electronic Data Deliverable
Master Specification
EAD Engineering and Analysis Division
BCD electron capture detector
ELCD electrolytic conductivity detector
EMMC Environmental Monitoring Management Council
EPA Environmental Protection Agency
FID flame ionization detector
FLAA flame atomic absorption
FOIA Freedom of Information Act ,
FR Federal Register
GC gas chromatography
GC/HRMS , gas chromatography/high resolution mass spectrometry
GC/LRMS gas chromatography/low resolution mass spectrometry
GC/MS gas chromatography/mass spectrometry
GFAA graphite furnace atomic absorption
HPLC high performance liquid chromatography
HRGC high resolution gas chromatography
HRMS high resolution mass spectrometry
ICP/AES inductively coupled plasma/atomic emission spectroscopy
ICP/MS inductively coupled plasma/mass spectrometry
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Streamlining Guide
H
IPR initial precision and recovery
IR. " infra-red spectroscopy
JAOAC Journal ofAOAC - International
LOQ limit of quantitation
MCAWW Methods for Chemical Analysis of Water and Waste
MCL maximum contaminant level
MDL method detection limit
ML minimum level
MS matrix spike
MSD matrix spike duplicate
MSDS material safety data sheet
NCASI National Council of the Paper Industry for Air and Stream Improvement, Inc.
NELAC National Environmental Laboratory Accreditation Committee
NERL-Ci National Exposure Research Laboratory - Cincinnati
NIST National Institute of Standards and Technology
NPD nitrogen phosphorous detector ,
NPDES National Pollutant Discharge Elimination System
NPDWR National Primary Drinking Water Regulations
NTTAA National Technology Transfer and Advancement Act of 1995
OECA Office of Enforcement and Compliance Assurance
OFR Office of Federal Register
OGC Office of General Counsel
OGWDW Office of Ground Water and Drinking Water
OPR ongoing precision and recovery
ORD Office of Research and Development
OST Office of Science and Technology
OSW Office of Solid Waste
OW Office of Water
PAH polynuclear aromatic hydrocarbon
PID photoionization detector
POTW publicly owned treatment works
PWS public water system
QA quality assurance
QC quality control
RF response factor
RPD relative percent difference
RR relative response
A-2
Draft, December 1996
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Acronyms and Symbols
RRT - relative-retention time
RSD relative standard deviation
RT retention time
SDWA Safe Drinking Water Act
SEM . standard error of the mean
SRM Standard Reference Material
TDS
TOC
TSS
USGS
total dissolved solids
total organic.carbon
total suspended solids
U.S. Geological Survey
WEF
WET
Water Environment Federation
whole effluent toxicity
Draft, December 1996
A-3
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Appendix B
Glossary
-------
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Glossary
Glossary
40 CFR part 136
40 CFR part 141
Title 40, part 136 of the Code of Federal Regulations. This
part specifies EPA's test procedures for the analysis of
pollutants regulated under the Clean Water Act.
Title 40, part 141 of the Code of Federal Regulations. This
part specifies EPA's National Primary Drinking Water
Regulations pursuant to the Safe Drinking Water Act; Subpart
C of 40 CFR part 141 lists analytical methods required for
monitoring under the Act.
95% confidence interval A statistical level indicating a 95 % probability that the
parameter variable is enclosed within the given data interval.
accuracy
aliquot
analysis of variance
analyte
analyte of concern
analysis
approved method
The degree of agreement between an observed value and an
accepted reference value. Accuracy includes random error
(precision) and systematic error (bias) that are caused by
sampling and analysis.
A representative portion of a sample. (QAMS)
A study of the effect of a set of qualitative variables on a
quantitative response variable, based on a decomposition of
the variance of the response variable.
The substance, a property of which is to be measured by an
analysis. (QAMS)
An analyte designated by EPA to adversely affect or have the
potential to adversely affect human health, the environment,
aesthetics, or the senses. Analytes of concern are listed in
approved methods.
The determination of the nature or proportion of one or more
constituents of a sample.
A testing procedure (analytical method) promulgated at 40
CFR parts 136,. 141,405-500, and other parts of the CFR that
support EPA's water programs. t -
average percent recovery The average of the recovery, expressed as percent. See
"recovery."
bias
A systematic or persistent distortion of a measurement process
that deprives the result of representativeness; i.e., the expected
Draft, December 1996
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Streamlining Guide
blank
calibration
calibration factor
calibration linearity
calibration verification
Code of Federal
Regulations
compliance
confidence interval
contract laboratory
correlation coefficient
sample measurement is different than the sample's true value.
A data quality indicator. (QAMS)
See "method blank."
The process of establishing the relationship between the
concentration or amount of material introduced into an
instrument or measurement process and the output signal.
The quotient of instrument response and concentration of a
standard obtained during instrument calibration. Unknown
sample concentrations are determined by multiplying the
determined calibration factor by the measured instrument
response.
The degree to which calibration points lie along a straight line.
Means of establishing that the instrument performance
remains within pre-established limits.
A codification of the general and permanent rules published in
the Federal Register by the Executive departments and
. agencies of the Federal Government.
\
A state of meeting all requirements.
The numerical interval constructed around a point estimated
of a population parameter, combined with a probability
statement (the confidence coefficient) linking it to the
population's true parameter value. If the same confidence
interval construction technique and assumptions are used to
calculate future intervals, they will include the unknown
population parameter with the same specified probability.
(EMMC)
Private, academic, or commercial laboratory under contract to
EPA or other organization to perform testing.
A number between -1 and 1 that indicates the degree of
linearity between two variables or, sets of numbers. The closer
to -1 or +1, the stronger the linear relationship between the
two (i.e., the better the correlation.) Values close to zero
suggest no correlation between the variables. The most
common correlation coefficient is the product-moment, a
measure of the degree of linear relationship between two
variables. (EMMC)
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Draft, December 1996
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Glossary
data quality objective
determinative technique
digestion
Qualitative and/or quantitative statement of the overall level of
uncertainty that a decision-maker is willing to accept in results
or decisions derived from environmental data. Data quality
objectives provide the statistical framework for planning and
managing environmental data operations consistent with the
data user's needs. (EMMC) . . - ,
The physical and/or chemical process by which measurement
of the identity and concentration of an analyte is made. For
most methods, the determinative technique consists of an
instrumental measurement. .
Solubilization of the analytes in sample by destruction of the
sample matrix. Most commonly performed in the
determination of metals.
direct final promulgation The promulgation of a final rule in the CFR without first
being proposed. This procedure is used when the rules are not
expected to generate significant negative comments.
discharge
discharge of pollutant
distillation
effluent
explicit flexibility
extraction
Generally, any spilling, leaking, pumping, pouring, emitting,
emptying or dumping (40 CFR 109.2; 110.1; 116.3); also, see
"discharge of a pollutant" (40 CFR 122.2); the medium that is
spilled, leaked, pumped, poured, emitted, emptied, or dumped.
Any addition of any pollutant or combination of pollutants to
(1) waters of the U.S. from any point source or (2) to the
waters of the contiguous zone or the ocean from any point
source other than a vessel or other floating craft which is
being used as a means of transportation (40 CFR 122.2;
401.11)
The process of heating a mixture to separate the more volatile
from the less volatile parts, then cooling and condensing the
resulting vapor so as to produce a more nearly pure or refined
substance: nonvolatile impurities remain in the residue.
(Webster's)
A medium that flows out of a point source, e.g., the discharge
from a sewage treatment plant.
Modifications that are explicitly allowed in an approved
method.
The process of selectively transferring a substance from one
phase to another or from one liquid to another with differing
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Streamlining Guide
extreme rank sum test
characteristics, then separating the phases or liquids to isolate
the substance; e.g., transferring organic analytes from an
aqueous liquid to an organic liquid.
A test to determine if laboratory performance significantly
deviates from that of another lab.
facility
Federal Register
front-end technique
A plant or group of plants within a single location that is
regulated under a single National Pollutant Discharge
Elimination System (NPDES) permit and/or SDWA. A
single facility may have multiple water supplies, discharges,
waste streams, or other environmental media that are subject
to compliance monitoring. For example, a single facility
within the Pulp, Paper, and Paperboard industrial category
may have a direct discharge, an indirect discharge, and an in-
process waste stream that are all subject to compliance
monitoring.
A daily publication that provides a uniform system for
publishing Presidential and Federal agency documents.
Documents published in the Federal Register make changes to
the CFR to keep the CFR current. (OFR)
Any technique in the analytical process that precedes the
determinative technique,, including all procedures, equipment,
solvents, etc. that are used in the preparation and cleanup of a
sample for analysis. Front-end techniques does not include
conditions and/or procedures for the collection, preservation,
shipment, and storage of the sample.
Guidelines and Format The document titled Guidelines and Format for Methods to be
Proposed at 40 CFR Parts 136 and 141;' available from the
National Technical Information Service (NTIS), U:S.
Department of Commerce, Springfield, Virginia, 22161 (703-
487-4600) as NTIS publication PB96-210448.
incorporation by reference A means for allowing the Federal agencies to comply with the
requirement to publish regulations in the Federal Register by
referring to materials already published elsewhere. The
material incorporated by reference has the force and effect of
law. (OFR)
industrial category ' A category listed in 40 CFR parts 405-503.
industrial subcategory A subcategory defined at 40 CFR parts 405-503.
B-4
Draft, December 1996
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Glossary
initial precision
and recovery
interference
interlaboratory
interlaboratory method
intralaboratory
The analysis of a minimum of four spiked replicate reference
matrix samples under the same conditions as will be used for
analysis of environmental samples. The IPR is used to
demonstrate that a laboratory is able to produce reliable results
.with the method prior to analysis of environmental samples.
A positive or negative effect on a measurement caused by a
substance other than the one being investigated. (QAD)
Occurring in multiple laboratories.
A study conducted according to the principles outlined in
Guidelines for Collaborative Study Procedures to Validate
Characteristics of a Method of Analysis; JAOAC78 No. 5,
1995; Statistical Manual of the Association of Official
Analytical Chemists, W.J. Youden and E.H. Steiner, 1975
(published by AOAC-Intemational, 481 N. Frederick St.,
Gaithersburg, MD 20877-2417; 301-924-7077); Use of
Statistics to Develop and Evaluate Analytical Methods
(published by AOAC-International); ASTM Standard D-2777
(published by ASTM, 100 Barr Harbour Drive, West
Conshocken, PA 19428-2959; 610-832-9500); or other well-
established and documented principles for interlaboratory
method validation studies.
Occurring within a single laboratory.
labeled compound
labeled compound
recovery
laboratory
log-normal
matrix
matrix effect
An isotopically labeled form of the native compound.
The percentage of the labeled compound recovered. See
"recovery." ,
A person that owns or leases a stationary or mobile facility in
which a sample is tested for an analyte.
A distribution of a random variable X such that the natural
logarithm of X is normally distributed.
The component or substrate that contains the analytes of
interest. (NELAC QS)
Variability in the analytical performance of a method that can
be attributed to the type of sample analyzed.
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Streamlining Guide
matrix spike
matrix spike duplicate
matrix type
measurement quality
objective
medium
method
method blank
method-defined analyte
method detection limit
A sample prepared by adding a known mass of target analyte
to a specified amount of a sample matrix for which an
independent estimate of target analyte concentration is
available. A matrix spike is used, for example, to determine
the effect of the matrix on a method's recovery efficiency.
(QAMS)
A replicate of the matrix spike to test precision. The
MS/MSD are used in combination to test the precision of an
analysis. (QAMS)
A sample medium with common characteristics across a given
industrial category or subcategory. For example, C-stage
effluents from chlorine bleach mills, effluent from the
continuous casting subcategory of the iron and steel industrial
category, POTW sludge, and in-process streams in the
Atlantic and Gulf Coast Hand-shucked Oyster Processing
subcategory are each a matrix type. For the purposes of this
initiative all drinking waters constitute a single matrix type.
Critical level which, if exceeded, is considered to append
additional, and possibly unacceptable, measurement
uncertainty to the corresponding data.
The physical phase of a sample matrix. Air, water, soil are
sample media.
A body of procedures and techniques for performing a task
(e.g. sampling, characterization, quantitation) systematically
presented in the order in which they are to be executed.
(QAMS)
A clean sample (absent of the analytes of interest and
interferences) processed simultaneously with and under the
same conditions as samples containing an analyte of interest
through all steps of the analytical procedure. (QAMS)
An analyte without a specific, known composition where the
analytical result depends totally on the measurement
procedure.
The minimum concentration of a substance that can be
measured and reported with 99% confidence that the analyte
concentration is greater than zero and is determined from
analysis of a sample in a given matrix containing the analyte.
B-6
Draft, December 1996
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Glossary
For an MDL study, it is essential that all sample processing
steps of the analytical method be included.
[The MDL results from estimating a method's sensitivity at the two lowest levels, zero
concentration, and the lowest concentration that the method is capable of distinguishing
from zero with a 99% probability.]
method modification
method validation
Methods and Criteria.
A change made to an approved method. The change may be
to a front-end technique or to the determinative technique.
A process by which a laboratory or vendor establishes the
performance of a new method or substantiates the
performance of a method modification.
The document titled: Analysis of Pollutants in Municipal
Water and Industrial Waste-water: Test Procedures and
Quality Control Acceptance Criteria; available from the
National Technical Information Service (NTIS), U.S.
Department of Commerce, Springfield, Virginia, 22161 (703-
487-4600) as NTIS publication PB96-210463, and
incorporated by reference into this part.
mid-point response factor The response factor at the concentration at which calibration is
verified.
minimum level
modified method
navigable waters
new method
The lowest concentration at which the entire analytical system
must give a recognizable signal and acceptable calibration
point for an analyte. It is equivalent to the concentration of the
lowest calibration standard analyzed by a specific analytical
procedure, assuming that all the method-specified sample
weights, volumes, and processing steps have been employed.
(40 CFR 132.2)
An approved method that has been modified to change a
front-end technique or the determinative technique, either
using method-specified flexibility or expanded flexibility
allowed under streamlining
All waters of the United States, including the territorial seas.
(40 CFR 110.1)
A method that employs a determinative technique for an
analyte of concern that differs from determinative techniques
employed for that analyte in methods previously approved at
40 CFR part 136 or 141. In addition, it must (1) employ a
determinative technique that is more sensitive and/or selective
(specific) than the determinative techniques in all methods
Draft, December 1996
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Streamlining Guide
previously approved for the analyte, (2) contain the
standardized QC elements detailed in Chapter 3 of the
Streamlining Guide, (3) specify, for all standardized QC
elements, QC acceptance criteria that have been developed in
accordance with the requirements described in Chapter 3 of
the Streamlining Guide, and (4) be documented in accordance
with the requirements detailed in the Guidelines and Format
for Methods to be Proposed at 40 CFR Parts 136 or 141 or
other standard format.
other approved methods
percent recovery
phthalate
precision
.Promulgated methods that are not designated as a reference
method, but continue to carry the same regulatory status.
100 times the recovery.
An ester of phthalic acid containing the radical QH4(COO)2=;
used for buffers, for standard solutions, and in vacuum pumps.
Certain phthalate esters are Priority Pollutants.
The degree to which a set of observations or measurements of
the same property, usually obtained under similar conditions,
conform to themselves; a data quality indicator. Precision is
usually expressed as standard deviation, variance, or range, in
either absolute or relative terms. (QAMS)
[The precision obtainable from an environmental measurement method may be estimated
from replicate analyses of subsamples taken from the same (homogenous) sample.
Generally speaking, the more carefully one executes the various steps of a method and
controls the variables affecting the method's capability, the more precise will be the
results. The use of a nonhomogeneous sample will compound the precision estimate w.ith
the sample variability.]
preparation
procedures
promulgated method
promulgation
public water system
Processing performed on a sample prior to analysis, e.g.
extraction, concentration, cleanup, etc.
A set of systematic instructions for performing an activity.
(QAD)
A method that has been published or incorporated by
reference into 40 CFR parts 136,141,405-500, or other parts
that support EPA's water programs.
Publication of a final rule in the FR.
A system for the provision to the public of piped water for
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Draft, December 1996
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Glossary
(PWS)
human consumption, if such system has at least fifteen service
connections or regularly serves an average of at least twenty-
five individuals daily at least 60 days out of the year. Such
term includes (1) any collection, treatment, storage, and
distribution facilities under control of the operator of such
system and used primarily in connection with such system,
and (2) any collection or pretreatment'storage facilities not
-under such control which are used primarily in connection
with such system. A public water system is either a
"community water system" or a "noncommunity water
system."
quality assurance
quality control
QC acceptance criteria
recovery
reference method
regulated entity
relative response
An integrated system of activities involving planning, quality
control, quality assessment, reporting, and quality
improvement to ensure that a product or service meets defined
standards of quality with a stated level of confidence.
(QAMS)
The overall system of technical activities whose purpose is to
measure and control the quality of a product or service so that
it meets the needs of users. The aim is to provide quality that.
is satisfactory, adequate, dependable, and economical.
(QAMS) '.-...
Performance specifications developed from validation data
and used to control the limits within which an analytical
method is operated. .
The total amount of the analyte found in the sample divided
by the amount of the analyte added into the sample as a spike.
f
A method that has been approved at 40 CFR part 136 or 141,
contains (or is supplemented with) standardized quality
control (QC) and QC acceptance criteria that define the
required level of performance, and has been designated as a
reference method in the tables appearing at 40 CFR part 136
or 141. The reference method serves as a standard against
which method modifications can be statistically compared.
Permittees, PWSs, POTWs, and other entities responsible for
compliance with provisions of the CWA or SDWA.
The ratio of the response of an analyte relative to the response
of a labeled compound.
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relative retention time The chromatographic elution time relative to an isotopically
labeled compound or internal standard.
relative standard deviation The standard deviation expressed as a percentage of the mean
(1 OOoVX); i.e., the coefficient of variation.
response factor The inverse of the calibration factor. The slope of the line.
responsible person/party See "regulated entity."
retention time Elution time specific to a given sample.
sample matrix
sample matrix effect
validation
sample medium
screening method
See "matrix." -
A test of the extent to which differences, if
'any, in method performance could be attributed to variability
between samples obtained from different industrial matrices,
facilities, or PWSs.
See "medium."
A method that employs a determinative technique for an
analyte of concern that differs from determinative techniques
employed for that analyte in methods previously approved at
40 CFR part 136 or 141. In addition, it must (1) be
demonstrated to produce a false negative probability of no
more than one percent, (2) contain the standardized QC
elements detailed in Chapter 3 of the Streamlining Guide, (3)
specify, for all standardized QC elements, QC acceptance
criteria that have been developed in accordance with the
requirements described in Chapter 3 of the Streamlining
Guide, and (4) be documented in accordance with the
requirements detailed in the Guidelines and Format for
Methods to be Proposed at 40 CFR Parts 136 or 141 or other
standard format.-
selectivity
sensitivity
spike
The capability of a method or instrument to respond to an
analyte in the presence of interferences.
The capability of a method or instrument to differentiate
between different amounts or concentrations of an analyte.
The process of adding a known amount of target analyte to a
sample; used to determine the recovery efficiency of the
method. (QAMS) ,
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Draft, December 1996
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Glossary
spike amount
stakeholder
A kiiown mass df analyte added to a sample and used to
determine the recovery of a method.
A party with a vested interest in a particular program. For
EPA's water methods program, such parties include
dischargers, permittees, analytical laboratories, vendors,
method-developing organizations, and local, regional, state,
and federal permitting and regulatory agencies.
The measure of the dispersion of observed values expressed as
the positive square root of the sum of the squares of the
difference between the individual values of a set and the
arithmetic mean of the set, divided by one less than the
number of values in the set.
standard error of the mean The standard deviation of the sampling distribution of the
mean; a measure of sampling error.
standard deviation •
standardized quality
control
straw man
streamlining
Streamlining Guide
Student's t distribution
Uniform performance testing procedures that ensure reliable
results. The procedures can include calibration linearity,
calibration verification, absolute and relative retention time
precision, initial precision and recovery, ongoing precision
and recovery, analysis of blanks, surrogate or labeled
compound recovery, matrix spike and matrix spike duplicate
recovery and precision, demonstration of method detection
limits, and analysis of a reference sample.
A draft document proposed for the purpose of generating
public interest, comments, and suggestions to possible
changes without committing EPA to a course of action.
A process to improve the performance of a program while
retaining the mechanisms to retain data quality (e.g., reducing
costs, resources, or wastes).
The document titled: Guide to Method Flexibility and
Approval of EPA Water Methods; available from the National
Technical information Service (NTIS), U.S. Department of
Commerce, Springfield, Virginia, 22161 (703-487-4600) as
NTIS publication PB96-210455 and incorporated by reference
into this part. .
A type of sampling distribution for a random variable. A
normal distribution divided by the square root of a chi-square
distribution divided by its degrees of freedom.
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surrogate
surrogate recovery
Tierl
Tier 2
TierS
A substance with properties that mimic the analyte of interest
that is unlikely to be found in an environmental sample and
that is added to the sample for quality control purposes.
(QAMS)
The recovery for a surrogate. See "recovery."
The application of a new or modified method in a single
laboratory to one or more matrices. Method validation
requirements are limited to single laboratory testing on the
matrix type or matrix types of interest.
The application of a new or modified method to samples from
a single matrix type in a single industrial category or
subcategory. Method validation requires an interlaboratory
study on samples collected from a minimum of 3 separate
facilities each in a minimum 3 laboratories to confirm method
performance or to establish QC acceptance criteria for the
method.
The application of a new or modified method to all matrix
types. Method validation requires an interlaboratory method
validation study or a study of 9 matrix types in 9 laboratories
to confirm method performance or to establish QC acceptance
criteria for the method.
variance
validate
A measure of the dispersion of a set of values. The sum of the
squares of the difference between the individual values of a
set and the arithmetic mean of the set, divided by one less than
the number of values in the set. (The square of the sample
standard deviation.) (QAMS)
Method validation
The above definitions are referenced to the following organizations:
EMMC Environmental Monitoring Management Council
NELAC QS National Environmental Laboratory Accreditation Conference, Quality
Systems
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Glossary
OFR
QAD
QAMS
Office of Federal Register
Quality Assurance Division, National Center for Environmental Research
and Quality Assurance, Office of Research and Development, USEPA
Quality Assurance Management Staff .
Draft, December 1996
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Appendix C
Current Method Flexibility
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Current Method Flexibility
This chapter provides a summary report of stakeholder inquiries and EPA responses concerning
the method flexibility allowed in the current 40 CFR 136 Appendix A analytical methods. These
correspondences, generated in 1994 and 1995, were one impetus for undertaking the initiative to
streamline the method approval process and method flexibility in the programs regulated by the Office of
Water. ,
The narrow range of the raised issues reflects the limited flexibility that is currently allowed. The
responses indicate the incremental approach that has been historically followed to improve test procedures.
This appendix is provided to facilitate a comparison between the proposed and existing method flexibility.
ISSUE # 1 - CRITERIA FOR DETERMINING ACCEPTABLE METHOD MODIFICATIONS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
1.5
8.1.2
EPA 821-B-93-001
OTHER PERTINENT
METHOD(s)
603
608,625
603,608,625
603,608,625
EQUIVALENT
SECTION(s)
1.4
1.5
8.1.2
EPA 821-B-93-001
7.5 Any modification to this method, beyond those expressly permitted, shall be considered as a major
modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and
136.5. Depending upon the nature of the modification and the extent of intended use, the applicant may
be required to demonstrate that the modifications -will produce equivalent results when applied to relevant
waste-waters.
8.1.2 In recognition of advances that are occurring in chromatography, the analyst is permitted certain
options (detailed in Section 11.1) to improve the separations or lower cost of measurements. Each time
such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
EPA 821-B-93-001 "Guidance On Evaluation, Resolution, and Documentation of Analytical Problems
Associated with Compliance Monitoring", page 10, Flexibility in Analytical Methods: "The analyst is
permitted to 'improve separations or lower the costs of analyses'provided that the results obtained are not
less precise and,accurate than the results obtained using the unmodified method".
Does this impact those areas in the method where the Agency has used words like "suggested", "should",
or "recommended"?
Response: Yes.
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Can changes be made to lower the cost of analyses, even if they are not specifically permitted in the
method, so long as the accuracy and precision guidelines in the method can be met?
Response - No. Some method changes, such as substituting a flame ionization detector for a mass
spectrometer in Method 624, constitute a new method and need to be brought to the permitting authority
for a ruling. On the other hand, some areas of method flexibility, such as those discussed in this
communication, have been reviewed by the Agency and judged to be reasonable in view of advances in
measurement technology.
ISSUE # 2 - CALIBRATION VERIFICATION
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
7.4
OTHER PERTINENT
METHOD(s)
603
608
625
EQUIVALENT
SECTION(s)
7.5
7.4
7.3 .
7.4 The working calibration carve or RF must be verified on each -working day by the measurement of a
QC Check Sample.
Our interpretation of "working day" is every 24 hours. Is that acceptable?
Response: No. A working day for most people is 8 hours. Some methods specify 12 hours. Either is
acceptable so long as calibration is verified. If calibration is not verified, samples analyzed during the
previous "working day" must be inspected for a possible adverse effects. If instrument performance is
degraded during the previous "working day," calibration must be verified or the instrument must be
recalibrated, and the samples reanalyzed.
ISSUE # 3 - REQUIRED FREQUENCY OF MATRIX SPIKES
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
8.1.4
EPA 821-B-93-001
OTHER PERTINENT
METHOD(s)
603,608,625
603,608,625
EQUIVALENT
SECTION(s)
8.1.4
EPA 821-B-93-001
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Current Method Flexibility
8.1.4 The laboratory must, on an on going basis, spike and analyze a minimum of 5% of all samples to
monitor and evaluate laboratory data quality. This procedure is described in Section 8.3:
8.3 The laboratory must, on an ongoing basis, spike at least 5% of the samples from each sample site
being monitored to assess accuracy. For laboratories analyzing 1 to 20 samples per month, at least one
spiked sample per month,is required.
This requirement, when applied to a laboratory, dedicated to a single discharge or a single set of
discharges, is straightforward. Its application to commercial laboratories that analyze a wide range of
discharge samples from many different facilities each month can be confusing. It could be interpreted to
mean that a commercial lab that analyzes less than 20 samples per month (10 for Methods 603 and 608)
from any one sampling site must spike.a sample from that site at least once a month (regardless of how
many spikes have been performed for other sampling sites). This could effectively mean that every
sample analyzed for every discharge client will need to be spiked. This would greatly increase the cost of
analysis to the regulated community. Alternatively, it could be interpreted to require that a commercial lab
spike 5% (10% for Methods 603 and 608) of its total sample volume unless it analyzes less than 20
discharge samples per month (10 for Methods 603 and 608), in which case it must spike at least one
sample per month. , ' - '
. • ':••"• \ ..-•"•'•• \ • , ' . •.
Which interpretation is correct?
Response: Neither. The hierarchy of requirements are:
(1)
(2)
(3)
The laboratory must analyze one spiked wastewater sample per month per method
used in that period.
The laboratory must analyze at least one spiked sample from each sample site. !
If the laboratory analyzes more than 20 samples from a site, at least 5% of the
samples must be spiked.
Two examples to illustrate: if, using Method 604, laboratory A contracts to analyze one sample per week
from a site over one year, and analyzes a total of 20 samples per month by Method 604 from this and other
sites, three spiked samples from the site must be analyzed during the year. The laboratory may choose
which sample to spike among the first twenty, the second twenty, and the last 12-20 If, using Method
604, laboratory B contracts to analyze one sample per quarter for a year, and analyzes a total of 20 samples
by Method 604 from this and other sites in the same month that the sample is analyzed, the laboratory
must spike one of the four samples. If the laboratories in these two examples analyzed no other samples
with Method 604 during the year, laboratory A would spike 12 samples out of 52 and laboratory B would
spike 4 of 4.
ISSUE #4- ONGOING METHOD ACCURACY DOCUMENTATION REQUIREMENTS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
Draft, December 1996
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METHOD 624
SECTION
8.6
OTHER PERTINENT
METHOD(s)
603,608,625
EQUIVALENT
SECTION(s)
8.5
8.6 As part of the QC program for the laboratory, method accuracy for -waste-water samples must be
assessed and records must be maintained. After the analysis of 5 spiked -waste-water samples as in section
8.3, calculate the average percent recovery and the standard deviation of the percent recovery... Update
the accuracy assessment for each parameter (on) a regular basis (e.g. after each 5 to 10 new accuracy
measurements).
Normally we focus our efforts on meeting the ongoing method QC criteria and the initial demonstration of
accuracy and precision. We maintain the data necessary to calculate the accuracy assessment if it were
ever requested. Is this acceptable? .
Response: Yes.
ISSUE # 5 - INTERNAL STANDARD COMPOUNDS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
7.3
OTHER PERTINENT
METHOD(s)
625
EQUIVALENT
SECTION(s)
7.2
7,3 Internal standard calibration procedure—To use this approach, the analyst must select three or more
internal standards that are similar in analytical behavior to the compounds of interest. The analyst must
farther demonstrate that the measurement of the internal standard is not affected by method or matrix
interferences. Some recommended internal standards are listed in Table 3.
Are internal standards not in Table 3 (Table 8 for Method 625) acceptable? For instance, would the 524.2
or 8240 internal standards be acceptable for use in Method 624? Minimizing the number of internal
standard solutions that the lab must maintain leads to substantial cost savings that are subsequently passed
on to the regulated community.
Response: Alternate internal standards are acceptable provided that method performance is not degraded
and the reason is justified and documented.
ISSUE # 6 - QUALITATIVE IDENTEBTCATION REQUIREMENTS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows: .
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Draft, December 1996
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Current Method Flexibility
METHOD 624
SECTION
12.1.3
OTHER PERTINENT
METHOD(s)
625
EQUIVALENT
SECTION(s)
• 14.1.3
72.7.3 The relative peak heights of the three characteristic masses in the EICPs must fall within +/- 20%
of the relative intensities of these masses in a reference mass spectrum. The reference mass spectrum can
be obtained from a standard analyzed in the GC/MS system or from a reference library.
When setting up the GC/MS method, if the laboratory sets the limits in the software to 20%, there is a
significant risk of false negatives due to coeluting compounds interfering with the ions of the target
analytes. However, if the limits are broadened to minimize the chance of false negatives, there is no
efficient means by which to measure this percentage. We believe that setting the ion ratio in the software
large enough to guard against the possibility of false negatives (40%) and then visually inspecting the
spectrum relative to the reference spectrum is within the flexibility allowed by the method. Does the
Agency agree? ,
Response: Yes. The software should be set up to force false positives. The analyst must then determine
which of the positives is false.,
Section 12.1 (14.1 for Method 625) states that one primary and at least two secondary ions are to be used
for quantisation. Tables 3 and 4 (Tables 4 and 5 for Method 625) list primary and secondary ions for the
various analytes involved, but do not always list two secondary ions. Can the analyst use professional
judgement to drop or add characteristic ions to account for interferences and other analytical problems?
Response: The analyst may choose alternate m/z's provided that the reason is justified and documented.
ISSUE # 7 - SURROGATE COMPOUND RECOVERY REQUIREMENTS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
8.5
OTHER PERTINENT
METHOD'(s)
625
EQUIVALENT
SECTION(s)
8.6
5.5 As a quality control check, the laboratory must spike all samples with the surrogate standard spiking
solutions as described in Section 11.4, and calculate the percent recovery of each surrogate compound.
All samples must be spiked with surrogate. No criteria are given. Can optional surrogate criteria be
developed using statistical techniques or by using the surrogate limits given in EPA method 8260 (8270
for Method 625)? , '
Response: Optional surrogate QC criteria can be used.
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ISSUE # 8 - REQUIRED CONCENTRATION OF MATRIX SPIKES
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
8.3.1
OTHER PERTINENT
METHOD(s)
603,625
EQUIVALENT
SECTION(s)
8.3.1
8.3.1 The concentration of the spike in the sample should be determined as follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a specific parameter in the sample is
being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5
times higher than the background concentration determined in Section 8.3.2, -whichever
concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample is not being checked against a
limit specific to that parameter, the spike should be at 20 ug/L or 1 to 5 times higher than the
background concentration determined in Section 8.3.2, whichever concentration would be larger.
Quite often the commercial laboratory is not aware that a sample is being tested for regulatory compliance
or what the regulatory limit might be. In addition, it is often impractical and expensive to determine
background levels before spiking and to vary spiking levels. A single spiking protocol at an acceptable
concentration level results in greater efficiencies and a lower cost to the regulated community. Is it
acceptable to spike at 20 ug/L (50 ug/L for Method 603, 100 ug/L for Method 625)?
Response: Yes, it is acceptable to alter the concentration of the spike so long as the concentration is (a)
greater than the background concentration and (b) less than or equal to the regulatory compliance level.
ISSUE # 9 - ACCEPTABLE TRAP MATERIALS AND DIMENSIONS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
5.2.2
11.1
OTHER PERTINENT
METHOD(s)
603
603
EQUIVALENT
SECTION(s)
5.2.2
10.1
5,2.2 The trap must be at least 25 cm long and have an inside diameter of at least 0.105 in. The trap
must be packed to contain the following minimum lengths of adsorbents: 1.0 cm of methyl silicone coated
packing (Section 8.3.2), 15 cm of2,6-dyphenylene oxide polymer (Section 6.3.1). and 8 cm of silica gel
(Section 8.3.3). The minimum specifications for the trap are illustrated in Figure 2.
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Current Method Flexibility
11.1 Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in
this table are retention times andMDL that can be achieved under these conditions. -An example of the
separations achieved by this column is shown in Figure 5. Other packed columns or chromatographic
conditions may be used if the requirements of Section 8.2 are met.
Is the use of newer traps, having different dimensions and packing material with improved (decreased)
retention of water and better desorption characteristics, considered "other chromatographic conditions" per
Section 11.1 (Section 10.1 for Method 603) and thereby acceptable, so long as the requirements of Section
8.2 are met? ,
Response: Yes. The Agency has agreed that extension of method flexibility to include trap materials arid
conditions is appropriate.
ISSUE # 10 - ACCEPTABILITY OF CAPILLARY COLUMNS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
5.3.2
8.1.2
11.1
OTHER PERTINENT
METHOD(s)
603
603
603
EQUIVALENT
SECTION(s)
5.4.1
8.1.2
10.1
5.3.2 Column—6 ft longx 0.1 in ID stainless steel or glass, packed-with 1% SP-1000 on Carbopack B
(60/80 mesh) or equivalent. This column was used to develop the method performance statements in
Section 14. Guidelines for the use of alternate column packings are providedJn Section ILL
8.1.2 In recognition of advances that are occurring in chromatography, the analyst is permitted certain
options (detailed in Section 11.1) to improve the separations or lower the cost of measurements. Each
time such a modification is made to the method, the analyst is required to repeat the procedure in Section
8.2. ' ' ' .
11.1 Table 1 summarizes the, recommended operating conditions for the gas chromatograph. Included in
this table are retention times andMDL that can be achieved under these conditions. An example of the
separations achieved by this column is shown inFigure 5. Other packed columns or chromatographic
conditions may be used if the requirements of Section 8.2 are met. EPA 821-B-93-001 "Guidance On
Evaluation, Resolution, and Documentation of Analytical Problems Associated with Compliance
Monitoring", page 10, Flexibility in Analytical Methods: "For example, the analyst is allowed to use
professional judgement in selecting packed or open tubular columns, operating temperature programs,
carrier gas or solvent flow rates, and detectors".
We believe the use of capillary columns is within the flexibility allowed in sections 8.1.2 and 11.1 (10.1
for Method 603). Does the Agency agree? ••'.''
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Streamlining Guide
Response: Yes. The Agency agrees that extension of method flexibility to include capillary columns is
appropriate. Of course, a hardware upgrade may be required to handle the sharper peaks produced by
capillary columns.
ISSUE # 11 - TRAP CONDITIONING REQUIREMENTS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
7.1
OTHER PERTINENT
METHOD(s)
603
EQUIVALENT
SECTION(s)
7.1
7.1 Assemble a purge and trap system that meets the specifications in Section 5.2. Condition the trap
overnight at 180-C by backflushing with an inert gas flow of at least 20 mL/min. Condition, the trap for 10
min once daily prior to use.
If the laboratory can adequately condition a trap in less time than "overnight", is this acceptable? For
example, if a sample foams and the trap must be replaced, if the trap is conditioned during the day and
analysis of a blank demonstrates that the system is clean, can analyses proceed?
Response: Yes.
ISSUE # 12 - PREPARATION OF CALIBRATION STANDARDS
The following citations are from Method 624. Identical or similar requirements are included in other
Methods as follows:
METHOD 624
SECTION
7.3.1
OTHER PERTINENT
METHOD(s)
603
EQUIVALENT
SECTION(s)
7.3.1
7.3.1 Prepare calibration standards at a minimum of three concentration levels for each parameter by
carefully adding 20.0 uL of one or more secondary dilution standards to 50, 250, or 500 mL of reagent
water. A25 uL syringe with a 0.006 in. ID needle should be used for this operation. One of the
calibration standards should be at a concentration near, but above, the MDL (Table 1) and the other
concentrations should correspond to the expected range of concentrations found in real samples or should
define the working range of the GC/MS system. These aqueous standards'can be stored up to 24 h. if held
in sealed vials with zero headspace as described in Section 9.2. If not so stored, they must be discarded
after Ih.
First, are syringes of other internal diameters acceptable?
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Current Method Flexibility
Response: Yes.
Second, from this paragraph it would seem that the Agency wants to hold the volume of the intermediate
standard pipetted constant and vary the size of the volumetrics. Jn other words, if we have to add 20 uL of
intermediate solution and we only have three final volumes to chose from, there are only three possible
, concentrations we can make from our intermediate solution. Would it be acceptable to vary the amount of
intermediate solution added or chose a different final volume when preparing these standards?
Response: Yes. The objective is to calibrate the instrument; the details may be varied.
ISSUE #13 - REQUIRED MASS ACQUISITION RANGE
This issue relates solely to Method 624. -
5.3.3 Mass spectrometer—Capable of scanning from 20 to 280 amu every 7s or less, utilizing 70 V
(nominal) electron energy in the electron impact ionization mode, and producing a mass spectrum which
meets all the criteria in Table 2 when 50 ng of 4-bromqfluorobenzene (BFB) is injected through the GC
inlet. This paragraph defines the necessary scan speed for the mass spec to be from 20 to 280 in seven
seconds or less. Does it also require that the scan range 20 to 280 be used for data acquisition? With this
scan range, methanol would be the predominate peak in the total ion chromatogram. We believe that
scanning from 33 to 280 is acceptable. This would still bracket all the characteristic ions of the analytes of
interest presented in the method and exclude methanol. Does the Agency agree?
Response: No. Scanning from m/z 20 is required in order to rigorously identify acrolein and adrylonitrile,
should they be present. If there is concern about the display of the total resolved ion chromatogram, the
dataican be displayed from m/z 45 upward and the m/z's resulting from air (nitrogen, oxygen, argon,
and methanol will not be visible.
ISSUE # 14 - SURROGATE COMPOUNDS, PREPARATION AND FINAL CONCENTRATIONS
This issue relates solely to Method 624.
6.7 Surrogate standard spiking solution— Select a minimum of three surrogate compounds from Table 3.
Prepare stock standard solutions for each surrogate standard in methanol as described in Section 6.5.
Prepare a surrogate standard spiking solution from these stock standards at a concentration of 15 ug/mL
in water. Store the solutions at 4-C in Teflon-sealed glass containers with a minimum ofheadspace. The
solutions should be checked frequently for stability. The addition oflOuL of this solution to 5 ml of
sample or standard is equivalent to a concentration of 30 iig/L of each surrogate standard.
TABLE 3. SUGGESTED SURROGATE AND INTERNAL STANDARDS
Compound
Retention
time (minf
Primary m/z
Secondary
m/z's
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Streamlining Guide
Benzene d-6
4-Bromqfluorobenzene
1,2-Dichloroethane d-4
1,4-Difluorobenzene
Ethylbenzene d-5
Ethylbenzene d-10
Fluorobenzene
Pentafluorobenzene
Bromochloromethane
2-Bromo-l-chloropropane
1,4-Dichlorobutane
17.0
28.3
12.1
19.6
26.4
26.4
18.4 .
23.5
9.3
> 19.2
25.8
84
95
102
114
111
98
96
168
128
77
55
174,176
63,88
70
49,130,51
79,156
90,92
(a)For chromatographic conditions, see Table 1.
Since Table 3 gives "Suggested Surrogate and Internal Standards", may alternative surrogates be utilized,
such as those used in 524.2 or 8240, or is the laboratory bound to those on this list? Minimizing the
number of surrogate solutions that the lab must maintain results in substantial cost savings that can
subsequently be passed on to the regulated community..
Response: Alternate surrogates may be used.
When preparing standard solutions can the concentrations and/or volumes of the surrogate solutions be
changed? Can the final concentration of the surrogates in the samples be changed? This would facilitate
the use of commercially prepared solutions thereby decreasing the cost of performing the analysis.
Response: Yes. Surrogate concentrations may be changed.
ISSUE # 15 - SURROGATE COMPOUND RECOVERY REQUIREMENTS
This issue relates solely to Method 624.
5.5 As a quality control check, the laboratory must spike all samples -with the surrogate standard spiking
solution as described in Section 11.4, and calculate the percent recovery of each surrogate compound.
All samples must be spiked with surrogate. No criteria are given. Can optional surrogate criteria be
developed using statistical techniques or by using the surrogate limits given in EPA method 8240?
Response: See issue #7.
ISSUE # 16 - ANALYSIS OF ACROLEIN AND ACRYLONITRILE BY METHOD 624
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Current Method Flexibility
This issue relates solely to Method 624.
1.2 The method may be extended to screen samples for acrolein (STORETNo. 34210, CAS No. 107-02-8)
and acrylonitrile (STORETNo. 34215, CAS No. 107-13-1), however, the preferred method for these two
compounds in (sic) Method 603.
Table 1C- List Of Approved Test Procedures For Non-Pesticide Organic Compounds, footnote #4:
Method 624 may be extended to screen samples for Acrolein and Acrylonitrile. However, when they are
known to be present the preferred method for these two compounds is method 603 or method 1624.
We believe that if Method Detection Limits (MDLs) are documented and if accuracy and precision criteria
in method 603 for Acrolein and Acrylonitrile can be met using method 624, that Acrolein and
Acrylonitrile can legitimately be reported (at or above reporting limits consistent with the documented
MDLs) from a method 624 analysis. Does the Agency agree?
Response: Yes, provided that the performance criteria and MDLs in Method 603 can be met using
Method 624. ,
ISSUE #17-SAMPLE PRESERVATION REQUIREMENTS
This issue relates solely to Method 624.
9.3 Experimental evidence indicates that some aromatic compounds, notably benzene, toluene, and ethyl
benzene are susceptible to rapid biological degradation under certain environmental conditions. (3)
Refrigeration alone may not be adequate to preserve these compounds in wastewaters for more than seven
days. For this reason, a separate sample should be collected, acidified, and analyzed when these
aromatics are to be determined. Collect about 500 mL of sample in a clean container. Adjust thepHof
the sample to about 2 by adding 1+1 HCl while stirring vigorously. CheckpHwith narrow range (1.4 to
2.8) pH paper. Fill a sample container as described in Section 9.2.
This preservation protocol could be interpreted to require three different sample, analyses (to permit 14 day
hold times) to determine the full 624 list (one sample for acrolein and acrylonitrile., one for purgeable
halocarbons, and one for purgeable aromatics).
Can the purgeable halocarbons be analyzed from an acidified sample with a pH <2? Can acrolein and
acrylonitrile be analyzed from an acidified sample with a pH <2 or is there some other preservation routine
that will allow for fewer analyses?
Response: EPA recommends acidification and refrigeration as the principle preservation procedures for
purgeable organic compounds. If the holding time is to be extended to 14 days, a minimum of two
samples will be required. The first for acrolein adjusted to pH 4-5 per footnoted to Table II of 40 CFR
part 136; the other to pH <2 with HCl per footnote 10 of this table. If free chlorine is present, it must be
reacted with sodium thiosulfate per Table II.
ISSUE # 18 - REQUIRED CONCENTRATION OF QC CHECK SAMPLE
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Streamlining Guide
This issue relates solely to Method 608.
8,2 To establish the ability to generate acceptable accuracy and precision, the analyst must perform the
following operations:
8.2.1 A quality control (QC) check sample concentrate is required containing each single-component
parameter of interest at the folio-wing concentrations in acetone: 4,4'-DDD, 10 ug/mL; 4,4'-DDT, 10
ug/mL; endosulfan II, 10 ug/mL; endosulfan sulfate, 10 ug/mL; endrin, 10 ug/mL; any other
single-component pesticide, 2 ug/mL. If this method is only to be used to analyze for PCBs, chlordane, or
toxaphene, the QC check sample concentrate should contain the most representative multicomponent
parameter at a concentration of 50 ug/mL in acetone. The QC check sample concentrate must be
obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support
Laboratory in Cincinnati, Ohio if available. If not available from that source, the QC check sample
concentrate must be obtained from another external source. If not available from either source above, the
QC check sample concentrate must be prepared by the laboratory using stock standards prepared
independently from those used for calibration.
8.2,2 Using apipet, prepare QC check samples at the test concentrations shown in Table 3 by adding
LOO mL ofQC check sample concentrate to each of four 1-L aliquots of reagent -water.
8.3.1 The concentration oj"the spike in the sample should'be determinedas follows:
8.3.1.1 If, as in compliance monitoring, the concentration of a specific parameter in the sample is
being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5
times higher than the background concentration determined in Section 8.3.2, whichever
concentration would be larger.
8.3.1.2 If the concentration of a specific parameter in the sample is not being checked against a
limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1
to 5 times higher than the background concentration determined in Section 8.3.2, -whichever
concentration-would be larger.
8.3.1.3 If it is impractical to determine background levels before spiking (e.g., maximum holding
times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if
any; or, if none (2) the larger of either 5 times higher than the expected background concentration
or the test concentration in Section 8.2.2.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Sections 8.2.1
or 8.3.2) to 1L of reagent water. The QC check standard, needs only to contain the parameters that failed
criteria in the test in Section 8.3.
As we understand the method, 1 mL of the QC Check standard from section 8.2.1 is added to 1 L of
sample to prepare a matrix spike. The same amount of QC Check standard would be added to 1 L of
reagent water to prepare a QC Check Sample. The samples are then concentrated to a final volume of 10
mL. This would result in the following concentrations in the extracts:
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Current Method Flexibility
PARAMETER
CONC. IN
EXTRACT
(ug/L)
Aldrin
a-BHC
b-BHC
d-BHC
g-BHC
Chlordane
4,4-DDD
4,4-DDE
4,4-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
200
200
200
200,
200
5000
1000
200
1000
200
200
1000
1000
1000
200
200
5000
5000
5000
5000
5000
5000
5000
5000
In all cases except Toxaphene these concentrations are above the normal linear range of an BCD detector
when set up to achieve method 608 detection limits. The following are the spike concentrations and upper
calibration limits we currently use:
CONC. IN UPPER CAL.
.EXTRACT LIMIT
PARAMETER (ug/L) (ug/L)
Aldrin
a-BHC
b-BHC
d-BHC
g-BHC
Chlordane
4,4-DDD
4,4-DDE
4,4-DDT
30
30
30
30
30
50
60
60
60
50 -.
50
50
50
50
1000
100
100
100
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Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
60
30
60
60
60
30
30
3000
500
500
500
500
,500
500
500
100
50
100
100
100
50
50
5000
1000
1000
1000
1000
1000
1000
1000
Are these spike concentrations acceptable?
Response: Yes, provided all method-specified QC criteria are met.
ISSUE #19-ACCEPTABLE SAMPLE EXTRACTION PROCEDURES
This issue relates solely to Method 608.
10.2 If the emulsion interface between layers is more than one-third the volume of the solvent layer, the
analyst must employ mechanical techniques to complete the phase separation. The optimum technique
depends upon the sample, but may include stirring, filtration of the emulsion through glass wool,
centrifugation, or other physical methods.
Allowances are made for the use of techniques to overcome emulsion problems. We have found that the
most effective technique for dealing with emulsions is the use of continuous liquid/liquid extractors. This
technique is not specifically mentioned here. Since wastewater samples routinely cause emulsion
problems, is continuous extraction an acceptable technique to use with this method?
Response: Yes, provided the procedure is an adaptation of Method 608 (neutral sample pH, methylene
chloride-based extraction solvent, extended contact time to assure extraction of analytes from solids) and
all method-specified QC criteria are met.
ISSUE # 20 - QUANTITATION PEAK REQUIREMENTS
This issue relates solely to Method 608.
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Current Method Flexibility
13.3 For multicomponent mixtures (chlordane, toxaphene, andPCBs) match retention times of peaks in
the standards -with peaks in the sample. Quantitate every identifiable peak unless interference -with
individual peaks persist after cleanup. Add peak height or peak area of each identified peak in the
chromatogram. Calculate as total response in the sample versus total response in the standard.
Please clarify what is meant by the phrase "every identifiable peak". The chromatogram of PCB or
multicomponent pesticides may contain over 100 peaks of various heights. Since many of the smaller
peaks disappear from low concentration standards and samples, we normally use only the largest, most
distinctive peaks for quantitation. This tends to keep responses more linear and provides more accurate
results at the lower concentration levels. Quantitation using all peaks tends to skew results near the
detection limits so that samples appear to be lower in concentration than they actually are. This
phenomenon is caused because the smaller peaks, which were used to develop the response factors, are no
longer detectable as part of the sample constituent.
Response: Use the largest number of peaks 'that will provide reliable quantitation of the compound. Five
peaks minimum is suggested.
ISSUE #21 - ACCEPTABILITY OF COMBINING ACID AND BASE/NEUTRAL EXTRACTS
PRIOR TO ANALYSIS "
This issue relates solely to Method 625.
10:6 For each fraction, assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used
in place of the K-D concentrator if the requirements of Section 8.2 are met.
Section 10.6 starts with the phrase "For each fraction", and goes on to describe the setup of a K-D
concentration apparatus. It also states that alternative concentration techniques can be used if the
. requirements in section 8.2 are met. We have found that the most efficient way to perform this step is by
concentrating the BN and A fractions together into one extract. This results in both an improvement in
recoveries and lower costs to the regulated community.
The increase in cost when the fractions are kept separate is dramatic because it carries throughout the
entire lab. Twice the amount of glassware is needed. Twice the amount of prep labor is needed to
perform the concentration step. Instrument time is doubled. Twice the number of reports are generated.
Data reduction is slowed.
Also, when the extracts are not combined there is a drop in the recoveries of the acid compounds. This is
caused because even at a pH greater than 11 the acid compounds are partially extracted into the basic
fraction. Once there, they are essentially lost to the analysis unless the fractions are later combined.
In the end, keeping the fractions separate results in no real increase in quality and a dramatic increase in
cost. Good resolution can still be maintained when the extracts are combined and the method detection
limits are still easily achievable. Is it acceptable to combine the BN and A fractions as long as the
requirements in Section 8.2 and the method detection limits can be met?
Draft, December 1996
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Streamlining Guide
Response: Yes and No. If the analytes can be reliably identified and quantified in each sample, the
extracts may be combined. If, however, the identification and quantisation of any analyte is adversely
affected by another analyte, a surrogate, or an interferant, the extracts must be analyzed separately. If
there is ambiguity, the extracts must be analyzed separately.
ISSUE # 22 - CHARACTERISTIC ION REQUIREMENTS
This issue relates solely to Method 625.
14.1 Obtain ElCPsfor the primary m/z and the two other masses listed in Tables '4 and 5. See Section 7.3
for masses to be used -with internal and surrogate standards. The following criteria must be met to make a
qualitative identification
Section 14.1 states that one primary and at least two secondary ions are to be used for qualitative
identification of all compounds. Can the analyst use professional judgement to drop or add characteristic
ions to account for interferences and other analytical difficulties?
Response: Yes, provided the identification of the analyte is as reliable as it would be if the specified m/z's
were used.
ISSUE # 23 - CHROMATOGRAPHIC RESOLUTION REQUIREMENTS
This issue relates solely to Method 625.
14.2 Structural isomers that have very similar mass spectra and less than 30 s difference in retention
time, can be explicitly identified only if the resolution between authentic isomers in a standard mix is
acceptable. Acceptable resolution is achieved if the baseline to valley height between the isomers is less
than 25% of the sum of the two peak heights. Otherwise, structural isomers are identified as isomeric
pairs.
What ramifications does this have on compliance monitoring where benzo(k)fluoranthene and
benzo(b)fluoranthene need to be identified? Should these compounds be reported as
"Benzofluoranthenes"? Is there any flexibility for analyst interpretation regarding isomer identification?
Response: If the isomers cannot be differentiated, the concentration should be checked against the lowest
regulatory concentration limit for the pair. In this instance, EPA recommends that a column that resolves
the pair be used.
ISSUE # 24 - QUANTITATION OF 2,3,7,8-TCDD
This issue relates solely to Method 625.
C-16
Draft, December 1996
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Current Method
1 7.1 If the sample must be screened for the presence of 2,3,7,8-TCDD, it is recommended that the
reference material not be handled in the laboratory unless extensive safety precautions are employed. It is
sufficient, to analyze the base/neutral extract by selected ion monitoring (SIM) GC/MS techniques, as
follows... - " >• .
Does the term "screen" imply that the method is non-quantitative for 2,3,7,8-TCDD? What should be
reported when performing this screen, "D" versus "ND"?
Response: Screen means that if 2,3,7,8-TCDD, is detected, the sample must be analyzed using an alternate
method specifically designed for the determination of 2,3,7,8-TCDD. EPA recommends Method 1613 for
this determination.
ISSUE # 25 - ALTERNATIVE CAPILLARY COLUMNS
The following citations are from Method 601. Identical or similar requirements are included in other
Methods as follows:
METHOD 601
SECTIONS
5.3.1
5.3.2
OTHER PERTINENT
METHOD(s)
602
624
EQUIVALENT
SECTION(s)
5.3.1
5.3.2
5.3.2
5.3,1 Column 1 - 6ft longx 0.082 in ID stainless steel or glass, packed with 5% 1,2,3-1200 and 1.75%
Bentone-34 on Supelcoport (100/120 mesh) or equivalent...
5.3.2 Column 2 - 8ft long xO.l in ID stainless steel or glass, packed -with 5% Tris(2-cyanoethoxy)propane
on Chromo W-AW (60/80 mesh) or equivalent...
Recently, new types of chromatographic columns have been developed that clearly demonstrate an
enhancement in the state-of the art. Can these chromatographic columns be used in Methods 601, 602 and
624?
Response: In response to numerous requests, on July 5, 1989, the Environmental Monitoring Systems
Laboratory (EMSL-Ci, now called NERL-Ci) recommended approval of the newer chromatographic
columns in Methods 601, 602, and 624 provided that the user demonstrates the achievement of
performance criteria, the performance criteria include accuracy, precision, and method detection limit as
outlined in section 8.2 of the method(s) and Appendix B of 40 CFR part 136. EMSL-Ci recommended
that the laboratory document the performance criteria prior to initiating any NPDES analyses.
Draft, December 1996
.C-17
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Streamlining Guide
ISSUE # 26 - COMBINATION OF 601 AND 602 METHODS
The following citations are from Method 601. Identical or similar requirements are included in other
Methods as follows:
METHOD 601
SECTIONS
5.3.3
OTHER PERTINENT
METHOD(s)
602
EQUIVALENT
SECTION(s)
5.3.3
5.3.3 Detector - Electrolytic conductivity or microcoulometric detector...
Can Methods 601 and 602 be combined with use of a photoionization detector in series with an
electrolytic conductivity detector?
Response: In response to numerous requests, on July 5, 1989, the Environmental Monitoring Systems
Laboratory (EMSL-Ci, now called NERL-Ci) recommended approval of the combination of Methods 601
and 602 with the use of a photoionization detector in series with an electrolytic conductivity detector
provided that the user demonstrates the achievement of performance criteria. The performance criteria
include accuracy, precision, and method detection limit as outlined in section 8.2 of the method(s) and
Appendix B of 40 CFR part 136. EMSL-Ci recommended that the laboratory document the performance
criteria prior to initiating any NPDES analyses.
ISSUE # 27 - ALTERNATIVE SORBENTS TRAPS
The following citations are from Method 601. Identical or similar requirements are included in other
Methods as follows:
METHOD 601
SECTIONS
5.2.2
OTHER PERTINENT
METHOD(s)
602
624
EQUIVALENT
SECTION(s)
5.2.2.1
5.2.2
5.2.2 ...The trap must be packed to contain the following minimum lengths of adsorbents: 1.0 cm of methyl
silicone coated packing (Section 6.3.3), 7.7 cm of 2,6-diphenylene oxide polymer (Section 6.3.2), 7.7 cm of
silica gel (Section 6.3.4), 7.7 cm of coconut charcoal (Section 6.3.1)...
Recently, new material have become available that appear to provide advantages over the sorbent traps
specified in the methods. Can these be used in place of the specified sorbents traps?
Response: On November 7, 1994, EMSL-Ci accepted of the use of alternative sorbents provided the data
acquired meets all quality control criteria described in Section 8 and provided the purge and desorption
procedures specified in the method are not changed. The performance criteria include accuracy, precision,
and method detection limit as outlined in section 8.2 of the method(s) and Appendix B of 40 CFR part
C-J8
Draft, December 1996
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Current Method Flexibility
136. EMSL-Ci recommended that the laboratory document the performance criteria prior to initiating any
NPDES analyses.
Although alternative adsorbents may be used, only some of the purging and desorption procedures can be
adjusted. The purging and desorption procedures were designed to achieve 100% purging efficiency and
recovery of the many regulated target analytes. The purge time and purge gas flow rate required to
efficiently purge the target analytes from the water samples are largely independent of the sorbent trapping
material. Decreasing the purging or desorption times or gas flows will have a negative impact on method
precision and may increase adverse matrix effects. Therefore, purge time and purge gas flow rate may not
be adjusted. Since many of the potential alternate sorbents may be thermally stable at temperatures higher
than 180 °C, however, the alternate traps may be desorbed and baked out at higher temperatures than
those described in the current method revisions. If higher temperatures are used, the analyst should
monitor the data for analyte and trap, decomposition. •
Draft, December 1996
C-19
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AppendixD
Suggested Data Elements
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Suggested Data Bemems
DEEMS VERSION 1.0
DATA ELEMENT DICTIONARY
DATA ELEMENT
DESCRIPTION
Acid_Reaction
Format: LimitecMList
Record: SampIe_and_Method
Record: Handling
Reaction of the sample to acid.
.Examples: Weak, Strong.
Same as in a Sample_and_Method record.
AIiquot_Amount
Format: Numeric
Record: Analysis
The amount of sample used for this analysis.
This usage of the word aliquot is not consistent with its
dictionary definition, but is standard for many chemists.
AIiquot_Amount_Units
Format: LimitedJList
.Record: Analysis
Units for Aliquot_Amount.
Alternate_Lab_Analysis_ID
Format: Identifier
Record: Analysis
Alternate lab identifier for an analysis. This value is for
information purposes only to facilitate tracking back into
the lab's systems.
Alternate_Lab_Sample_ID
Format: Identifier
Record: Sample_and_Method
Alternate lab identifier for a sample. This value is for
information purposes only to facilitate tracking back into
the lab's systems. It might be used when the lab has both
a lab-wide sample id and a different, department specific
for particular methods.
Amount_Added
Format: Numeric
Record: Result
Specifies a known amount of analyte that has been
spiked into the aliquot. Used with method QC samples
of QC_Category Blank_Spike, Spike,
Spike_Duplicate and Blank_Spike_Duplicate.
Draft December 1996
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analyte
Spike analytes should have 'Analyte_Type=Spike'.
Same as in a Result record extended so Amount_Added
can now refer to spikes, surrogates, tracers, standard
additions, and calibration standards where known
amounts of analytes have been added to samples for'QC
purposes.
'Analyte_Type=Spike' should be specified for spiked
analytes unless some other Analyte_Type is more
appropriate or which analytes were spiked is known
based on a QC_Type associated with this data.
Amount_Added_Error
Format: Numeric
Record: Result
Record: Analyte
The one sigma error in the estimate of the
Amount_Added.
Same as in a Result record.
Amount_Added_Error_Units
Format: LimitedJList
Record: Result
Record: Analyte
Units for Amount_Added_Error.
If the client specifies that the
Amount_Added_Error_Units must be the same as the
Amount_Added_Units, the Amount_Added_Error_Units
need not be specified.
Same as in a Result record.
Amount_Added_Units
Format: LimitedJList
Record: Result
Record: Analyte
Units for Amount_Added.
If the client specifies that the Amount_Added_Units
. must be the same as the ResultJLTnits, the
Amount_Added_Units need not be specified.
Same as in a Result record.
D-2
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Analysis_Batch
Format: Identifier
Record: Analysis
An identifier for a batch-of analyses on one instrument
associated with the level of detail at which the instrument
is checked to be in control.. • '.
Example: Analyses QC'd by the same continuing
calibration or similar_QC.
AnaIysis_Duration
Format: Numeric
Record: Analysis
Record: Analyte
The duration of the instrumentalanalysis.
Example: Radiochemical count time.
The duration of the instrumental analysis for this analyte.
Example: ICP integration time.
Analysis_Duration_Units
Format: Limited_List
Record: Analysis
Record: Analyte
Units for Analysis_Duration.
Units for Analysis_Duration.
Analysis_Group
Format: Identifier
Record: Analysis_Group
Record: Analysis
Required
A lab defined code for an Analysis_Group.
If an Analysis_Group is needed to fully identify what
was done, the Lab_Analysis_ID's in related Analysis ,
records might be constructed as the Analysis_Group ,
code combined with a suffix. For example, in dual
column GC, the GC data system often has a code for the
pair of analyses, which can be used as the
Analysis_Group identifier. Adding a column number to
this identifier gives a suitable Lab^_Analysis_ID.
The Analysis_Group this analysis is part of.
The Client_Method_ID or Analysis_Type should imply
whether or not an Analysis_Group is needed.
Draft, December 1996
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Result
If there is any ambiguity about which analyses underlie
this result, the Analysis_Group that identifies these
analyses.
AnaIysis_Request_n>
Format: Identifier
Record: SampIe_and_Method
Client's code for the paperwork that authorizes the
analyses of specific samples by listed methods.
Sometimes this is identical to the chain of custody
identifier.
Analysis_Type
Format: LimitedJList
Record: Analysis
Conditionally Required
Client's code to define the type of analysis. This code is
only needed if more than one analysis is done per
Analysis_Group.
Examples:
1. For dual column GC, this code identifies the type of
column (first or second) used. In current CLP practice,
the column identifier (really a manufacturer's code)
might be used for this value in lieu of a CLP-specified
value.
2. If several measurements are averaged to produce the
final result, codes for the first, second,... analyses done.
3. When doing a method of standard additions, this code
identifies the first, second,...analyses done. For example,
CLP codes are MSAO, MSA1,...
4. When every sample is spiked to measure the linear
response of the method, this code identifies the spiked
and unspiked analyses. This technique is used in some
radiochemistry methods (some versions of Tritium and
(Total Uranium), but it is rare to report the spiked
analysis except in the raw data, so no standard codes
exist.
5. When the method involves a secondary measurement
of some factor necessary to compute the result, this code
D-4
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: AnaIysis_Group
identifies the secondary analysis. For example, some
methods for PU-241 by liquid scintillation require a
separate alpha count of the tracer to determine the yield.
6. If client rules are to report only one (best) result after
reanalyses or dilutions, this code could classify each
analysis in these terms.
Client's code to define the type of Analysis_Group. This
code is only needed if more than one type of
Analysis_Group applies to one Sample_and_Methpd or
Instrument_QC record.
Example: For CLP Inorganics Method of Standard
Additions, Analysis_Groups are needed for normal and
Analytical Spike groups as well as the MSA groups.
Analyst
Format: Text
Record: Handling
Record: Analysis
Record: Cleanup
Name or initials for the analyst doing the work described
in this record.
Same as in a Handling record.
Same as in a Handling record.
Analyte_Name
Format: Text
Record: Result
Record: Analyte
Record: Analyte_Comparison
Record: Peak_Comparison
Lab assigned chemical name for the analyte. For GCMS
TlCs (Tentatively Identified Compounds), this name may
come from a mass spectral library.
Same as in a Result record
AnalyteJMame for the analyte to compare to.
Analyte_Name for the analyte to compare to.
Analyte_Type
Format: LimitedJList
Record: Result
Conditionally Required
In a Result record, required values, ignoring case, are:
Spike — This analyte has been spiked.
Draft, December 1996
D-5
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analyte
TIC — This analyte is non-routine and is tentatively
identified.
This field is not used for a routine analyte.
Same as in a Result record with the.following required
values, ignoring case, in addition to Spike and TIC:
Internal_Standard — Defined as per CLP usage.
Surrogate — Defined as per CLP usage.
System_Monitoring_Compound_ — Defined as per CLP
usage.
Tracer — Like an internal standard except it is added at
the beginning of sample preparation, rather than just
before analysis.
AnaIytical_Error
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
The estimated one sigma error in the result due to all
effects related to analysis by the lab.
Same as in a Result record extended to anything
considered to be the result of any analysis. Within an
Analysis_Group record, applies to a mean or other value
computed from several analyses.
Same as in an Analyte record when results are measured
per peak.
Analytical_Error_Units
Format: LimitedJList
Record: Result
Record: Analyte
Units for AnalyticalJError.
If the client specifies that the AnalyticalJBrrorJlJnits
must be the same as the ResultJLJnits, the
Analytical_Error_Units need not be specified.
Same as in a Result record.
D-6
Draft, December 1998
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Peak
Same as in a Result record.
Analyzed
Format: Date
Record: Analysis
Analysis date.
ApparatusJCD
Format: Identifier
Record: Analysis
Record: Handling
Record: Cleanup
The lab's code for the apparatus used to process an
aliquot.
Example: An identifier for a Purge and Trap device.
The lab's code for the apparatus used to process a
sample.
Example: An identifier for a TCLP device.
The lab's code for the apparatus used to cleanup an
aliquot.
Example: An identifier for a GPC device.
Artifacts
Format: Text
Record: Sample_and_Method
Record: Handling
Method defined concept used to report anomalies in the
sample.
Same as in a Sample_and_Methpd record.
Autosampler
Format: Limited_List
Record: Analysis
Whether an autosampler was used.
Background_Correction
Format: Limited List
Record: Analysis
Whether or not background correction was done.
Background_Raw_Data
Format: LimitedJList
Record: Analysis
Whether raw data was generated when background
correction was done.
Draft,. December 1996
D-7
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Example, used for CLP Inorganics ICP.
Background_Type
Format: LimitedJList
Record: Analysis
Record: Analyte
Record: Peak
The type of background correction done.
Example: CLP Inorganics Furnace AA distinguishes
Smith-Hieftje, Deuterium Arc, and Zeeman types.
Same as in an Analyte record, except specific to an
analyte.
Same as in an Analyte record, except specific to a peak.
B!as_Error_Ratio
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
For method QC of QC_Category, Blank_Spike, and
Blank_Spike_Duplicate, the difference between the
result and amount added as a fraction of the square root
of sum of squares of the one sigma analytical error and
one sigma amount added error.
Same as in Result records except applied to the results of
analyses in an analysis group rather than a QC sample
and original pair.
Same as in an Analyte record when results are measured
per peak.
BillingJDD
Format: Identifier
Record: Sample_and_Method
Client's code to submit with the data for billing purposes.
BoilingJPoint
Format: Numeric
Record: Sample_and_Method
Record: Handling
Boiling point of the sample.
Same as in a Sample_and_Method record.
Boiling Point Units
D-8
Draft, December 1996
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Suggested. Data Elements
DATA ELEMENT
DESCRIPTION
Format: Limited_List
Record: Sample_and_Method
Record: Handling
Units for the Boiling_Point.
Units for the BoilingJPoint.
Bottles
Format: Numeric
Record: Sample_and_Method
Number of sample bottles.
Bottle_ID
Format: Identifier
Record: Sample_and_Method
Record: Analysis
Identifier for the bottle containing the sample being
analyzed.
May repeat in one record if several bottles are treated as
one sample.
Identifier for the bottle containing the aliquot being
analyzed.
May repeat in one record if several bottles are used to
prepare one aliquot.
Calibration_Factor
Format: Numeric
Record: Analyte
Record: Peak
Factor used to convert measured to final results.
Same as in an Analyte record, except applied to a single
peak. ; - ' .
Calibration_Factor_Units
Format: Limited_List
Record: Analyte
Record: Peak
Units for Calibration_Factor
Units for Calibration Factor.
CAS_Number
Format: Identifier
Record: Result
The Chemical Abstract Service number for the analyte.
Only use values assigned by the Chemical Abstracts
Service with this field.
Values, can be entered with or without hyphen delimiters.
Draft, December 1996
D-9
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analyte
Record: Analyte_Comparison
Record: Peak_Comparison
Same as in a Result record.
CAS_Number for the analyte to compare to.
CAS_Number for the analyte to compare to.
Checksum
Format: Numeric
Record: All
A value based on all other data in a record that can be
used to check EDD integrity. This field can be used in
any record. Its value applies to the record it is in.
The required algorithm to compute the data for this field
is as follows:
For all data in a record, starting with the record type line,
ending before the next record type line or end of the data
stream, and ignoring:
1. The carriage return and linefeed at the end of each
line.
2. Any optional leading spaces in 'record:' and
'field='lines.
3. The entire line with the checksum field.
Compute the sum of the ASCII codes of all non-ignored
characters. Report this sum as an integer following the
'checksum='.
Clarity
Format: LimitedJList
Record: Sample_and_Method
Record: Handling
Record: Analysis
Clarity of the sample as received.
Examples: Clear, Cloudy, Opaque.
Clarity of the sample after the handling described in this
record.
Clarity of the aliquot after preparation.
D-10
Draft, December 1996
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Suggested-Data Elefnents
DATA ELEMENT
DESCRIPTION
Record: Cleanup
Clarity of the aliquot after the cleanup described in this
record.
Cleaned_Up
Format: Date
Record: Cleanup
Date of cleanup of this aliquot.
Cleanup_Batch
Format: Identifier
Record: Cleanup
The lab's identifier for a batch of aliquots cleaned up
together. The definition of a cleanup batch depends on
the method but might be linked to cleanup specific QC
samples such as GPC calibrations.
Example: All analyses associated with one GPC
calibration would be in one Cleanup_Batch of
CleanupJType GPC. The Instrument_QC in the batch
might have QCJFype GPC_Calibration.
Cleanup_ID
Format: Identifier
Record: Cleanup
The lab's identifier for this cleanup event for this aliquot.
Cleanup_Type
Format: Limited_List
Record: Instrument_QC
Record: Cleanup
For Portability
For instrument QC with QCJLinkage 'Cleanup_Batch', a
code that identifies the type of cleanup this QC pertains
to. The field's value must match that specified as the
Cleanup_Type for cleanups of associated analyses.
A code the specifies the type of cleanup. Valid values
might be specified for each Client_Method_ID.
Examples: GPC, Florisil, and Sulfur.
Clieht_Analysis_D3
Format: Identifier
Record: Analysis .
An optional client defined identifier for this analysis.
Examples: In the CLP, required analysis identifiers like
VBLKxy and INDALxy.
CIient_Analyte_ID
Draft, December 1996
D-11
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Format: Identifier
Record: Result
Record: Analyte
Record: AnalytejComparison
Record: Peak_Comparison
Required
The client's code for the analyte. This code should be the
basis on which the client recognizes the analyte.
Same as in a Result record.
Client_Analyte_ID for the analyte to compare to.
Client_Analyte_ID for the analyte to compare to. If not
specified, it is assumed to be the same as the analyte for
the Peak record this Peak_Comparison record is in.
ClientJTO
Format: LimitedJList
Record: Sample_and_Method
Record: Instrument_QC
For Portability
An identifier for the person or organization ordering the
analysis. Often client defined.
This value is necessary to allow one client to read data
reported in a format specified by another. To be fully
reliable, Client_ID's must be unique across all potential
clients. Someday they might be assigned by a central
group.
Examples: EPA Region, AFCID (Air Force Client ID),
Customer.
Same as in Sample_and_Method records.
CIient_Method_ID
Format: LimitedJList
Record: Sample_and_Method
Required
The client's code for the work to be done. The complete
code many be a composite of a number of values, such as
a CLP method code (OLM02.0), a fraction
(Semivolatiles) and a level (Low).
Full details about the meaning of fields and relationships
in the EDD are defined relative to the combination of this
value and the MatrixJD. Values for the
Client_Method_ID and MatrixJD should be specified in
the client's DEEMS implementation, possibly by
referencing the Client's Statement of Work (SOW).
D-12
Draft, December 1996
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Suggested Data
DATA ELEMENT
DESCRIPTION
Record: Instrument_QC
The Client_Method_ID is not a generic method number
that only identifies the analytical process. It must
address issues such as the number and types of QC
samples expected, what types of reanalyses and dilutions
are expected, and how to report final results when
reanalyses and\or dilutions are done. '
NOTE: The 'Client_ID' is required to make this code
unique across client boundaries.
Same as in Sample_and_Method records.
CIient_Name
Format: Text
Record: SampIe_and_Method
Record: Instrument_QC
Descriptive name for the person or organization ordering
the analysis. May be lab defined.
Examples: EPA Region, AFCID (Air Force Client ID),
Customer.
Same as in Sample_and_Method records.
Client_ReanaIysis_Type
Format: LimitedJList
Record: Sample_and_Method
Conditionally Required
If the client wants results for reanalyses done by this
method to be reported separately, the client defined code
to identify the reanalysis. The Client_Method_ID,
Client_Sample_ID and Client_Reanalysis_Type together
should uniquely identify the data associated with this
record except possibly for lab generated QC samples.
Reanalysis is defined as generally as possible to include
notions such as reextraction, dilution, and rework.
Example: DL, RE and REDL as used in the CLP.
CIient_SampIe_ID
Format:, Identifier
Record: Sample_and_Method
Required . ,
Client's identifier for a sample. This should be the basis
on which the client identifies the sample. However, not
all clients define values for lab generated QC samples.
Example: EPA Sample Number
Draft, December 1996
D-13
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Collected
Format: Date
Record: SampIe_and_Method
Date the sample was collected. If collected over a range
of dates, this is the start date.
CollectedJEnd
Format: Date
Record: SampIe_and_Method
If the sample was collected over a range of dates, the end
of the collection period.
Color
Format: LimitedJList
Record: Sample_and_Method
Record: Handling
Record: Analysis
Record: Cleanup
Color of the sample as received.
Color of the sample after the handling described by this
record.
Color of the sample after preparation
Color of the aliquot after the cleanup described by this
record.
Column
Format: Text
Record: Analysis
Record: Cleanup
Name of the column used for analysis
Name of the column used for this Cleanup.
Example: GPC column identifier.
Column_Internal_Diameter
Format: Numeric
Record: Analysis
Internal diameter of the analytical column.
Column_Internal_Diameter_Units
Format: LimitedJList
Record: Analysis
Units for Column Internal Diameter.
Comment
Format: Text
Repeals OK
D-14
Draft, December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: All
A free-form comment that can occur in any record. Its
value applies to the data in the record it is in. The exact
location of a Comment field in a record is not
significant. There can be many Comment fields in one
record. The order in which these occur may be
significant to their meaning.
Comment fields, as opposed to ';comments', are meant to
be related to data reported in other fields in the same
record. Readers are not required to take any action based
on these comments, but they might choose to record
them as text comments in their database.
Composite.
Format: LimitedJList
Record: Sample_and_Method
If the sample is a composite.
Conductance .
Format: Numeric
Record: SampIe_and_Method
Conductance of the sample.
Conductance_units
Format: LimitedJList
Record: SampIe_and_Method
Units for Conductance.
Confirmation_AnaIysis_ID
Format: Identifier
Record: Analysis
Record: Analysis_Group
Identifier for an analysis.that confirms the results of this
analysis.
Example: Confirmatory GCMS Lab File ID in CLP
Pesticides.
Same as in Analysis record except confirming results
from this Analysis_Group.
Consolidation
Format: LimitedJList
Record: Sample_and_Method
Degree of consolidation of the sample. Weak, Moderate
etc.
Correction_Factor
Format: Numeric
Draft, December 1996
D-15
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: AnaIyte_Comparison
The correction factor for the peak this record is in, based
on iriteranalyte effects from the analyte named in this
record.
Correlation_Coefficient
Format: Numeric
Record: Analyte
Record: Peak
The correlation coefficient resulting from linear
regression of data. Used for an analyte in an
Analysis_Group record.
Same as in an Analyte record when results are measured
per peak.
Counting_Error
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
For methods based on counting discrete events, such as
are common in radiochemistry, the one sigma error in the
net count rate, usually scaled to the same units as the
result. A more precise definition of Counting_Error may
specified for each method. •
Same as in a Result record extended to anything
considered to be the result of any analysis. Within an
Analysis_Group record, applies to a mean or other value
computed from several analyses.
Same as in an Analyte record when results are measured
per peak.
Counting_Error_Units
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
Units for CountingJError.
If the client specifies that the Counting_Error_Units must
be the same as the Result_Units, the
Counting_Error_Units need not be specified.
Same as in a Result record.
Same as in a Result record.
D-16
Draft, December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Created
Format: Date
Record: Sample_and_Method
The date a QC sample was generated or derived in the
lab.
CustodyJQ}
Format: Identifier
Record: Sample_and_Method
Client's code for the chain of custody document
associated with receipt of this sample in the lab.
Date_Format
Format: Limited_List
Record: Header
A value that specifies the format of all date/time values
that follow this Header record. Allowed values for this
field are listed with the description of allowed date
formats for field values. A required Date_Format value
may be specified by the client or implementation.
Density
Format: Numeric
Record: SampIe_and_Method
Record: Handling
The density of the sample.
\ • .
The density of the sample after the handling described by
this record.
Detection_Limit
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
Detection limit for the analyte being measured.
Same as in a Result record extended to anything
considered to be the result of any analysis. Within an
Analysis_Group record, applies to a mean or other value
computed from several analyses. For Instrument_QC,
the value might be an instrument detection limit.
Same as in an Analyte record when results are measured
per peak.
Detection_Limit_Type
Format: LimitedJList
Record: Result
One of a list of client defined acronyms that specify the
type of detection limit.
Draft, December 1996
D-17
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analyte
Record: Peak
Examples: CRDL, MDA, MDL, IDL.
Same as in a Result record.
Same as in a Result record.
Detection_Limit_tInits
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
Units for DetectionJLimit.
Same as in a Result record.
Same as in a Result record.
Detector_Type '
Format: LimitedJList
Record: Analysis
The type of detector used in the instrumental analysis.
This is not an instrument identifier.
Examples: FID, GCMS.
DifierenceJErrorJRatio
Format: Numeric
Record: Result
The absolute value of the difference of two values as
fraction of the square root of sum of squares of their one
sigma analytical errors. Used with method QC of
QC_Category Duplicate,
Serial_Dilution,Spike_Duplicate and
Blank_Spike_Duplicate.
Record: Analyte
Record: Peak
Same as in Result records except applied to the results of
analyses in an analysis group rather than a QC sample
and original pair.
Same as in an Analyte record when results are measured
per peak.
Dilution
Format: Numeric
D-18
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Analysis
The overall dilution of the sample aliquot. A value of
one should correspond to nominal conditions for the
method. Values less than one correspond to
concentrations. Exactly which factors are included in the
dilution may depend on the. method.
Dilutions
Format: Numeric
Record: Analysis
Number of dilutions done to this^ aliquot.
Drift
Format: Numeric
Record: Analysis
Record: Analyte
Record: Peak
The difference between the actual location of a peak and
its predicted position. For alpha spectroscopy, Drift is
computed using the tracer peak.
Same as in an Analysis record except applied to a
specific analyte.
Same as in an Analysis record except applied to a
specific peak.
DriftJJnits
Format: Limited_List
Record: Analyte
Record: Analysis
Record: Peak
Units for Drift.
Units for Drift.
Units for Drift.
EDDJQD
Format: LimitedJList
Record: Header
Required
Must have the value DOE_EM_EDD. It can be checked
by readers to determine that following data are in a
DEEMS compatible format. Since this field need not be
the first line in a Header record, readers need to be
prepared to read all the Header record lines before
making this pheck.
EDD_Implementation_ID
Format: Limited_List
Record: Header
Required
A value specified in a DEEMS implementation
document as the identifier of the implementation. This
Draft, December 1996
D-19
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
value should be checked by readers to determine that
following data are in a processible format. For example,
an implementation might specify what records and data
elements are required in the.EDD, including any
implementation defined fields.
Since this field need not be the first line in a Header
record, readers need to be prepared to read all the fields
in this record before checking this value.
EDD_Inaplementation_Version
Format: LimitedJList
Record: Header
Required
A value specified in each revision of a DEEMS
implementation document. The value in an EDD
indicates the version of the implementation that
following data is compatible with. Reader programs may
have to adapt their behavior based on this value. In
particular, the list of implementation defined fields may
change with version number.
Implementors should assign version numbers so that later
versions have later alphabetical version numbers.
EDDJVersion
Format: Limited_List
Record: Header
Required
Specified in each revision of this document. Specified
by the writer of an EDD to indicate the version of the
DEEMS that following data is compatible with. Reader
programs may have to adapt their behavior based on this
value. In particular, the list of DEEMS defined fields
may change with version number.
Efficiency
Format: Numeric
Record: Analysis
Efficiency of the instrument as a percent. Usually used
in radiochemistry to mean the counts detected as a
percentage of the decays actually occurring.
Record: Analyte
Same as in an Analysis record except applied to a
specific analyte.
D-20
Draft December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Peak
Same as in an Analysis record except applied to a
specific analyte and peak.
\ Energy
Format: Numeric
Record: Peak
Record: Peak_Comparison
The energy of an emission.
Same as in a Peak record.
Energy_Units
Format: Limited_List
Record: Peak
Record: Peak_Comparison
Units for Energy.
Units for Energy.
Equipment_Batch
Format: Identifier
Record: SampIe_and_Method
An identifier for a batch of samples collected using the
same equipment in a defined period of time.
Operationally, this batch associates a field equipment
blank with a group of samples. This value is currently
often not known to the lab. It might be merged with lab
data by a validator.
Field_SampIe_ID
Format: Identifier
Record: SampIe_and_Method
Identifier assigned to a sample by the sampler, not the
client. This value is currently often not known to the lab.
It could be useful as link into the sampling records
system.
Final_Amount
Format: Numeric
Record: Analysis
Record: Cleanup
The amount of sample remaining after final preparation
for.analysis.
Amount of material coming out of cleanup.
FinaI_AmountJUmts
Format: LimitedJList
Record: Analysis
Record: Cleanup
Units for Final_Amount.
Units for Final Amount.
Draft, December 1996
D-21
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
FlowJRate
Format: Numeric
Record: Analysis
Rate of flow of gas or liquid mobile phase for GC or
HPLC. . ' „•
FIow_Rate_Units
Format: Limited_List
Record: Analysis
Units for Flow Rate.
Fraction
Format: Limited_List
Record: Sample_and_Method
The fraction of a sample, based on a physical or chemical
separation, to which the method is applied.
Frequency
Format: Numeric
Record: Peak
Record: Peak_Comparison
The frequency of an emission or absorption.
Same as in a Peak record.
Frequency_Units
Format: LimitedJList
Record: Peak
Record: Peak_Comparison
Units for Frequency.
Units for Frequency.
GeneratingjSystem_ID
Format: Identifier
Record: Header
A lab defined value that identifies the software system
used to generate the EDD. This value may be built into
commercial software. The reader may use this value to
adapt to known quirks of the generating system.
Generating_System_Version
Format: Text
Record: Header
A lab defined version number for the software system
used to generate the EDD.
Gradient
Format: Numeric
D-22
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Analysis
Temperature gradient for GC and mobile phase gradient
forHPLG.
Gradient_Units
Format: Limited_List
Record: Analysis
Units for Gradient.
Handled
Format: Date
Record: Handling
Date of handling of this sample.
Handling_Batch
Format: Identifier
Record: Handling
The lab's identifier for a batch of samples handled
together. The definition of a handling batch depends on
the method but might be linked to handling specific QC
samples.
Example: All samples associated with one TCLP
apparatus blank would be in one HandlingJBatch of
Cleanup_Type TCLP. The method QC sample in the
batch might have QCJType TCLPJBlank,
Handling_Duration
Format: Numeric
Record: Handling
The duration of the handling.
Example: TCLP leaching time.
HandIing_Duration_Units
Format: LimitedJList
Record: Handling
Units for HandlingJDuration.
HandlingJFactor
Format: Numeric
Record: Handling
A factor that reflects processing done early in sample
handling.
For example, used in radiochemistry with a hot lab that
does preliminary processing prior to more routine
activities.
HandIing_Factor_Units
Draft, December 1996
D-23
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Format: Limited_List
Record: Handling
Units for Handling_Factor.
HandlingJDD
Format: Identifier
Record: Handling
The lab's identifier for this handling event for this
sample.
HandlingJType
Format: Limited_List
Record: Sample_and_Method
Record: Handling
Conditionally Required
For a method QC sample with QCJLinkage
'Handling_Batch', a code that identifies the type of
handling this QC pertains to. The field's value must
match that specified as the Handling_Type for handlings
of associated samples.
Code that describes preliminary processing done to a
sample prior to aliquotting.
Examples: Ashed, Decanted, Distilled, Drained, Dried,
Filtered, Leached. .
HeatedJPurge
Format: LimitedJList
Record: Analysis
Whether volatiles analysis used a heated purge.
Initial_Amount
Format: Numeric
Record: Cleanup
Amount of material going into cleanup.
Initial_Amount_Units
Format: LimitedJList
Record: Cleanup
Units for Initial Amount.
Injection_Volume
Format: Numeric
Record: Analysis
The volume of sample injected into the instrument.
Injection_Vblume_Units
Format: LimitedJList
Record: Analysis
Units for InjectionJVolume.
D-24
Draft, December 1996
-------
Suggested Date Elements
DATA ELEMENT
DESCRIPTION
Instrument_ID
Format: Identifier
Record: Analysis
The lab's code for an instrument.
Instrument_Serial_Number
Format: Text
Record: Analysis
The serial number of the instrument used for analysis.
Note, this is not a numeric field.
Interelement_Correction
Format: Limited_Ljst
Record: Analysis
Whether ICP interelement correction factors were
applied.
Lab_Address
Format: Text
Record: Sample_and_Method
Repeats OK
Address of the lab doing this analysis.
May repeat in one record as needed to report a multi-line
address.
Lab_Analysis_D3
Format: Identifier
Record: Analysis
Required
The lab's identifier for an analysis. This value should be
unique at least for all analyses in one lab reporting batch
in the context of one method. ^
Example: Lab file ID as used with GCMS analyses,
planchet as used in radiochemistry.
Record: Result
If there is any ambiguity about which analysis underlies
this result, the Lab_Analysis_ID of this analysis.
Example: In CLP Inorganics, to identify from which of
several dilutions the reported result is chosen.
Lab_Analyte_ID
Format: Identifier
Record: Result
Record: Analyte
For traceability
The lab's code for the analyte. This code gives
traceability into the lab's systems.
Same as in a Result record.
Draft, December 1996
D-25
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Peak_Comparison
Record: Analyte_Comparison
Lab_Analyte_ID for the analyte to compare to. If not
specified, it is assumed to be the same as the analyte for
the Peak record this Peak^Comparison record is in.
Lab_Analyte_ID for the analyte to compare to.
Lab_Contact
Format: Text
Record: Sample_and_Method
The person at the lab to contact with questions about this
data.
Lab_Contract
Format: Text
Record: Sample_and_Method
Contract number under which the lab analyzes the
samples. Client defined.
Lab_Data_Package_ID
Format: Identifier
Record: SampIe_and_Method
Lab's code for the data package this data is part of. This
code applies to a single deliverable. Use
Lab_Reporting_Batch for the logical notion of a group of
samples reported as a unit.'
For example, a document number the lab assigns to the
physical data package or a file name for an electronic
deliverable.
Lab_Data_Package_Name
Format: Text
Record: SampIe_and_Method
Lab's title for the data package this data is part of.
Lab_Data_Package_Version
Format: Text
Record: Sample_and_Method
If the lab resubmits a data package, this field can be used
to distinguish the different versions.
Lab_ID
Format: Limited_List
Record: Sample_and_Method
Required
Identifier for the lab doing this analysis. Often client
defined.
D-26
Draft, December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Instrument_QC
Same as in Sample_and_Method records.
Lab_Manager
Format: Text
Record: Sample_and_Method
The person at the lab who takes final responsibility for
this data.
Lab_Manager_Title
Format: Text
Record: Sample_and_Method
The corporate title of the Lab_Manager.
Lab_Method_ID
Format: Identifier
Record: Sample_and_Method
Record: Instrument_QC
For Traceability
The lab's code for the method used. Unlike the
Client_Method_ID, this ID is only used to identify work
done in the context of a lab defined sample, so it need
not have a globally defined meaning by itself.
Same as in Sample_and_Method records.
Lab_Method_Name
_ Format: Text
Record: SampIe_and_Method
Record: Instrument_QC
The lab's descriptive name for this method.
Same as in Sample_and_Method records.
Lab_Name .
Format: Text
Record: Sample_and_Method
Record: Instrument_QC
Descriptive name for the lab doing this analysis. Often
lab defined.
Same as in Sample_and_Method records.
Lab_Narrative_ID
Format: Identifier
Record: SampIe_and_Method
Lab's code for any narrative document associated with
this data.
Lab_Qualifier
Format: Limited List
Repeats OK
Draft, December 1996
D-27
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Result
Record: Analyte
Record: Peak
Record: Analyte_Comparison
Record: Peak_Comparison
A result qualifier code assigned by the lab, based on
client defined rules and values. This field may repeat as
many times as needed to report multiple codes per result.
Same as in the Result record.
Same as in the Result record.
Same as in the Result record.
Same as in the Result record.
Lab_Qualifiers
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
Record: Analyte_Comparison
Record: Peak_Comparison
A string of single letter result qualifiers assigned by the
lab, based on client defined rules and values.
Same as in the Result record.
Same as in the Result record.
Same as in the Result record.
Same as in the Result record.
Lab_Reanalysis_Suffix
Format: Identifier
Record: Sample_andJVfethod
For Traceability
If the client wants results for reanalyses done by this
method to be reported separately, the lab defined code to
help identify the reanalysis. The Lab_Method_ID,
Lab_Sample_ID and Lab_Reanalysis_Suffix together
should uniquely identify the data associated with this
record.
LabJReceipt ,
Format: Date
Record: Sample_and_Method
Date the sample was received in the lab.
Lab Reported
Format: Date
Record: Sample_and_Method
Date these data were reported by the lab.
D-28
Draft, December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Lab_Reportin^_Batch
Format: Identifier
Record: SampIe_and_Method
An identifier for a batch of samples reported as a group
by the lab. In addition to its use for administrative
purposes, this batch can be used to link certain QC
samples to regular ones, for example, a CLP storage
blank.
Example: Sample Delivery Group (SDG) as in the CLP.
Lab_Result_Status
Format: Limited_List
Record: SampIe_and_Method
Record: Result
Lab assigned status, such as preliminary or final, for
results for this sample and method. A client might define
allowed values for this field.
Lab assigned status, such as preliminary or final, for this
result. A client might define allowed values for this
field.
Lab_Sample_ID
Format: Identifier '
Record: Sample_and_Method
For Traceability
Lab's identifier for a sample. This code is the primary
link into the lab's record keeping system. It is not
necessarily one-to-one with the Client_Sample_ID.
Level
Format: LimitedJList
Record: SampIe_and_Method
Approximate level of analytes in the sample, usually
specified in client defined concentration ranges and
determined via a screening procedure.
Examples: Low, Medium, High.
Location_ID
Format: Identifier
Record: Sample_and_Method
Identifier for the sampling location at a site. Often client
defined.
Examples: Operable unit, well, tank, station, facility
(building), installation, aggregate area.
Draft, December 1996
D-29
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Location_Name
Format: Text
Record: Sample_and_Method
Descriptive name for the sampling location at a site.
May be lab defined.
Examples: Operable unit, well, tank, station, facility
(building), installation, aggregate area.
LotJNumber
Format: Text
Record: Cleanup
Manufacturer's batch number for something used in this
cleanup.
Example: Florisil cartridge lot number.
Mass_Charge_Ratio
Format: Numeric
Record: Peak
Record: Peak_Comparison
The mass/charge relationship recorded in MS detection.
Same as in a Peak record. ,
MatrixJD
Format: LimitedJList
Record: SampIe_and_Method
Required
A code for the sample matrix or media (e.g., soil, water).
Should be client defined. This value, combined with the
Client_Method_ID, defines to the reader method details
that are implementation specific!
Matrix_Name
Format: Text
Record: Sample_and_Method
A description of the sample matrix or media. Often lab
defined.
MeltingJPoint
Format: Numeric
Record: Sample_and_Method
The temperature at which the sample melts.
Melting_Point_Units
Format: Limited List
D-30
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Sample_and_Method
Units for MeltingJPoint.
Method_Batch
Format: Identifier
Record: Sample_and_Method
An identifier for a batch of samples analyzed by one
method and treated as a group for QC purposes. A
method batch should group samples with similar
matrices and potential interferences. This is a broader
grouping than a preparation batch. In particular, a
reanalysis of a sample stays in the same method batch,
while it is likely to be in a different preparation batch.
Operationally, this batch associates sample dependent
QC such as duplicates and matrix spikes with a group of
samples.
Example: All samples of one matrix and level, analyzed
by a CLP semivolatiles method and reported in one
SDG.
Organism_Class
Format: Limited_List
Record: SampIe_and_Method
A broad classification of a sample organism. Not
necessarily intended to be the taxonomic class, but that is
a possible value.
Example: Animal, Commercial Animal, Fish, or Plant.
OrganismJLength
Format: Numeric
Record: SampIe_and_Method
Length of an organism.
Orgattism_Length_Units
Format: LimitedJList
Record: Sample_and_Method
Units for OrganismJLength.
OrganismJPortion
Format: LimitedJList
Record: Sample_and_Method
Portion of an organism used for analysis.
OrganismjSex
Format: Limited List
Draft, December 1996
D-31
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: SampIe_and_Method
Sex of an organism: Male or Female.
Original_Client_Reanalysis_Type
Format: LimitedJList
Record: SampIe_and_Method
Conditionally Required
For a method QC sample with QC_Category Duplicate,
Serial_Dilution, Spike or Spike_Duplicate there must be
an associated regular sample the QC sample is derived
from. This sample is called the original. The value of
Original_Client_Reanalysis_Type matches that of the
Client_Reanalysis_Type for this original sample.
Original_Client_Sample_ID
Format: Identifier
Record: SampIe_and_Method
Conditionally Required
For a method QC sample of QC_Category Duplicate,
SerialJDilution, Spike or Spike_Duplicate there must be
an associated regular sample the QC sample is derived
from. This sample is called the original. The value of
Original_Client_Sample_ID matches that of the
Client_Sample_ID for this original sample.
For a method QC sample of QC_Category
Blank_Spike_Duplicate, the value of
Original_Client_Sample_ID matches that of the
Client_Sample_ID for the associated Blank_Spike.
Original_Lab_Reanalysis_Suffix
Format: Identifier
Record: SampIe_and_Method
For Traceability
For a method QC sample with QC_Categofy Duplicate,
SerialJDilution, Spike or Spike_Duplicate there must be
an associated regular sample the QC sample is derived
from. This sample is called the original. The value of
Original_Lab_Reanalysis_Suffix matches that of the
Lab_Reanalysis_Suffix for this original sample.
OrigmalJLabJSampleJDD
Format: Identifier
Record: Sample_and_Method
For a method QC sample with QC_Category Duplicate,
Serial_Dilution, Spike or Spike_Duplicate there must be
an associated regular sample the QC sample is derived
from. This sample is called the original. The value of
D-32
Draft, December 1996
-------
Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Original_Lab_Sample_ID matches that of the
Lab_Sample_ID for this original sample.
For a method QC sample with QC_Category
Blank_Spike_Duplicate, the value of
Original_Lab_Sample_ID matches that of the
Lab_Sample_ID for the associated Blank_Spike.
PeakJD
Format: Identifier
Record: Result
Record: Analyte
Record: Peak
Record: Peak_Comparison
Conditionally Required
If there is any ambiguity about which peak underlies this
result, the Peak_ID of that peak.
. If there is'any ambiguity about which peak underlies this
analyte's result, the PeakJD of that peak.
A lab specified value, possibly based on client specified
rules, that identifies a peak associated with an analyte.
Peak_ID is conceptually similar to Client_Analyte_ID,
except it identifies a peak rather than an analyte. Its
value should be unique, among all peaks for one analyte.,
but not necessarily have physical meaning.
Examples: nominal mass for GCMS peaks, integer
wavelength for ICP peaks, sequence number (1,2,...) for
multicomponent GC peaks.
Peak identifier for the peak to compare to. It is
combined with the Lab_Analyte_ID in the same
Peak_Comparison record to fully specify the peak to
compare to.
Percent_Breakdown
Format: Numeric
Record: Analyte
Record: Peak
The percent breakdown (DDT/Endrin) reported for CLP
pesticides.
Same as in an Analyte record when results are measured
per peak..
Percent_Difference
Format: Numeric
Draft, December 1996
D-33
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Result
Record: Analyte
Record: Peak
Record: Peak_Comparison
The difference between two measured values as
percentage of one of them. The denominator value is
usually the more certain one, although details can be
method specific.
Used with method QC of QC_Category Serial Dilution.
Same as in Result records except applied to the results of
analyses in an analysis group rather than a QC sample
and original pair.
Same as in an Analyte record when results are measured
per peak.
Same as in a Result record except used to compare
values in two Peak_Comparison records.
PercentJVlatch
Format: Numeric
Record: Analyte
Percent match of an analyte as compared with a library
mass spectrum.
PercentJMoisture
Format: Numeric
Record: Sample_and_Method
Record: Handling
Percent of sample composed of water.
Percent of sample composed of water after the handling
described by this record.
Percent_Phase
Format: Numeric
Record: Sample_and_Method
Record: Handling
Percent of sample in analyzed phase. This field may
generalize ones like Percent_Solids.
Percent of sample in analyzed phase after the handling
described by this record.
Percent_Preparation_Error
Format: Numeric
Record: Analysis
Same as in a Result record, except applies to all results
from this analysis.
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Result
Record: Analyte
The uncertainty introduced into the final result by all lab
activities other than instrumental analysis. Expressed as
a percentage of the result value at one sigma.
Same as in a Result record..
Percent_Ratio
Format: Numeric
Record: Peak_Comparison
The response of the peak this Peak_Comparison record is
in as a percentage of the response of the peak identified
by the PeakJD'and Lab_Analyte_ID in this record.
Used with mass spectral peaks in System Monitoring
Compounds.
PercentJRecovery
Format: Numeric
Record: Result
For method QC of QC_Category Blank_Spike and
Blank_Spike_Duplicate, the result as a percentage of the
amount added.
Record: Analyte
Record: Peak
For method QC of QC_Category Spike and
SpikeJDuplicate, the spiked result minus the original
result as a percentage of the amount added.
Same as in Result records except applied to the results
from an analysis or analyses in an analysis group rather
than a QC sample and original pair.
Same as in an Analyte record when results are measured
per peak.
Percent_ReIative_Abimdance
Format: Numeric
Record: Peak
The response of this peak as a percentage of the largest
peak response for this analyte.
Percent_Relative_Standard_Deviation
Format: Numeric
Record: Analyte
The standard deviation as a percentage of the mean.
Used for an analyte in an Analysis_Group record.
Draft, December 1996
D-35
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Peak
Record: Peak_Comparison
Same as in an Analyte record when results are measured
per peak.
Same as in an Analyte record except applied to
Peak_Comparison values.
Percent_Solids
Format: Numeric
Record: Sample_and_Method
Record: Handling
Percent of the sample composed of solid material.
Percent of the sample composed of solid material after
the handling described by this record.
Percent_Valley
Format: Numeric
Record: Analyte
Record: Peak_Comparison
The valley between this analyte and another one, as a
percentage of the height of the shorter one. The second
analyte is assumed to be known based on the method.
The valley between the peak this Peak_Comparison
record is in and the peak identified by the Peak_ID and
Lab_Analyte_ID in this record as a percentage of the
height of the shorter one.
pH
Format: Numeric
Record: Sample_and_Method
Record: Handling
The negative of the logarithm of the hydrogen ion
potential.
Same as in a Sample_and_Method record.
Phase_AnaIyzed
Format: LimitedJList
Record: Sample_and_Method
That portion of a multiphase sample actually analyzed.
Preparation_Batch
Format: Identifier
Record: Analysis
An identifier for a batch of aliquots that are prepared
together. For methods with no processing prior to
D-36
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
analysis, the preparation batch can be simply a group of
aliquots selected for analysis at roughly the same time.
Preparation batches are used to link analyses of regular
samples with lab generated method QC samples of
QC_Category Blank, BlankjSpike and
Blank_Spike_Duplicate, such as method blanks, lab
control samples and duplicate lab control samples.
Preparation_Type
Format: LimitedJList
Record: Analysis
A client defined code for the basic type of preparation
done.
Example: Extraction technique for semivolatiles. Could
be a 3000 series SW-846 method code.
Prepared
Format: Date
Record: Analysis
Preparation date. Preparation is used generally to include
method specific techniques such as extraction, digestion
and separation.
Preservative
Format: Text
Record: Sample_and_Method
Preservative added to the sample.
PreservedJBy
Format: Text
Record: Sample_and_Method
Organization that added preservative to the sample.
Priority_ID
Format: Limited_List
Record: Sample_and_Method
Client's code that identifies the priority assigned to this
data. The priority may affect the desired turn around
time and the cost of analysis.
Examples: Rush or quick turn around work.
Procedure_ID
Format: Identifier
Record: Analysis
Identifier for the lab's procedure (SOP) for this analysis.
Draft, December 1996
D-37
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Handling
Record: Cleanup
Identifier for the lab's procedure (SOP) for this handling.
Identifier for the lab's procedure (SOP) for this cleanup.
Pro cedure_Name
Format: Text
Record: Analysis
Record: Handling
Record: Cleanup
Description of the lab's procedure (SOP) for this
analysis.
i
Description of the lab's procedure (SOP) for this
handling.
Description of the lab's procedure (SOP) for this
cleanup.
ProjectJO)
Format: Identifier
Record: Sample_and_Method
Identifier for the project this sample is a part of. Often
client defined. Typically, a project consists of samples
from one site collected over some defined period of time.
Examples: Case no, Episode, Sampling round.
Project_Name
Format: Text
Record: Sample_and_Method
Descriptive name for the project this sample is a part of.
May be lab defined.
Examples: Case no, Episode, Sampling round.
QC_Category
Format: Limited_List
Record: SampIe_and_Method
For Portability
DEEMS defined code that specifies basic properties of a
method QC sample. In a Sample_and_Method record,
allowed values, with case ignored, are:
Blank — A QC sample with 'nothing' in it. Examples:
Field, equipment, method (reagent), sulfur, and storage
blanks.
D-38
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Blank_Spike — A QC sample with a known amount
added to a blank. Examples: lab control sample, QC
check samples and interference check samples.
Duplicate — A reanalysis of a regular sample done for
QC purposes. Examples: duplicates and splits.
Blank_Spike Duplicate— A reanalysis of a Blank_Spike.
Serial_Dilution — A dilution and reanalysis of a regular
sample done for QC purposes.
Spike ~ A reanalysis of a regular sample with a known
amount added and done for QC purposes.
Examples: matrix spikes, post digestion spikes and
analytical spikes. ,
Spike_Duplicate — A second reanalysis of a regular
sample with a known amount added and done for QC
purposes. There must be another sample with
QC_Category "Spike" with the same original sample.
QC_Linkage
Format: LimitedJList
Record: SampIe_and_Method
For Portability of QC
For a method QC sample,, specifies which batch is the
basis for the association between the QC sample and
regular ones. Allowed values, ignoring case, include the
following fields that define batches:
Sampling_Batch
EquipmentJBatch
ShippingJBatch
Lab_Reporting_Batch
MethodJBatch
Handling_Batch
Preparation_Batch
Analysis_Batch
If QC_Linkage is 'HandlingJBatch', there should be a
Handling_Type field in the Sample_and_Method record
whose value clarifies which type of handling batch is
intended.
Draft, December 1996
D-39
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Instrument_QC
Example: In a Sample_and_Method record, if the
QCJType is Lab_Duplicate, the QC_Category is
Duplicate and the QC_Linkage is MethodJBatch, a
reader knows that this data for is a client defined type of
QC called a Lab_Duplicate, that it is processed with rules
typical for Duplicates and that it is to be associated with
other Sample_and_Method records with the same value
for the MethodJBatch field. QCJLinkage is most useful
if the batch it names is a required field in appropriate
records, based on implementation rules.
The correct linkage for a field QC sample, may not be
known to the lab, so must be merged with lab data at a
later time.
Same as in a Sample_arid_Method Record except
allowed values for instrument QC, ignoring case, are
Cleanup_Batch, Preparation_Batch, Analysis_Batch and
Run_Batch.
If QC_Linkage is 'Cleanup_Batch', there should be a
Cleanup_Type field in the Instrument_QC record whose
value clarifies which type of cleanup batch is intended.
QQJType
Format: LimitedJList
Record: SampIe_and_Method
Record: Instrument_QC
For a method QC sample, the client's code for the type of
QC. In the context of the Client_Method_ID and
Matrix_ID, this code determines all special processing
rules for the QC sample. The presence of this field in the
Sample_and_Method record with a value allowed by the
implementation defines the sample as a method QC
sample.
A lab may not know that certain samples are field QC.
In this case the lab reports them as regular samples and
their type is changed later, possibly by the validator.
For instrument QC, a client defined code that specifies
what type of instrument QC data follows. In the context
D-40
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
of the Client_Method_ID, the value must imply enough
detail for^the reader to understand the method specific
details of the following Analysis_Group, Analysis,
Cleanup, Analyte, Peak, Peak_Comparison and
Analyte_Comparison records.
Quantitation_Limif
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
Quantisation limit for the analyte being measured.
Same as in a Result recqrd extended to anything
considered to be the result of any analysis. Within an
Analysis_Group record, applies to a mean or other value
computed from several analyses. .
Same as in an Analyte record when results are measured
per peak.
Quantitation_Limit_Type
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
One of a list of client defined acronyms that specify the
type of quantitation limit.
Examples: CRQL, PQL, SQL.
Same as in a Result record. .
Same as in a Result record.
QuantitationJLimitJQnits
Format: Limited_List
Record: Result
Record: Analyte
Record: Peak
Units for QuantitationJLimit. .
If the client specifies that the Quantitation_Limit_Units
must be the same as the ResultjLJnits, the
Quantitation_Limit_Units heed not be specified.
Same as in a Result record ••
Same as in a Result record.
Quench
Format: Numeric
Draft, December 1996
D-41
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analysis
Result of quench calculation for scintillation counters.
Refractive_Index
Format: Numeric
Record: SampIe_and_Method
Refractive index of sample.
Relative_Percent_Difference
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
Record: Peak_Comparison
The absolute value of the difference of two values as a
percentage of their average.
Used with method QC of QC_Category Duplicate,
SpikeJDuplicate and Blank_Spike_Duplicate.
Same as in Result records except applied to the results of
analyses in an analysis group rather than a QC sample
and original pair.
Same as in an Analyte record when results are measured
per peak.
Same as in a Result record except used to compare
values in two Peak_Comparison records.
ReIative_Response_Factor
Format: Numeric
Record: Analyte
Record: Peak_Comparison
The relative response factor for this analyte, based on the
assumption that the method specifies the analyte to
compare to and which peaks to use.
The relative response factor of the peak this
Peak_Comparison record is in compared to the peak
identified by the Peak_ID and Lab_Analyte_ID in this
record.
A relative response factor is the ratio of two response
factors, one for each peak. A response factor is the ratio
of a response to an amount added.
Requestor_ID
Format: Identifier
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Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Sample_and_Method
An identifier for the organization that requested that this
sample be analyzed. May not be the same as the client,
which specifies the SOW to follow.
Requestor_Name
Format: Text
Record: SampIe_and_Method
A name for the organization that requested that this
.samplebe analyzed.
Required_Detection_Limit
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
A contractually specified upper limit for the detection
limit for the analyte being measured. Depending on
client and method specific rules, required detection limits
might be scaled by factors such as dilution and percent
moisture prior to reporting.
Same as in a Result record.
Same as in a Result record. '
Required_Detectionr_Limit_Units
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
Units for Required_Detection_Limit.
If the client specifies that the
Required_Detection_Limit_Units must be the same as,
the Result_Units, me DetectionJLimitJLJnits need not be
specified. -
Same as in a Result record.
Same as in, a Result record.
Residue
Format: Numeric
Record: Analysis,
Solid material remaining after preparation of an aliquot.
ResidueJDnits
Format: Limited_List
Record: Analysis
Units for Residue.
Draft, December 1996
D-43
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Resolution
Format: Numeric
Record: Analysis
Record: Analyte
Record: Peak
A possibly sample and method dependent estimate of the
resolution of the instrument used in the analysis. For
example, in isotopic alpha spectroscopy, the width of the
tracer peak.
A possibly sample and method dependent estimate of the
resolution of the instrument that applies to the analysis
and analyte.
Resolution for this peak. Details of how resolution is
computed depend on the method.
Resolution_Units
Format: LimitedJList
Record: Analysis
Record: Analyte
Record: Peak
Units for Resolution.
Units for Resolution.
Units for Resolution.
Response
Format: Numeric
Record: Analyte
Record: Peak
Response from a detector. Can be any type of response
from ICP, AA, GC, MS, etc. Often, these are unitless
numbers relating to a signal from the detector.
Examples: Area, height, count rate.
Same as in an Analyte record, except for a single peak.
Example: individual Aroclor peak concentrations used
for CLP reporting.
Response_Units
Format: LimitedJList
Record: Analyte
Record: Peak
Units for Response.
Units for Response.
D-44
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Result
Format: Numeric
Record: Result
Record: Analyte
Record: Peak
Reportable result for the analyte.
Example: Concentration;
Same as in a Result record extended to anything
considered to be the result of any analysis. Within an
Analysis_Group record, applies to a mean or other value
computed from several analyses.
Same as in an Analyte record when results are measured
per peak. '
Result_Limit_Lower
Format: Numeric
Record: Result
Record: Analyte
Lower limit for a result based on external knowledge
about the sample. Units are the same as for Results.
Same as in the Result record.
Result_Limit_Upper
Format: Numeric
Record: Result
Record: Analyte
Upper limit for a result based on external knowledge
about the sample. Units are the same as for Results.'
Same as in the Result record.
Result_Units
Format: LimitedJList
Record: Result
Record: Analyte
Record: Peak
Units for Result.
Same as in a Result record.
Same as in a Result record.
Retention_Time
Format: Numeric
Record: Result
The time between injection and detection for mobile
phase separation techniques such as GC and HPLC.
(Time format hh:mm:ss is not allowed.)
Draft, December 1996
D-45
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Analyte
Record: Peak
In a result record, this is the retention time from the
analysis underlying this result.
Same as in a result record. .Used when there is a well
defined retention time for the analyte, not just for a peak
measurement for the analyte. For example, this applies
to GCMS analyses.
Same as in a Result record except for a single peak.
Used with techniques like GC where there can be
multiple peaks with different retention times for one
analyte.
Retention_Time_High
Format: Numeric
Record: Analyte
Record: Peak
High limit for a retention time window. Units are
specified with Retention_Time_Units.
Same as in an Analyte record, except for a single peak.
Retention_Time_Low
Format: Numeric
Record: Analyte
Record: Peak
Low limit for a retention time window. Units are
specified with Retention_Time_Units.
Same as in an Analyte record, except for a single peak.
Retention_Time_Umts
Format: Limited_List
Record: Result
Record: Analyte
Record: Peak
Units for Retention_Time.
Units for Retention_Time.
Units for Retention Time.
Rim_Batch
Format: Identifier
Record: Analysis
An identifier for a batch of analyses that make up a run, a
sequence of analyses during which the instrument is
continuously in control.
D-46
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Example: A batch of samples analyzed on one instrument
under the control of one initial calibration or similar
Instrument_QC.
Sample_Amount
Format: Numeric
Record: Sample_and_Method
Record: Handling
Weight or volume of sample as received by the lab.
Weight or volume of sample after the handling described
by this record.
Sample_Amount_Units
Format: LimitedJList
Record: SampIe_and_Method
Record: Handling
Units for Sample_Amount.
Units for the Sample_Amount.
SamplingJBatch
Format: Identifier
Record: SampIe_and_Method
An identifier for a batch of samples collected together.
Operationally, this batch associates a field blank with a
group of samples. This value is currently often not
known to the lab. It might be merged with lab data by a
validator.
Screen_Value
Format: Numeric
Record: SampIe_and_Method
Result from a screening analysis of the sample, as in an
alpha particle screen.
Screen_Value_Units
Format: LimitedJList
Record: SampIe_and_Method
Units for Screen Value.
Services_ID
Format: Identifier ^
Record: Sample_and_Method
Client's code for optional services performed for this
data.
This includes nonstahdard work, such as modified
detection limits, or changed QC requirements.
Draft, December 1996
D-47
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Examples: Special Analytical Services (SAS) number or
Analytical Service Level.
ShippingJSatch
Format: Identifier
Record: SampIe_and_Method
An identifier for a batch of samples shipped together,
such as in the same crate, cooler or ice chest.
Operationally, this batch associates a trip blank with a
group of samples. This value, as defined by the shippers,
is currently often not known to the lab. It might be -
merged with lab data by a validator.
SiteJD
Format: Identifier
Record: SampIe_and_Method
Identifier for the broadly defined site where the sample
was collected. Often client defined.
Site_Name
Format: Text
Record: SampIe_and_Method
Descriptive name for the broadly defined site where the
sample was collected. May be lab defined.
Standard_Deviation
Format: Numeric
Record: Analyte
Record: Peak
Record: Peak_Comparison
The standard deviation of several measurements of one
analyte. Used for an analyte in an Analysis_Group
record.
Same as in an Analyte record when results are measured
per peak.
Same as in an Analyte record when reporting peak
comparisons.
Standard_Deviation_Units
Format: LimitedJList
Record: Analyte
Units for Standard_Deviation.
If the client specifies that the Standard_Deviation_Units
• must be the same as the ResultJUnits, the
Standard_Deviation_Units need not be specified.
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Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: Peak
Record: Peak_Comparison
Same as in an Analyte record when results are measured
per peak.
Same as in an Analyte record except applied to
Peak_Comparison values. .
Standard_ID
Format: Identifier
Record: Analysis
Lab's identification for a standard, such as a spiking
material, used in this analysis.
Standard_Source
Format: Text
Record: Analysis
Source for a standard used in this analysis.
Suspended_Solids
Format: Numeric
Record: Sample_and_Method
Record: Handling
Solids remaining on the filter paper after filtration of a
water or other liquid sample.
Same as in a Sample_and_Method record.
Suspended_SoIids_Units
Format: Limited_List
Record: Sample_and_Method
Record: Handling
Units for Suspended_Solids.
Units for Suspended_Solids.
Temperature
Format: Numeric
Record: Sample_and_Method
Temperature of the sample as received.
Temperature_units
Format: Limited_List
Record: SampIe_and_Method
Units for temperature.
Texture
Format: Limited_List
Record: SampIe_and_Method
Descriptive information about a solid sample.
Draft, December 1996
D-49
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Handling
Example: Fine, medium and coarse; or: boulder, pebble
and sand; or: round and angular; or uniform and
irregular.
Descriptive information about a solid sample after the
handling described by this record.
Turbidity
Format: Numeric
Record: Sample_and_Method
Turbidity of the sample.
TurbidityJUnits
Format: LimitedJList
Record: Sample_and_Method
Units for Turbidity.
Validated
Format: Date
Record: SampIe_and_Method
Date validation completed.
Validation_QuaUfier
Format: LimitedJList
Record: Result
Repeats OK
A result qualifier code assigned by the validator, based
on client defined rules and values. This field is only used
with results for regular samples. This field may repeat as
many times as needed per result to report multiple codes,
Validation_Qualifiers
Format: Limited_List
Record: Result
A string of single letter result qualifiers assigned by the
validator, based on client defined rules and values. This
field is only used with results for regular samples.
Validator_Address
Format: Text
Record: SampIe_and_Method
Repeats OK
Address of the validator doing the validation. May
repeat in one record as needed to report a multi-line
address.
Validator_Contact
Format: Text
D-5O
Draft, December 1996
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Suggested Data Elements
DATA ELEMENT
DESCRIPTION
Record: SampIe_and_Method
The person at the validator to contact with questions
about this data.
VaIidator_Contract
Format: Text
Record: Sample_and_Method
Contract number under which the validator validates the
samples. Client defined.
Validator_Data_Package_ID
Format: Identifier ;
Record: Sample_and _Method
Validator's code for the data package this data is part of.
Validator_Data_Package_Name
Format: Text -
Record: SampIe_and_Method
Validator's title for the data package this data is part of.
Validator_Data_Package_y ersion
Format: Text
Record: Sample_and_Method
If the validator resubmits a data package, this field can be
used to distinguish the different versions.
ValidatorJD
Format: LimitedJList
Record: Sample_and_Method
Identification for the validator doing the validation.
Often client defined.
This and other 'validatorj fields are not typically known
to the lab. They are included for use by validators who
might receive a lab EDD, validate it and pass on an
updated EDD to the client.
Validator_Manager
Format: Text
Record: Sample_and_Method
The person at the validator who takes final responsibility
for this data:
Validator_Manager_Title
Format: Text
Record: SampIe_and_Method
The corporate title of the Validator_Manager.
VaIidator_Method_ID
Format: Identifier
Draft, December 1996
D-51
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Streamlining Guide
DATA ELEMENT
DESCRIPTION
Record: Sample_and_Method
The validator's code for the work it does.
Validator_Method_Name
Format: Text
Record: SampIe_and_Method
The validator's descriptive name for the work it does
when validating data analyzed by this method.
Validator_Name
Format: Text
Record: SampIe_and_Method
Descriptive name for the validator doing the validation.
Often validator defined.
Validator_Narrative_ID
Format: Identifier
Record: Sample_and_Method
Validator's code for any narrative document associated
with this data.
VaIidator_Receipt
Format: Date
Record: Sample_and_Method
Date sample data received by the validator.
ValidatorJReported
Format: Date
Record: Sample_and_Method
Date this work reported by the validator.
Wavelength
Format: Numeric
Record: Peak
Record: Peak_Comparison
The wavelength used for an analytical measurement; e.g.,
UV/vis, GFAA and ICP.
Same as hi a Peak record.
WavelengthJQnits
Format: LimitedJList
Record: Peak
Record: Peak_Comparison
Units for Wavelength.
Units for Wavelength.
Yield
Format: Numeric
D-52
Draft, December 1996
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Suggested Date Elements
DATA ELEMENT
DESCRIPTION
Record:- Analysis
A measure of the success of the preparation part of the
method as a percent. For radiochemistry, the number of
atoms of interest making it through sample preparation as
a percentage of the number in the aliquot.
Draft, December 1996
D-53
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Appendix E
Equivalency Checklists
-------
-------
Equivalency Checklists
The Checklist for Initial Demonstration of Method Performance, Checklist for Continuing
Demonstration of Method Performance, and Certification Statement (collectively called "Checklists") and
instructions for their completion are provided in this appendix. The Checklists, as drafted by the
Environmental Monitoring Management Council (EMMC), were developed for general application across
all EPA programs. As a result, the Checklists contain several categories that are not relevant to Office of
Water's methods approval program; these categories will be indicated by "NA" (not applicable). The
EMMC instructions have been annotated to clarify each checklist item's applicability to the streamlined
methods approval program. Annotated sections are highlighted within text boxes as shown in Figure E-l.
Streamlining:
Annotated instructions.
Figure E-50. Example Annotated Box
Draft, December 1996
E-1
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Streamlining Guide
Checklist for Initial Demonstration of Method Performance
7/13/96
For the demonstration of equivalency, provide a checklist for each matrix in each
medium.
Page of
Date:
Laboratory Name & Address:
Facility Name:
Discharge Point ID:
EPA Program and Applicable Regulation:
Medium:
(e.g., wastewater, drinking water, soil, air, waste solid, leachate, sludge, other)
Analyte or Class of Analytes:
(e.g., barium, trace metals, benzene, volatile organics, etc.)
Initial Demonstration of Method Performance (1)
Category
1. Written method (addressing all elements in the
EMMC format) attached -
2. Title, number and date/rev, of "reference method",
if applicable (3)
3. Copy of the reference method, if applicable,
maintained at facility
4. Differences between PBM and reference method
(if applicable) attached
5. Concentrations of calibration standards
6. %RSD or correlation coefficient of calibration
regression
7. Performance range tested (with units)
Performance
Criteria (2)
Based on
Measurement
Reference Quality
Method Objective
Results
Obtained
Perf.
Spec.
Achieved
•to
1
E-2
Draft, December 1996
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Equivalency Checklists
Initial Demonstration of Method Performance (1)
Category
8. Sample(s) used in initial demonstration have
recommended preservative, where applicable.
9. Sample(s) used in initial demonstration met
recommended holding times, where applicable
10. Interferences
11. Qualitative identification criteria used
12. Performance Evaluation studies performed for
analytes of interest, where available:
Latest study sponsor and title:
Latest study number:
13. Analysis of external reference material
14. Source of reference material
15. Surrogates used, if applicable
16. Concentrations of surrogates, if applicable
17. Recoveries of surrogates appropriate to the
proposed use, if applicable
18. Sample preparation ' ,
19. Clean-up procedures
20. Method Blank Result
21. Matrix (reagent water, drinking water, sand,
waste solid, ambient air, etc.)
22. Spiking system, appropriate to method and
application
23. Spike concentrations (w/ units corresponding to
final sample concentration)
24, Source of spiking material
25. Number of replicate spikes
26. Precision (analyte by analyte);
Performance .
Criteria (2)
Based on
Measurement
Reference Quality
Method Objective
•
-
Results
Obtained
Pert.
Spec.
Achieved
V)
-
,
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Initial Demonstration of Method Performance (1)
Category
27. Bias (analyte by analyte)
28. Detection Limit (w/ units; analyte by analyte)
29. Confirmation of Detection Limit, if applicable
30. Quantitation Limit (w/ units: analyte by analyte)
31. Qualitative Confirmation
32. Frequency of performance of the Initial
Demonstration
33. Other criterion (specify)
34. Other criterion (specify)
Performance
Criteria (2J
Based on
Measurement
Reference Quality
Method Objective
Results
Obtained
;
Perf.
Spec.
Achieved
(/)
1 Provide a detailed narrative description of the initial "demonstration.
2 For muiti-analyte methods, enter "see attachment" and attach a list or table containing the
anafyte-specific performance criteria from the reference method or those needed to satisfy
measurement quality objectives.
3 If a reference method is the source of the performance criteria, the reference method should
be appropriate to the required application, and the listed criteria should be fully consistent with
that reference method.
Name and signature of each analyst involved in the initial demonstration of
method performance (includes all steps in the proposed method/modification):
Name
Signature
Date
Name
Signature
Date
Name
Signature
Date
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The certification above must accompany this form each time it is submitted.
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Checklist for Continuing Demonstration of Method Performance
For the demonstration of equivalency, provide a checklist for each matrix in each
medium.
Date: Page of
Laboratory Name & Address:
Facility Name:
Discharge Point ID:
EPA Program and Applicable Regulation:
Medium:
(e.g., wastewater, drinking water, soil, air, waste solid, leachate, sludge, other)
Analyte or Class of Analytes:
(e.g., barium, trace metals, benzene, volatile organics, etc.)
Continuing Demonstration of Method Performance
Category
1. Method blank result (taken through all steps in the
procedure)
2. Concentrations of calibration standards used to verify
working range (with units), where applicable
3. Calibration verification
4, Laboratory Control Sample
5, External QC sample (where available)
6. Performance evaluation (PE) studies, if applicable
Latest study sponsor and title:
Latest study number
7. List analytes for which results were "not acceptable" in PE
study
8. Surrogates used, if applicable
9. Concentration of surrogates, if applicable
10. Recovery of surrogates (acceptance range for multi-
analyte methods), if applicable
11. Matrix
Required
Frequency
—
-
Specific
Perf.
Criteria
—
Results
Obtained
'
—
Perf.
Spec.
Achieved
..•00
—
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Continuing Demonstration of Method Performance
Category
12. Matrix spike compounds
1 3. Concentration of matrix spike compounds
14. Recoveries of matrix spike compounds
14a. Recoveries of matrix spike duplicate compounds.
15. Qualitative identification criteria used
16. Precision (analyte by analyte)
17. Other category (specify)
1 8. Other category (specify)
Required
Frequency
Specific
Pert.
Criteria
Results
Obtained
Pert.
Spec.
Achieved
(vO
Name and signature of each analyst involved in continuing demonstration of
method performance (includes all steps in the proposed method/modification):
Name
Signature
Date
Name
Signature
Date
Name Signature Date
The certification above must accompany this form each time it is submitted.
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Certification Statement 7/13/95
Date: Page of
Laboratory Name & Address:
Facility Name:
Discharge Point ID:
EPA Program and Applicable Regulation:
Medium:
(e.g., water, soil, air)
Analyte or Class of Analytes:
(e.g., barium, trace metals, benzene, volatile organics, etc.; Attach separate list,
as needed.)
We, the undersigned, CERTIFY that:
1. The method(s) in use at this facility for the analysis/analyses of samples for the programs of the
U.S. Environmental Protection Agency have met the Initial and any required Continuing Demonstration of
Method Performance Criteria specified by EPA.
2. A copy of the method used to perform these analyses, written in EMMC format, and copies of
the reference method and laboratory-specific SOPs are available for all personnel on-site.
3. The data and checklists associated with the initial and continuing demonstration of method
performance are true, accurate, complete and self-explanatory1.
4. All raw data (including a copy of this certification form) necessary to reconstruct and validate
these performance related analyses have been retained at the facility, and that the associated information
is well organized and available for review by authorized inspectors.
Facility Manager's Name and Title Signature
Date
Quality Assurance Officer's Name Signature
Date
This certification form must be completed when the method is originally certified, each time a continuing
demonstration of method performance is documented, and whenever a change of personnel involves the
Facility Manager or the Quality Assurance Officer.
1 True: Consistent with supporting data.
Accurate: Based on good laboratory practices consistent with sound scientific principles/practices.
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Complete: Includes the results of all supporting performance testing.
Self-Explanatory: Data properly labeled and stored so that the results are clear and require no additional
explanation.
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EMMC Checklists Instructions
Checklists Overview:
The Checklists were arrived.at through consensus among EPA's programs by developing performance
"categories" that allow use of the same Checklists across the Agency's various programs/projects. ,Xhe
Checklists may be applied to screening and field techniques as well as laboratory procedures.
Implementation of the Checklists is program-specific and a category that does not apply within a given
EPA program will be indicated by NA (not applicable).' Criteria for a specific EPA program are to be
filled in under the "Performance Criteria" column; e.g., an Office of Water Reference Method may specify
20% RSD or a correlation coefficient of 0.995 for the category that specifies calibration linearity, whereas
an Office of Solid Waste Project may specify a Measurement Quality Objective of 12% RSD or a
correlation coefficient of 0.998 for this category.
For each EPA program, the Checklists are to be completed for each matrix within each medium for all
matrices and media to which an alternate method or method modification applies.
Streamlining:
EMMC's definition of media is equivalent to Streamlining's matrix type.
Each completed Checklist must be retained on file at the laboratory that uses the performance-based
method (PBM) or method modification and at the regulated facility from which samples are collected, and
must be submitted to the appropriate Regulatory Authority upon request to support analysis of those
samples to which the PBM or modified method was applied.
Streamlining:
Under the streamlining, the term "new method" is used in place of PBM.
Header:
Each page of the checklist contains six lines of header information, consisting of:
* Pate (enter the date that the checklist was completed—Program/Project implementation plans
should indicate whether the checklist must be submitted to the Regulatory Authority, as well as, retained
on file at the laboratory and regulated facility).
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* Laboratory Name & Address (If a commercial contract laboratory uses the method on behalf
of one or more applicable clients, enter the name and address of the laboratory.)
* Facility Name (enter the name of the water treatment facility, system, or regulated facility or
other program or project specified entity where the facility maintains an on-site analytical laboratory. If
the method is being employed by a commercial contract laboratory on behalf of one or more applicable
clients, enter the name of the laboratory followed by a listing of the appropriate clients).
Streamlining:
This field is optional. Identify the facility from which the matrix samples were taken.
* Discharge Point Identification Number (enter the discharge point identification number, If
applicable).
* EPA Program & Applicable Regulationfenter the name of the Agency Program or Project to
whom the results will be reported, or under the auspices of which the data are collected, e.g., "CAA" for
Clean Air Act monitoring and "SDWA" for analyses associated with the Safe Drinking Water Act).
* Medium (enter the type of environmental sample, e.g., drinking water—NOTE a separate
checklist should be prepared for each medium, e.g., for checklists associated with performance-based
methods for SDWA, enter "Drinking Water" as the matrix type. As the evaluations of a performance-
based method will involve matrix-specific performance measures, a separate checklist would be prepared
for each matrix. The "medium is the environmental sample type to which the performance-based method
applies, whereas the performance category "matrix"; appearing in the body of the checklists refers to the
specific sample type within the "Medium" that was spiked ,e.g., for "Medium" hazardous waste, the
checklist category "Matrix" may be solvent waste.
Streamlining:
Enter the matrix instead of the medium.
* Analyte or Class of Analvtes where available (As many methods apply to a large number of
analytes, it is not practical to list every analyte in this field, as indicated on the form, the class of analytes
may be specified here, i.e., volatile organics. However, if such a classification is used, a separate list of
analytes and their respective Chemical Abstract Service Registry Numbers (CAS #) must be attached to
the checklist).
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initial Demonstration of Method Performance Checklist:
The Initial Demonstration of Method Performance involves multiple spikes into a defined sample
matrix (e.g., wastewater medium, paper plant effluent matrix), to demonstrate that the
Performance-based Method meets the Program or Project Performance Criteria based on the
performance of established "Reference Method" or based on "Measurement Quality Objectives"
(formerly called Data Quality Objectives). This exercise is patterned after the "Initial
Demonstration of Capability" delineated hi a number of the Agency's published methods
(Reference Methods).
Footnote #1 indicates that a detailed narrative description of the initial demonstration procedure
is to be provided.
Footnote #2 indicates that for multi-analyte methods, the range of performance criteria for the
analytes may be entered, but an analyte-specific performance criteria is to be attached. In
general, when using the checklists, if the criteria or performance are lengthy, attach as a
separate sheet, and enter "see attached" for this item.
Footnote #3 indicates that if a reference method is the source of the performance criteria, the
reference method should be appropriate to the required application and the listed criteria should
be fully consistent with that reference method. The reference method name and EPA number
(where applicable) should be delineated in the program/project implementation plan, e.g., by the
Program Office or the Project Officer/Manager.
There are 34 numbered entries in the body of the checklist--M?7jE:: UNDER NORMAL
CIRCUMSTANCES, IT WOULD NEVER BE ACCEPTABLE TO ANSWER "NO" TO ANY
OF THESE PERFORMANCE CATEGORIES, OR FAIL TO ATTACH THE REQUESTED
b£ATERL4LS:
Streamlining:
Categories which do not apply to streamlining method validation will be marked with "NA".
#1. Written Method (addressing all elements in the EMMC format)
The details of the method used for analysis must be described in a version of the method written
in EMMC format. The EMMC method format includes the following: 1.0 Scope & Application;
2.0 Summary of Method; 3.0 Definitions; 4.0 Interferences; 5,0 Safety; 6;0 Equipment &
Supplies; 7.0 Reagents & Standards; 8.0 Sample Collection, Preservation & Storage; 9.0 Quality
Control; 10.0 Calibration & Standardization; 11.0 Procedures; 12.0 Data Analysis &
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Calculations; 13.0 Method Performance; 14.0 Pollution Prevention; 15.0 Waste Management;
16.0 References; 17.0 Tables, Diagrams, Flowcharts & Validation Data., While this format may
differ from that used in standard operation procedures (SOPs) in a given laboratory, the use of a
consistent format is essential for the efficient and effective evaluation by inspectors, program arid
project managers/officers. ,
Streamlining:
See the Guidelines and Format for Methods to be Proposed at 40 CFR Part 136 or Part 141 ( EPA-
82 l-B-96-003) for detailed guidance on method format.
#2. Title. Number and date/revision of "Reference Method" if applicable.
For Example Polychlorinated Dioxins and Furans, EPA Method 1613, Revision B, October,
1994.
#3. Copy of the reference method, if applicable, maintained at the facility.
A copy of the reference method must be kept available for all laboratory personnel, however, it
need not be attached to the checklist itself.
#4. Differences between PBM and reference method attached.
The laboratory must summarize the differences between the reference method and the
performance-based method and attach this summary to the checklist. This summary should focus
on significant difference in techniques (e.g., changes beyond the flexibility allowed hi the
reference method), not minor deviations such as the glassware used,
#5. Concentrations of calibration standards.
The range of the concentrations of materials used to establish the relationship between the
response of the measurement system and analyte concentration. This range must bracket any
action, decision or regulatory limit. In addition, this range must include the concentration range
for which sample results are measured and reported (when samples are measured after sample
dilution/concentration).
#6. % RSD or Slope/Correlation Coefficient of Calibration Regression.
This performance category refers to quantitative measures describing the relationship between
the amount of material introduced into the measurement system and the response of the system,
e.g., analytical instrument. A linear response is generally expected and is typically measured as
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either a linear regression or inorganic analytes, or as the relative standard deviation (or
coefficient of variation) of the response factors or calibration factors for organic analytes.
Traditional performance specifications considered any regression line with a correlation
coefficient (r) of 0.995 or greater as linear. Also, for organic analytes, a relative standard
deviation (RSD) of 25% or less is considered linear. The calibration relationship, however, is not
necessarily limited to a linear relationship. However, it should be remembered if the
Program/Project Office or Officer/Managers specifies other calibration relationships, e.g.,
quadratic fit, more calibration standards are generally necessary to accurately established the
calibration. If applicable a calibration curve, graphical representation of the instrument response
versus the concentration of the calibration standards, should be attached.
#7. Performance Range Tested (with units).
This range must reflect the actual range of sample concentrations that were tested and must
include the concentration units. Since the procedures may include routine sample dilution or
concentration, the performance range may be broader than the range of the concentrations of the
calibration standards.
#8. garoplesfs) used in initial demonstration have recommended preservative, where
applicable.
Unless preservation have been specifically evaluated, this entry should be taken directly from the
reference method/standard. If preservation has been evaluated, include the study description and
conclusions of that evaluation, with a reference to the specific study description. The data must
be attached.
#9. Samplesfs) used in the initial demonstration must be within the recommended holding
tiroes, where applicable.
Unless holding time (time from when a sample is collected until analysis) has been specifically
evaluated, this entry should be taken directly from the reference method/standard. If holding
time has been evaluated, include the study description and conclusions of that evaluation here,
with a reference to the specific study description. The data must be attached.
#10. interferences.
s
Enter information on any known or suspected interferences with the performance-based method.
Such interferences are difficult to predict in many cases, but may be indicated by unacceptable
spike recoveries in environmental matrices, especially when such recovery problems were not
noted in testing a clean matrix such as reagent water. The inferences associated with the
reference method are to be indicated, as well as, the affect of these interferences on the
performance-base method.
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#11. Qualitative identification criteria used.
Enter all relevant criteria used for identification, including such items as retention time, spectral
wavelengths, ion abundance ratios. If the instrumental techniques for the Performance-based
method are similar to the reference method, use the reference method as a guide when specifying
identification criteria. If the list of criteria is lengthy, attach it on a separate sheet, and enter "see
attached" for this item.
#12. Performance Evaluation Studies performed for analytes of interest, where available
(last study sponsor and title:; last study number:).
Several EPA Programs conduct periodic performance evaluation (PE) studies. Organizations
outside of the Agency also may conduct such studies. Enter the sponsor, title, and date of the
most recent study hi which the performance-based method was applied to the matrix of interest.
For the performance-based method to be acceptable, the performance on such studies must be
"fully successful", Le., within the study QC acceptance criteria.
#13. Analysis of external reference material.
Enter the results of analyses on reference material from a source different from that used to
prepare calibration standards (where applicable). This performance category is especially
important if Performance Evaluation Studies are not available for the analytes of interest.
Streamlining:
Analysis of a reference, sample is one. of streamlining's standardized QC elements. The most common
reference sample is a Reference Material from the National Institute of Standards and Technology.
EPA will provide further guidance on its streamlining reference sample program when EPA initiates
its pilot study of the streamlined methods approval process.
#14. Source of reference material.
Enter criteria, if applicable, for traceability of materials used to verify the accuracy of the results,
e.g., obtained from the National Institute of Science and Technology (NIST).
#15. Surrogates used if applicable.
'Surrogates may be added to samples prior to preparation, as a test of the entire analytical
procedure. These compounds are typically brominated, fiuorinated or isotopically labeled
compounds, with structural similarities to the analytes of interest. Also, they are not expected to
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be present in environmental samples. Surrogates are often used in the analysis for organic
analytes. Enter the names of the surrogate compounds hi this category.
#16. Concentrations of surrogates (if applicable).
Enter the concentration of surrogates once spiked into the sample (i.e., final concentration).
#17. Recoveries of Surrogates appropriate to the proposed use (if applicable).
Enter the summary of the surrogate recovery limits and attached a detailed listing if more space
is needed.
#18. Sample Preparation.
Enter necessary preliminary treatments necessary, e.g., digestion, distillation and/or extraction.
A detailed listing may be attached if more space is needed.
#19. Clean-up Procedures.
Enter necessary intermediatory steps necessary to prior to the determinative step (instrumental
analysis), e.g., GPC, copper sulfate, alumina/Florisil treatment, etc.
#20. Method Blank Result. •
A clean matrix (i.e., does not contain the analytes of interest) that is carried through the entire
analytical procedure, including all sample handling, preparation, extraction, digestion, cleanup
and instrumental procedures. The volume or weight of the blank should be the same as that used
for sample analyses. The method blank is used to evaluate the levels of analytes that may be
introduced into the samples as a result of background contamination in the laboratory. Enter the
analyte/s and concentration measured hi the blank.
#21. Matrix (reagent water, drinking water, soil, waste solid, air, etc.).
Refers to the specific sample type within the broader "Medium" that was spiked, e.g., for
Medium": "Hazardous Waste" an example matrix spiked as part of the initial demonstration of
method performance might be-"solvent waste".
Streamlining:
Enter the same matrix as specified in the header.
I
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#22. Spiking System, appropriate to the method and application.
Enter the procedure by which a known amount of analyte/s ("spike") was added to the sample
matrix. This may include the solvent that is employed and the technique to be employed (e.g.,
permeation tube, or volumetric pipet delivery techniques spiked onto a soil sample and allowed
to equilibrate 1 day, etc.). Solid matrices are often difficult to spike and considerable detailed
narrative may be necessary to delineate the procedure. For spikes onto aqueous samples
generally a water miscible solvent is specified.
#23. Spike levels (w/units corresponding to final sample concentration).
Enter the amount of the analyte/s ("spike") that was added to the sample matrix in terms of the
final concentration in the sample matrix.
Streamlining: . , »
Under streamlining, initial spikes, also known as initial precision and recovery (IPR) standards, will
be performed in reagent water. Using reagent water will allow the comparison of IPR spike
•recoveries determined with the modified method against IPR criteria specified in the reference method
because reference method IPR specifications are developed from reagent water spikes.
#24. Source of spiking material.
Enter the organization or vendor from which the "spiking" material was obtained. This should
include specific identification information, e.g., lot#, catalogue number, etc.
#25. Number of Replicate Spikes.
The initial demonstration of method performance involves the analyses of replicate spikes into a
defined sample matrix category #21). Enter the number of such replicates. In general at least 4
replicates should be prepared and analyzed independently.
i
#26. Precision (analyte by analyte).
<*
Precision is a measure of agreement among individual determinations. Statistical measures of
precision include standard deviation, relative standard deviation or percent difference.
#27. Bias fanalvte bv analvteX
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Bias refers to the systematic or persistent distortion of a measurement process which causes
errors in one direction. Bias is often measured at the ratio of the measured value to the "true"
value or nominal value. Bias is often (erroneously) used interchangeably with "accuracy",
despite the fact that the two terms are complementary, that is, high "accuracy" implies low
"bias", and vice versa. Enter the name of the Bias measure (% recovery, difference from true,
etc.), the numeric value with associated units for each analyte obtained for each analyte spiked in
the initial demonstration procedure.
Streamlining:
Bias is not required under streamlining. This field is not applicable.
#28. Detection Limit (w/units; analyte by analyte).
A general term for the lowest concentration at which an analyte can be detected and identified.
There are various measures of detection which include Limit of Detection and Method Detection
Limit. Enter the detection measure (e.g., "MDL") and the analytical result with units for each
analyte in the matrix (#21).
Streamlining:
For method modifications, enter the detection limits specified in the reference method. For new
methods, enter the calculated detection limits.
#29. Confirmation of Detection Limit.
In addition to spikes into the matrix of interest (#21) it may be beneficial to perform the detection
measurements in a clean matrix, e.g., laboratory pure water. Results of the spikes in the clean
matrix are frequently available in the Agency's published methods. Determining MDLs hi a
clean matrix using the performance-based method will allow a comparison to the MDLs
published in the Agency methods.
Also, the detection limit technique may specify specific procedures to verify that the obtained
limit is correct, e.g., the "iterative process" detailed in the 40 CFR Part 136, Appendix B, MDL
procedures.
#30. Quantitation Limit fw7 units: analvte bv analvtel
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The lowest concentration that the analyte can be reported with sufficient certainty that an
unqualified numeric value is reportable. Measures of Quantitation limits include the Minimum *
Level (ML), Interim Minimum Level (IML), Practical Quantitation Level (PQL), and Limit of
Quantitation (LOQ). Enter the measure of Quantitation limit, and the units for each analyte.
' ' ' i
#31. Qualitative confirmation.
Enter all relevant criteria used for identification, including such items as: retention time; use of a
second chr.omatographic column; use of second (different) analytical technique; spectral
wavelengths; and ion abundance ratios. If the instrumental techniques for the modified method
,are similar to those of the reference method, use the reference method as a guide when specifying
confirmation criteria. If the list of criteria is lengthy, attach it on a separate sheet, and enter "see
attached" for this item.
f
#32. Frequency (initial Demonstration to be performed.
Enter the frequency that the initial demonstration has to be repeated, e.g., with each new
instrument or once a year, which ever is more frequent.
#33-#34. Other Criteria.
Enter omer necessary program/project specific method performance categories.
Streamlining:
Under streamlining Categories 33 and 34 are used as follows:
#33. Matrix Spike/Matrix Spike Duplicate.
Enter the percent recoveries of analytes spiked into the sample matrix. For method modifications,
only one set of matrix spike/matrix spike duplicate (MS/MSD) samples. For new methods, two sets
of MS/MSD samples must be analyzed to provide sufficient data for QC acceptance criteria
development.
#34. Matrix Spike/Matrix Spike Duplicate Relative Percent Deviation.
Enter the calculated relative percent deviation between the MS and MSD analyte recoveries.
Signatures:
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The name, signature and date of each analyst involved in the initial demonstration of method
performance is to be provided at the bottom of the check sheet.
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Continuing Demonstration of Capability Checklist:
The process by which a laboratory documents that their previously established performance.of an
analytical procedure continues to meet performance specifications as delineated in this checklist.
#1. Method Blank.
A clean matrix (i.e., does not contain the analytes of interest) that is carried through the entire
analytical procedure, including all sample handling, preparation, extraction, digestion, cleanup
and instrumental procedures. The volume or weight of the blank should be the same as that used
for sample analyses. The method blank is used to evaluate the levels of analytes that may be
introduced into the samples as a result of background contamination in the laboratory. Enter the
analyte/s and concentration measured in the blank.
#2. Concentrations of calibration standards used to verify working range, where applicable
(include units).
The range of the concentrations of materials used to confirm the established relationship between
the response of the measurement system and analyte concentration. This range must bracket any
action, decision or regulatory limit. In addition, this range must include the concentration range
for which sample results are measured and reported (when samples are measured after sample
dilution/concentration). Enter the concentrations of the calibration standards.
#3. Calibration Verification. - .- .
A means of confirming that the previously determined calibration relationship still holds. This
process typically involves the analyses of two standards with concentrations which bracket the
concentrations measured in the sample/s. Enter the procedure to be used to verify the calibration
and the results obtained for each analyte.
#4. Calibration check standard.
A single analytical standard introduced into the instrument as a means of establishing that the ~
previously determined calibration relationship still holds. Enter the concentrations and result for
each analyte.
#5. External QC sample (where applicable).
Enter the results of analyses for reference material (e.g., Quality Control samples/ampules) from
a source different from that used to prepare calibration standards (where applicable). Enter the
concentration, as well as, the source of this material. This performance category is of particular
importance if Performance Evaluation studies are not available for the analytes of interest.
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#6. Performance Evaluation studies performed for analytes of interest, where available
(Last study sponsor and title;; Last study number:).
Several EPA Programs conduct periodic performance evaluation (PE) studies. Other
organizations, outside of the Agency, also conduct such studies. Enter the sponsor, title, and date
of the most recent study in which the performance-based method was applied to the matrix of
interest. For the Performance-based method to be acceptable the performance on such studies
must be "fully successful", Le., within the study QC acceptance criteria.
# 7. List of analytes for which results were "not acceptable" in PE study.
#8. Surrogate Compounds used, if applicable.
Surrogates may be added to samples prior to preparation, as a test of the entire analytical
procedure. These compounds are typically brominated, fluorinated or isotopically labeled
compounds, with structural similarities to the analytes of interest. They are compounds not
expected to be present in environmental samples. Surrogates are often used in analyses for
organic analytes. Enter the names of the surrogate compounds in this performance category.
#9. Concentration of surrogates (if applicable).
Enter the concentration of surrogates once spiked into the sample (i.e., final concentration), with
units.
t
#10. Recoveries of Surrogates appropriate to the proposed use (if applicable).
Enter the summary of the surrogate recovery limits and attached a detailed listing (each surrogate
compound), if more space is needed.
#11. Matrix (reagent water, drinking water, soil, waste solid, air, etc.).
Refers to the specific sample type within the broader "Medium" that was spiked, e.g., for
"Medium": "Hazardous Waste" an example "matrix", spiked as part of the initial demonstration
of method performance, might be "solvent waste".
#12. Matrix Spike Compounds.
*
In preparing a matrix spike a known amount of analyte is added to an aliquot of a real-world
sample matrix. This aliquot is analyzed to help evaluate the effects of the sample matrix on the
analytical procedure. Matrix spike results are typically used to calculate recovery of analytes as
a measure of bias for that matrix. Enter the analytes spiked.
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#13. Matrix Spike Concentrations (w/units corresponding to final sample concentration).
Enter the amount of the analyte/s ("spike") that was added to the sample matrix in terms of the
final concentration in the sample matrix.
#14. Recovery of Matrix Spike (w/units).
The ratio of the standard deviation of a series of at least three measurements to the mean of the
measurements. This value is often expressed as a percentage of the mean.
Note: Some programs/projects have utilized matrix spike duplicates (a separate duplicate of
the matrix spike) to help verify the matrix spike result and to provide precision data for
analytes which are not frequently found in real-world samples, Le., duplication of non-detects
provides little information concerning the precision of the method. .
#15. Qualitative identification criteria used.
Enter all relevant criteria used for identification, including such items as retention tunes, spectral
wavelengths, ion abundance ratios. If the instrumental techniques for the Performance-based
method are similar to the reference method, use the reference method as a guide when specifying
identification criteria. If the list of criteria is lengthy, attach it on a separate sheet, and enter "see
attached" for this item.
#16. Sample Preparation.
Enter necessary preliminary treatments necessary, e.g., digestion, distillation and/or extraction.
A detailed listing may be attached if more space is needed.
#17. Clean-up Procedures.
Enter necessary intermediatory steps necessary to prior to the determinative step (instrumental
analysis), e.g., GPC, copper sulfate, alumina/forisil treatment, etc.
#18. Confirmation.
j»
Qualitative identification criteria used. Enter all relevant criteria used for identification,
including such items as: retention time; use of second chromatographic column; use of second
(different) analytical technique; spectral wavelengths, ion abundance rations. If the instrumental
techniques for the Performance-based method are similar to the reference method, use the
reference method as a guide when specifying confirmation criteria. If the list of criteria is
lengthy, attach it on a separate sheet, and enter "see attached" for this item.
Draft, December 1996
E-23
-------
Streamlining Guide
#19-20. Other.
Enter other necessary program/project specific method performance categories.
/
Signatures'.
The name, signature and date of each analyst involved in the continuing demonstration of
method performance is to be provided at the bottom of the checklist.
E-24
Draft, December 1996
-------
Equivalency Checklists
This section provides an example of completed checklists and associated'laboratory data. The data
were obtained from a contract laboratory's testing of Method 1613, "Tetra- Through Octa-Chlorinated
Dioxins and Furans by Isotope Dilution HRGC/HRMS". Method 1613 is approved for use in drinking
water at 40 CFR 141.24 (59 FR 62468), and proposed for use in wastewater (56 FR 62468) and the Pulp,
Paper, and Paperboard category at 40 CFR part 430 (58 CFR 66078).
The information is technically detailed, and intended for data reviewers familiar with analytical
methods. This example is provided to serve as an additional form of guidance for completing the
checklists.
Draft, December 1996
E-25
-------
Streamlining Guide
Checklist for Initial Demonstration of Method Performance
7/13/96
For the demonstration of equivalency, provide a checklist for each matrix in each
medium.
Date: February 2,1994 Page of
Laboratory Name & Address: ABC Analytical, Inc., Anytown, USA
Facility Name: PaperMill#l
Discharge Point ID: N/A
EPA Program and Applicable Regulation: CWA Effluent Guidelines
Medium: Water
(e.g., water, soil, air)
Analyte or Class of Analytes: PolychlorinatedDioxins and Furans
(e.g., barium, trace metals, benzene, volatile organics, etc.; Attach separate list, as
needed.)
Initial Demonstration of Method Performance (1)
Category
1. Written method (addressing all elements in the
EMMC format) attached
2. Title, number and date/rev, of "reference method",
if applicable (3)
3. Copy of the reference method, if applicable,
maintained at facility
4. Differences between the modified and reference
method (if applicable) attached
5. Concentrations of calibration standards
6. %RSD or correlation coefficient of calibration
regression
7. Performance range tested (with units)
8. Sample(s) used in initial demonstration have
recommended preservative, where applicable.
Performance
Criteria (2)
Based on
Measurement
Reference Quality
Method Objective
Attach 1
Attach 2
Attach 3
Results
Obtained
EPA Method
1613 Rev. B
Attach 1
Attach 2
Attach 3
Pert.
Spec.
Achieved
w
«x
•
*x
N/A
•
•
•
N/A
£-25
Draft, December 1996
-------
, Equivalency Checklists
initial Demonstration of Method Performance (1)
Category
^
9. Samples(s) used in initial demonstration met
recommended holding times, where applicable
10. Interferences
11. Qualitative identification criteria used
12. Performance Evaluation studies performed for
analytes of interest, where available:
Latest study sponsor and title:
Latest study number:
13. Analysis of external reference material
14. Source of reference material
15. Surrogates used, if applicable
16. Concentrations of surrogates, if applicable
17. Recoveries of surrogates appropriate to the
proposed use,
if applicable
18. Sample preparation
19. Clean-up procedures
20. Method Blank Result
21. Matrix (reagent water, drinking water, waste solid,
etc.)
22. Spiking system, appropriate to method and
application
23. Spike concentrations (w/ units corresponding to
final sample concentration)
24. Source of spiking material
Perfo
Crite
Base
,
Reference
Method
Attach 4
Attach 5
Attach 6&8
Attach 6&8
Attach 6&8
Extraction
'
Attach 8
volumetric
pipet
Attach 6
rmance
xia(2)
don
Measurement
Quality
Objective
Results
Obtained
Attach 4
Attach 5
John Doe,
PE Study,
1234
Attach 6 &
8
Attach 6 &
8
Attach 6 &
8
Extraction
Attach 8
Paper Mill
Effluent
volumetric
pipet
Attach 6
Acme
Standards
lot #105
cat #41
Pert.
Spec.
Achieved
•00
f'
•
•
•
N/A
N/A
•
•
S
•
N/A
•
•
•
•
•
Draft, December 1996
E-27
-------
Streamlining Guide
Initial Demonstration of Method Performance (1)
Category
25. Number of replicate spikes
26. Precision (analyte by analyte)
27. Bias (analyte by analyte)
28. Detection Limit (w/ units; analyte by analyte)
29. Confirmation of Detection Limit, if applicable
30. Quantitation Limit (w/ units: analyte by analyte)
31. Qualitative Confirmation
32. Frequency of performance of the Initial
Demonstration
33. Other criterion (specify)
34. Other criterion (specify)
Performance
Criteria (2)
Based on
Measurement
Reference Quality
Method Objective
at least four
Attach 7
Attach 9
Attach 5
Annual
-
Results
Obtained
four
Attach 7
Attach 9
Attach 5
Annual
Peri.
Spec.
Achieved
(/)
•
•
N/A
N/A
N/A
•
•
•
N/A
N/A
Provide a detailed narrative description of the initial demonstration.
2
For multi-analyte methods, enter "see attachment" and attach a list or table containing the analyte-
specific performance criteria from the reference method or those needed to satisfy measurement quality
objectives.
3
If a reference method is the source of the performance criteria, the reference method should be
appropriate to the required application, and the listed criteria should be fully consistent with that reference
method.
Name and signature of each analyst involved in the initial demonstration of method
performance (includes all steps in the proposed method/modification):
John Doe
2/2/94
Name
Signature
Date
Name
Signature
Date
Name
Signature
Date
£-28
Draft, December 1996
-------
Equivalency Checklists
The certification above must accompany this form each time it is submitted.
Draft, December 1996
E-29
-------
Streamlining Guide
Certification Statement
Date: February 2,1994 Page _1 of _1
Laboratory Name & Address: ABC Analytical, Inc., Anytown, USA
Facility Name: Paper Mitt #1
Discharge Point ID: N/A
EPA Program and Applicable Regulation: CWA Effluent Guidelines
Medium: Water
(e.g., water, soil, air)
Analyte or Class of Analytes: Poly chlorinated Vioxins and Furans
(e.g., barium, trace metals, benzene, volatile organics, etc.; Attach separate list, as
needed.)
We, the undersigned, CERTIFY that:
1. The method(s) in use at this facility for the analysis/analyses of
samples for the programs of the U.S. Environmental Protection Agency have met
the Initial and any required Continuing Demonstration of Method Performance
Criteria specified by EPA.
2. A copy of the method used to perform these analyses, written in EMMC
format, and copies of the reference method and laboratory-specific SOPs are
available for all personnel on-site.
3. The data and checklists associated with the initial and continuing
demonstration of method performance are true, accurate, complete and self-
explanatory (l) . '
4. All raw data (including a copy of this certification form) necessary
to reconstruct and validate these performance related analyses have been
retained at the facility, and that the associated information is well
organized and available for review by authorized inspectors.
Jane Doe, Laboratory Manacrer
Facility Manager's Name and Title
John Doe. Chemist
Quality Assurance Officer's Name
Signature
Signature
2/2/94
Date
2/2/94
Date
This certification form must be completed when the method is originally
certified, each time a continuing demonstration, of method performance is
documented, and whenever a change of personnel involves the Facility Manager
or the Quality Assurance Officer.
(1) True: Consistent with supporting data. .
£-30
Draft, December 1996
-------
Equivalency Checklists
Accurate: Based on good laboratory practices consistent with sound
scientific principles/practices.
Complete: Includes the results of all supporting performance
testing.; ' ' . ' ••• •
Self-Explanatory: Data properly labeled and stored so that the
results are clear and require no additional explanation.
Draft, December 1996
£-37
-------
Streamlining Guide
Attachment 1
Concentration^) of Calibration Solution(s)
Compound
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
l3Cir2,3,7,8-TCDD
"C)r2,3,7,8-TCDF
"C,rl,2,3,7,8-PeCDD
13C,rl,2,3,7,8-PeCDF
"C,r2,3,4,7,8-PeCDF
"C,rl,2,3,4,7,8-HxCDD
IJC,rl,2,3,6,7,8-HxCDD
l}C,rl,2,3,4,7,8-HxCDF
"C,rl,2,3,6,7,8-HxCDF
"C,rl,2,3,7,8,9-HxCDF
l3e,r2,3,4,6,7,8-HxCDF
1JC,rl,2,3,4,6,7,8-HpCDD
"C,rl,2,3,4,6,7,8-HpCDF
"Cls-l,2,3,4,7,8,9-HpCDF
"C12-OCDD
Cleanup Standard
37CU-2,3,7,8-TCDD
Internal Standards
"C,rl,2,3,4-TCDD
"C,r 1 ,2,3,7,8,9-HxCDD
CS1
(ng/mL)
0.5
0.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5.0
5.0
100
100
100
100
100
100
. 100
100
100
100
100
100
100
100
200
0.5
100
100
Specification in Reference Method
CS2 CSS CS4 CSS
(ng/mL) (ng/mL) (ng/mL) (ng/mL)
2
2
10
10
10
10
10
10
10
10
10
10
10
10
10
20
20
100
100
100
100
100 '
100
100
100
100
100
100
100
100
100
200
2
100
100
10
10
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
10
100
100
40
40
200
200
200
200
200
200
200
200
200
200
200
200
200
400
400
100
100
100
100
100
100
100
100
100
100
100
100 .
100
100
200
40
100
100
200
200 .
1000
1000
1000
1000
1000.
1000
1000
1000
1000
1000
1000
1000
1000
2000
2000
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
200
100
100
Result Obtained
(Concentrations
Used)
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same .
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
Same
.Same
£-32
Draft, December 1996
-------
Equivalency Checklists
Attachment 2
Percent Relative Standard Deviation (%RSD)
Compound
2,3,7,8-TCDD
2,3,7,8-JCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
' 2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1 ,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13CI2-l,2,3,7,8-PeCDF
13C12-2,3,4,7,8-PeCDF
I3Ci2-l,2,3,4,7,8-HxCDD
' 13C,rl,2,3,6,7,8-HxCDD
"CI2-1 ,2,3 ,4J,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13C12-1 ,2,3,7,8,9-HxCDF
!3C12-2,3,4,6,7,8-HxCDF
I3C12-l,2,3,4,6,7,8-HpCDD
13CI2-l,2,3,4,6,7,8-HpCDF
, 13C12-l,2,3,4,7,8,9-Hpc'DF^
I3C,2-OGDD
Cleanup Standard
37Cl4-2,3/7,8-TCDD
Specification in
Reference Method (%)
< 20
< 20
< 20
< 20
< 20 '
< 20
<20
< 20
< 20
< 20^
. . < 20
< 20
< 20
< 20
< 20
< 20
< 20
< 35
< 35
< 35
• < 35
< 35
< 35
< 35
<: 35
< 35
< 35
< 35
< 35
< 35
. < 35
< 35
< 35
Result
Obtained (%)
4.5
7.3
3.6
2.7
2.8
5.5
2.0
2.8
1.6
3.0
4.4
5.4
5.6
4.1
3.4
2.5
1.9
2.0
3.0
5.1
6.8
6.1
8.1
1.7
7.8
3.3
8.9
4.8
5.0
4.9
8.3'
9.3
15
Draft, December 1996
E-33
-------
Streamlining Guide
Attachment 3
Performance Range
Compound
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Specification in Reference
Method (pg/L)
10 - 4000
10 - 4000
50 - 20,000
50-20,000
50 - 20,000
50 - 20,000
50 - 20,000.
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
100 - 40,000
100 - 40,000
Result Obtained
(pg/L)
10 - 4000
10-4000
50-20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50 - 20,000
50-20,000
50 - 20,000
100 - 40,000
. 100-40,000
£-34
Draft, December 1996
-------
Equivalency Checklists
Attachment 4
Specificity in Presence of Interferences
Compound
1,2,3,4-TCDD
1,2,7,8-TCDD
1,4,7,8-TCDD
1,2,3,7-TCDD
1,2,3,8-TCDD
2,3,7,8-TCDD
Specification in Reference
Method (%)
The height of the valley
between the most closely
eluted isomers and the 2,3,-
7,8- isomers is less than 25
percent.
'
Result Obtained
(%)
.0
0
0
0
0
0
Draft, December 1996
E-35
-------
Streamlining Guide
Attachment 5
Qualitative Identification Criteria
Criteria
Specification in Reference Method (%)
Specification
Achieved (Y/N)
Mass-to-charge ratios
(ra/z's)
Signal-to-noise ratios
Ion abundance ratios
The signals for the two exact m/z's being monitored must
be present and must maximize within ± 2 seconds of one
another.
The signal-to-noise ratio of each of the two exact m/z's
must be greater than or equal to 2.5 for sample extracts and
greater than or equal to 10 for calibration standards.
The ratio of the integrated ion currents for the two exact
m/z's being monitored must be within the limits of the table
below.
Theoretical Ion Abundance Ratios and QC Limits
Number of
Chlorine Atoms
4(2)
5
6
6(3)
7
7(4)
8
m/z's
Forming Ratio
M/M+2
M+2/M+4
M+2/M+4
M/M+2
M+2/M+4
M/M+2
M+2/M+4
Theoretical
Ratio
0.77
1.55
1.24
0.51
1.05
0.44
0.89
QC
Lower
0.65
1.32
1.05
0.43
0.88
0.37
0.76
Limits (1)
Upper
0.89
1.78
1.43
0.59
1.20
0.51
1.02
(1) QC limits represent ±15% windows around the theoretical ion abundance ratios.
(2) Does not apply to 37Cl4-2,3,7,8-TCDD (cleanup standard).
(3) Used for 13C,2-HxCDF only.
(4) Used for 13C12-HpCDF only.
E-36
Draft, December 1996
-------
Equivalency Checklists
Attachment 6
IPR Spike Levels, Surrogates Used, and Surrogate Recovery Limits
Concentration Found
Spike Level
(l)(ng/mL) EPR-i IPR-2 - IPR-3 BPR-4
Compound , (ng/mL) (ng/mL) (ng/mL) (ng/mL)
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD .
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
. 1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
• 2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD •
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
P%ir§Cli%S»^ ^~
^c^*»'j'>""2» 3. V -O~j[ C^£?r %,
13^* *»'! o A *7 S— "pp/ "* 1 Vrj ^
l^!2-I,273,7,8"-PeCT>F* ~%
ftl3^ir2j3»4»7.^rWa>F< ' "^
( ^^C^ -"I 2 *^ 4 *7 ft— TT'yf'T'VT*^
^^^i-j-ty^-L ^ .<£ . j> j r> - . / - X™ ri yCu .jt^JL* ^
^fGi2-l,243A7,8-HxCI>F
;^i2-l5t3^r7,8pHxCDF*
v-'f"l^1^ ^1 ^t ^ -*7 O Q JtT-y f**l "yi-?
^(^2-2,3,4,6,7,8,-EbtCpF '-^
ri^-l2,3Xf^8-HpCDD
jj'Ctj-i^l^ej^-apCDF^ •
|g'd|M7'8'|HpCpF^ ,
37Cl4-2,3,7,8-TCDD
10
10
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
•""Tjdvy^
''loo!^ *•
i loo ,\
, - ,I6p^
/-__ 'iob t^
^100^'"
•^ ^106^ * ;
^ ^t* 100'^ * ,
-J.OO
'; '. 100
''" 100 / '.
^IttT
? < '100,- ,
' '' 100 , ,
10
9.5
9.5
46.7
46.4 ."
47.7
45.6
48.3
52.4
49.6 .
49.4
46.0
47.5
49.5
46.3
48.1
98.4
84,9
77,6 ~
' 78-1 < -A
69-7i ~*
,68.7
- JS7.0 '
1 104.4\
, 77.3. ^
« 54.8 " '
" 49& " "
77.4 *
96.1 -'
_ 81,2 , '/
52J2
8f.9 ~ -
8.4 ~"
9.9
10.0
48.4
48.7
48.7
47.2
51 9
j \.,y
53 7
•J-J. /
50.0
52.6
48.0
50.4
54.5
49.4
51.0
115.9
89.2
80".2
"ft79.9 "
- 66.2
S , 69-5 -
66.9
106.3
•" 80.1^'
57.8
, 53.9
- '82.2.",
98.4
78.'4
50,9
- 85.1
8.0
9.9
9.7
49.0
49.2
49.5
48 0
^O.v
^7 7
.j^.z.
49.7
52.7
48.8 ,
50.1
S5 9
•jtj •£*
50.4
52.3
106.4
97.2
/" 83.6
81.3
\70.0 -'„,
71.8 -
67.8
,108.9'
78i8 „
80.8
71.9
* >82.3 ,
103.7
80.4 _,-
71.7
^ 88.9 -
8.0
10.0
10.0
48.3
49.0
50.5
4Q 8
^j'.O
^A 3
49.9
54 i
«J*T. A
48.1
48.4
51 Q
ji.y
49.9
49.6
107.0
92.8
™82.7
79.2
69.7
70.6 *
65tl
108.3 " '
85.0
70.7 ^
62.6 <
89.1 '
112'.9
89.1
64.5 •
97.2
^_._<_
Note:
The shaded compounds are the surrogates (labeled compounds) required by the reference
method. The labeled compound recovery limits are 25 - 150%.
ALL NATIVE AND LABELED COMPOUNDS REQUIRED BY THE METHOD WERE
SPIKED AT THE APPROPRIATE LEVEL.
Draft, December 1996
E-37
-------
Streamlining Guide
Attachment 7
DPR Precision and Recovery Limits
Specification in Reference Method
(1)
s X
Compound
(ng/mL)
(ng/mL)
Specification in Reference
Method (1)'
s X
(ng/mL) (ng/mL)
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
13C,,-2,3,7,8-TCDD
13C,r2,3,7,8-TCDF
"C,rl,2,3,7,8-PeCDD
"C12-l,2,3,7,8-PeCDF
13C,r2,3,4,7,8-PeCDF
13C,rl,2,3,4,7,8-HxCDD
"CI2-1 ,2,3,6,7,8,-HxCDD
»Clz-l,2,3,4,7,8-HxCDF
1JC,rl,2,3,6,7,8-HxCDF
I3C,rl,2,3,778,9-HxCDF
l3C,r2,3,4,6,7,8-HxCDF
"Cp-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8-HpCDF
l3CI2-l,2,3,4,7,8,9-HpCDF
"C12-OCDD
"Cl4-2,3,7,8-TCDD
1.1
0.5
1.5
1.5
3.4
5.3
3.7
5.6
3.7
1.9
3.6
2.2
3.3
2.6
2.9
11.3
-5.8
16.0
18.4
21.2
15.9
20.1 .
18.7
24.1
14.5
11.5
14.8
10.4
20.4
18.8
22.9
43.9
-
8.0-
8.2-
44.2-
44.1-
, 45.7 -
40.6-
47.5-
35.6 -
41.7-
47.0-
46.6-
. 44.8-
39.6-
43.9 -
49.5-
73.8-
74.0-
25.0-
25.0-
25.0-
25.0 -
25.0-
25.0-
25.0-
25.0-
25.0-
25.0-
25.0-
25.0-
25.0-
25.0-
50.0-
2.5-
12,5
12.8 '
53.1
55.2
58.7
64.6
50.6
73.9
54.5
54.2
54.0
52.8
58.0
55.4
52.1
149.1
128.7
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
150.0
300.0
15.0
0.2
0.2
1.0
1.3
1.2
1.7
1.8
2.1
0.2
1.9
1.2
1.4
2.6
1.8
1.8
7.2
5.2
2.7
1.3
1.8
1-3
1.1
1.1
3.3
12.0
9.9
4.8
7.5
4.7
10.0
5.5
10.6
-
9.8
9.8
48.1
48.3
49.1
47.6
50.7
54.4
49.8 .
52.2
47.7
49.1
52.8
49.0
50.2
106.9
91.0
81.0
79.6
68.9
70.2
66.7
108.0
80!3
66.0
59.5
82.8 .
102.8
82.3 •
59.8
89.3
133.0
8.0
(1) s = standard deviation of the concentration, X = average concentration.
E-38
Draft, December 1996
-------
Equivalency Checklists
Attachment 8
Method Blank
Compound
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4',7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF .
OCDD
OCDF
I3C12-2,3,7,8-TCDD
I3C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C,2-l,2,3,7,8-PeCDF
I3CI2-2,3,4,7,8-PeCDF
I3C12-l,2,3,4,7,8-HxCDD
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,6,7,8-HxCDF
13CI2-l,2,3,7,8,9-HxCDF
13CI2-2,3,4,6,7,8-HxCDF
I3Cj2-i,2,3,4,6,7,8-HpCDD
13C12-1 ,2,3,4,6,7,8-HpCDF
13C,2-1 ,2,3,4,7,8,9-HpCDF
13C12-OCDD
Cleanup Standard
37Cl4-2,3,7,8-TCDD
Specification in
Reference Method (1)
. pg/L
< 10
< 10
< 50
<50
< 50
< 50
< 50
<50
• < 50
< 50
< 50
< 50
< 50
<50
<50
< 100
< 100
% Recovery
25-150 .s
, 25 - 150
' 25 - 150 •
25 - 150
25 - 150
25 - 150
25 - 150
25 - 150
25 - 150
25-150
25 - 150
25-150
25 - 150
25 - 150
25-150
25 - 150
Result Obtained
pg/L
< 10
< 10
< 50
< 50
< 50
< 50
< 50
< 50
< 50
<-50
< 50
< 50
< 50
<50
< 50
< 100
< 100
% Recovery
76
72
65
67
61
92
86
68
58
104
75
82
69'
93
73
94
(1) For native analytes, the concentration found must be below the Minimum Level for_that analyte.
For labeled compounds, the percent recovery must be within the limit of 25 - 150%.
Note: All labeled compounds were spiked at the same level as for the IPR requirements.
Draft, December 1996
E-39
-------
Streamlining Guide
Attachment 9
Minimum Levels
Compound
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Specification
Method i
Minimum
Level (pg/L)
10
10
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
in Reference
pg/L) (1)
Signal-to-
noise ratio
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
Result Obtained
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
> 10
(1) The peaks representing the native analytes in the CS1 calibration standard must have a signal-to-
noise ratio greater than or equal to 10.
E-40
Draft, December 1996
-------
-------
-------
Appendix F
Inorganic Criteria
-------
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Appendix G
Bibliography
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Bibliography
Bibliography
Legislative Acts
Federal Water Pollution Control Act, aTweKJe^£>y the Clean .Water Act, 33 U.S.C.A. §§1251-1387.
National Technology and Advancement Act of 1995, 16 U.S.C. § 3701.
Public Health Service Act, amended by the Safe Drinking Water Act, 42 U.S.C.A. §§ 300f to 300j - 26.
\
Executive Initiatives
Environmental Technology Initiative, State of the Union Speech, February 17, 1993.
Reinventing Government Initiative, From Red Tape to Results: Creating a Government That Works Better
and Costs Less. September 7, 1993. .
Code of Federal Regulations
Guidelines Establishing Test Procedures for the Analysis of Pollutants, 40 CFR part 136, et. sec.
National Primary Drinking Water Regulations, 40 CFR part 141, et. sec.
Other
Department of Energy Environmental Management Electronic Data Deliverable Master Specification.
June 1,1995. Version 1.0.
Guidance on Evaluation, Resolution, and Documentation of Analytical Problems Associated
-with Compliance Monitoring, EPA 821-B-93-001
Guidance on the Evaluation of Safe Drinking Water Act Compliance Monitoring Results from
Performance-based Methods. July draft, 1995. USEPA OGWDW
Collaborative Guidelines, JAOAC 78 No. 5, 1995.
Interlaboratory Validation of U.S. Environmental Protection Agency Method 1625A. July 1984.
SRI International. ' ,
The Detection Limit. Environmental Science Technology., Vol. 22, No. 8, p. 856. 1988. P. Steven Porter.
Protocol for Approval of Alternate Test Procedures for Inorganic and Organic Analytesfor
National Pollution Discharge Elimination Systems. Revision 1.3. January 1986. U.S. EPA,
ORD,NERL-Ci.
Draft, December 1996
G-1
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Streamlining Guide
Protocol for Nationwide Approval for New and Revised Methods for Inorganic and Organic Analyies in
National Primary Drinking Water Regulations Monitoring. Revision I.S.January 1996. U.S.
EPA,ORD,NERL-Ci.
Standard Practice for Determination of Precision and Bias of Applicable Methods of Committee D-19 on
Water. Aug. 29, 1986. ASTM. D2777-86.
Use of Statistics to Develop and Evaluate Analytical Methods, Wemimont, Grant T., Spendley, William
ed. AOAC-International.
G-2
Draft, December 1996
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