&EPA
United States
Environmental
Agency
Protocol for EPA Approval of
Alternate Test Procedures for
Organic and Inorganic Analytes in
Wastewater and Drinking Water
March 1999
-------
U.S. Environmental Protection Agency
Office of Water
Engineering and Analysis Division
1200 Pennsylvania Avenue, NW (4303T)
Washington, DC 20460
EPA821-B-98-002
March 1999
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Foreword
This document provides instructions for validation, submission, and EPA approval of
applications for approval of alternate test procedures (ATPs) that determine inorganic and organic
analytes. This document serves as a supplement to the ATP guidelines at 40 CFR 136.4, 136.5, and
141.27. This ATP protocol has been revised to significantly reduce the number of analyses necessary to
demonstrate method equivalency by removing the requirement for side-by-side analyses using two
different methods. Instead, applicats are required to demonstrate method equivalency by meeting quality
control (QC) acceptance criteria associated with EPA-designated approved methods for different
combinations of regulated analyte and determinative technique.
Under EPA's ATP program, a method developer may apply to gain approval for the use of an
alternate procedure to test for a specific regulated constituent. EPA anticipates that the standardized
procedures described herein will expedite the approval of ATPs, encourage the development of
innovative technologies, and enhance the overall utility of the EPA-approved methods for compliance
monitoring under the National Pollution Discharge Elimination System (NPDES) permit program and
national primary drinking water regulations (NPDWRs).
This protocol applies to modifications of an EPA-approved method or a procedure that uses the
same determinative technique and measures the same analyte(s) of interest as an approved method.
Methods that use a different determinative technique to measure the same analyte(s) of interest as an
approved method are considered new methods. The requirements for EPA approval of new methods are
detailed in a separate protocol.
This document is not a legal instrument and does not establish or affect legal obligations under
Federal regulations. EPA reserves the right to change this protocol without prior notice.
Questions or comment regarding this document or the ATP program should be directed to:
William Telliard
Analytical Methods Staff
Engineering and Analysis Division (4303-T)
U.S. EPA Office of Water, Office of Science and Technology
1200 Pennsylvania Ave NW
Washington DC 20460
202-566-1061
202-566-1053 (facsimile)
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ATP Protocol for Organic and Inorganic Analytes
1.0 INTRODUCTION 1
1.1 Background and Objectives 1
1.2 Tiered System for Validation of Alternate Test Procedures 2
1.3 Scope of Alternate Test Procedures 2
1.3.1 EPA-Designated Approved Methods 2
1.3.2 Modifications to Front-end Techniques 3
1.3.3 Adding New Target Analytes 3
2.0 APPLICATION REQUIREMENTS 4
2.1 Submission Addresses 4
2.2 Application Information 5
2.2.1 Justification for ATP 6
2.2.2 Standard EPA Method Format 6
2.2.3 Method Comparison Table 6
2.2.4 Validation Study Report 7
2.2.5 Method Information and Documentation to Facilitate EPA Preparation of Preamble
and Docket 7
2.3 Proprietary Information in Applications 8
3.0 METHOD VALIDATION 9
3.1 Introduction 9
3.2 Summary of Validation Requirements 9
3.3 Tier 1, 2, and 3 Validation Studies 11
3.3.1 Tier 1 Validation Studies for Wastewater and Drinking Water 12
3.3.2 Tier 2 Validation Studies for Wastewater and Drinking Water 13
3.3.3 Tier 3 Validation Studies (for Wastewater Only) 14
3.4 Development of a Validation Study Plan 15
3.4.1 Background 15
3.4.2 Objectives 15
3.4.3 Study Management 15
3.4.4 Technical Approach 16
3.4.5 Data Reporting and Evaluation 16
3.4.6 Limitations 16
3.5 Detailed Procedures for Conducting Validation Studies 16
3.5.1 Method Compilation 16
3.5.2 Method Detection Limit Study 16
3.5.3 Calibration 17
3.5.4 Initial Precision and Recovery 17
3.5.5 Field Sample Analyses 17
3.5.6 Ongoing Precision and Recovery 18
3.5.7 Calibration Verification 18
3.5.8 Contamination Level in Blanks 19
3.5.9 Surrogate or Labeled Compound Recovery 19
3.5.10 Absolute and Relative Retention Time 19
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ATP Protocol for Organic and Inorganic Analytes
3.5.11 New Analytes 19
3.6 Validation Study Report 20
3.6.1 Background 20
3.6.2 Study Design and Objectives 21
3.6.3 Study Implementation 21
3.6.4 Data Reporting and Validation 21
3.6.5 Results 21
3.6.6 Data Analysis/Discussion 22
3.6.7 Conclusions 22
3.6.8 Appendix A - The Method 22
3.6.9 Appendix B - Validation Study Plan 22
3.6.10 Appendix C - Supporting Data 22
4.0 EPA REVIEW AND APPROVAL 24
4.1 EPA Review of Applications 24
4.2 Approval Recommendation 25
4.3 Rulemaking Process 25
5.0 REFERENCES 26
6.0 APPENDIX A - ATP APPLICATION FORM 27
7.0 APPENDIX B - HEADQUARTERS AND REGIONAL ATP CONTACTS 28
8.0 APPENDIX C - STANDARD EPA METHOD FORMAT 29
9.0 APPENDIX D - EQUIVALENCY CHECKLISTS 31
9.1 Checklists and Instructions for Use 31
9.2 Example of Completed Checklists 45
9.3 Data Reporting Form 50
10.0 APPENDIX E - QUALITY CONTROL ACCEPTANCE CRITERIA 52
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ATP Protocol for Organic and Inorganic Analytes
1.0 INTRODUCTION
1.1 Background and Objectives
As required by the Clean Water Act (CWA) and Safe Drinking Water Act (SDWA), the U.S.
Environmental Protection Agency (EPA) promulgates guidelines establishing test procedures (analytical
methods) for data gathering and compliance monitoring under National Pollution Discharge Elimination
System (NPDES) permits and national primary drinking water regulations (NPDWRs). These test
procedures are approved at 40 Code of Federal Regulations (CFR) part 136 for wastewater and 40 CFR
part 141 for drinking water. In addition, the guidelines at 40 CFR 136.4 and 136.5 and 40 CFR 141.27,
allow entities to apply for Agency permission to use an alternate test procedure (ATP) in place of an
approved method. These guidelines are the basis for the Agency's alternate test procedure (ATP) program
for water methods that is administered by the Office of Water, Office of Science and Technology,
Analytical Methods Staff (AMS).
Under the ATP program, an organization or individual may submit an application for approval of a
modified version of an approved method or a procedure that uses the same determinative technique and
measures the same analyte(s) of interest as an approved method, to be used as an alternate to an approved
method. The applicant is responsible for validating its proposed alternate test procedure. The Agency
reviews the ATP validation package, approves or disapproves the application, and for nationwide
applications, promulgates successful ATPs in the CFR.
With the goal of making the ATP program more accessible while maintaining data quality, EPA
has revised its chemical ATP protocol to replace the side-by-side comparative validation study with a three-
tiered validation protocol. This revised ATP protocol significantly reduces the number of analyses
necessary to demonstrate method equivalency by removing the requirement for side-by-side analyses using
two different methods. Instead, applicants demonstrate method equivalency by meeting quality control
(QC) acceptance criteria associated with EPA-designated approved methods for different combinations of
regulated analyte and determinative technique.
An ATP is a modification of an approved method or a procedure that uses the same determinative
technique and measures the same analyte(s) of interest as the approved method. The use of a different
determinative technique to measure the same analyte(s) of interest as an approved method is considered a
new method. The requirements for EPA approval of new methods are detailed in a separate protocol.
The ATP program provides chemists with the opportunity to use best professional judgement to
enhance compliance monitoring and encourages use of innovative technologies. Approval for an ATP may
be sought when the alternate procedure reduces analytical costs, overcomes matrix interferences problems,
improves laboratory productivity, or reduces the amount of hazardous materials used and/or produced in
the laboratory.
Any person or organization may apply to gain approval for the use of an ATP for determination of
a specific constituent which is regulated under the NPDES permit program or the NPDWRs. Under the
protocol, the ATP applicant may develop and validate its proposed ATP either using the procedures
described in this document or the classical interlaboratory validation procedures provided by organizations
such as ASTM1 and AOAC-International.2'3
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ATP Protocol for Organic and Inorganic Analytes
1.2 Tiered System for Validation of Alternate Test Procedures
EPA recognizes that a formal interlaboratory method validation may not be suitable for all
situations and 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 that
classifies the intended use of a method and requires a method validation study that reflects the level of use
associated with each tier. For method equivalency demonstration in the tiered validation system, EPA has
specified approved methods that contain (or are supplemented with) QC acceptance criteria (Appendix E)
for most combinations of analyte and determinative technique. An applicant is required to demonstrate that
its ATP is able to meet the QC acceptance criteria of the EPA-designated approved method (or other EPA-
specified document) for the applicable combination of analyte and determinative technique. The three
method validation tiers are listed below.
Tier 1 ATPs may only be used by a single laboratory facility (limited-use) for one or more matrix type(s).
A matrix type is defined as a sample medium (e.g., air, soil, water, sludge) with common characteristics
across a given industrial subcategory. For example, C-stage effluents from chlorine bleach mills, effluent
from the continuous casting subcategory of the iron and steel industrial category, publicly owned treatment
works (POTW) sludge, and in-process streams in the Atlantic and Gulf Coast Hand-shucked Oyster
Processing subcategory are each a matrix type. Tier 1 validation requirements are for single-laboratory
testing in the matrix type(s) of interest.
Tier 2 ATPs may be used by all laboratories (nationwide use) for only one matrix type. Validation
requirements are for a three-laboratory validation study.
Tier 3 ATPs may used by all laboratories (nationwide use) for all matrix types. Validation requirements
are for a nine-laboratory validation study.
1.3 Scope of Alternate Test Procedures
This protocol for validation, submission, and approval of an ATP offers flexibility to modify
approved methods, provided that a laboratory demonstrates and documents that the modified method
produces results equal or superior to those produced by the EPA-designated approved method for the
applicable combination of analyte and determinative technique.
1.3.1 EPA-Designated Approved Methods
The ATP process is based on the use of designated QC acceptance criteria against which method
modifications are tested for equivalency. Using QC acceptance criteria as the performance measure allows
EPA to implement a more efficient ATP program.
An approved method, which contains (or is supplemented with) standardized QC procedures and
QC acceptance criteria, has been designated for each combination of regulated analyte and determinative
technique (Appendix E for inorganic methods, organic methods have QC acceptance criteria in the text of
the method). The QC acceptance criteria associated with the EPA-designated approved method are the
performance criteria against which ATPs of methods employing that combination of analyte and
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ATP Protocol for Organic and Inorganic Analytes
determinative technique are tested. Method equivalency is demonstrated when results produced by an ATP
meet or exceed the QC acceptance criteria associated with the EPA-designated approved method.
1.3.2 Modifications to Front-end Techniques
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.
Laboratories may modify any and all front-end techniques provided the modification is not explicitly
prohibited in the approved method that is being modified and provided the modification can be
demonstrated to produce results equal or superior to results produced by an EPA-designated approved
method for each combination of analyte and determinative technique. 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. However, if changing the chemistry of the method
might affect the extract holding times specified in the approved method, a new extract holding time study
must be performed. 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.
1.3.3 A dding New Target A nalytes
EPA will permit method developers to modify 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 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, public water supply (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 this ATP
protocol, developers can obtain approval for adding analytes to an approved method if the conditions below
are met:
(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 by the applicant and employed for determination of
the target analyte; see Protocol for EPA Approval of New Methods for Organic and
Inorganic Analytes in Wastewater and Drinking Water.
(3) 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. (This criterion precludes "method shopping," whereby a user might add
analytes to an approved method with less rigid sample collection or holding time criteria.)
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2.0 APPLICATION REQUIREMENTS
Every ATP application shall be made in triplicate and include a completed ATP application form
(provided in Appendix A) with required attachments.
2.1 Submission Addresses
A summary of where to submit ATP applications and the approval authorities for each tier level is
provided in Table 1.
Table 1: Submission of Alternate Test Procedure Applications
TIER
TieM
Tier 2
TierS
LEVEL OF
USE
Limited Use
for
Waste water
Nationwide
Use
Nationwide
Use
APPLICANT
EPA Regional laboratories
States, commercial
laboratories, individual
dischargers, or permitees in
States that do not have
authority
States, commercial
laboratories, individual
dischargers, or permitees in
States that have authority
All applicants
All applicants
SUBMIT
APPLICATION TO1
EPA Regional
Administrator
(Regional ATP
Coordinator)2
EPA Regional
Administrator
(Regional ATP
Coordinator)2
Director of State
Agency issuing the
NPDES permit2
Director, Analytical
Methods Staff, EPA
Headquarters
Director, Analytical
Methods Staff, EPA
Headquarters
APPROVAL
AUTHORITY
EPA Regional
Administrator
EPA
Administrator
EPA
Administrator
1 See Appendix B for EPA addresses.
2 The Regional Administrator may choose to forward Tier 1 (LU) applications to the Director of the
Analytical Methods Staff (AMS) for an approval recommendation.
Upon receipt of the application, the AMS ATP staff will assign an identification number to the application.
The applicant should use the identification number in all future communications concerning the application.
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2.2 Application Information
Information required on the ATP application form includes: the name and address of the applicant;
the date of submission of the application; the method number and title of the proposed ATP; the EPA-
approved method that was modified to develop the proposed ATP, the EPA-designated approved method
that will be used for demonstration of equivalency; the analytes(s) for which the ATP is proposed; the type
of application (i.e., wastewater, drinking water, or a combined wastewater/drinking water application); the
level of use desired (i.e., limited use or nationwide use); the tier level at which the proposed ATP will be
validated; and the applicant's NPDES permit number, the issuing agency, the type of permit and the
discharge serial number if applicable.
The following items should be submitted with the application: the justification for proposing the
ATP; the proposed ATP prepared in standard EPA format; a method comparison table that gives a side-by-
side comparison of the proposed ATP and the EPA-approved method that was modified; the method
validation study report, including supporting data; and, for nationwide applications that will undergo
rulemaking, method development information and documentation that EPA can use in preparing the
preamble and docket for the proposed rule.
All of the above-listed attachments do not need to be submitted with the initial application. If an
applicant is unsure whether or not a modification is allowed within the method-specified flexibility, the
applicant may request EPA to determine the necessity for a full ATP validation. The minimum
information required for EPA to begin reviewing an application is the completed application form, the
proposed method in standard EPA format, and the method comparison table. From this information,
EPA can determine whether a full ATP validation is required or whether the proposed modification is
within the inherent flexibility of the approved method.
Additionally, before proceeding with ATP validation, an applicant may choose to submit its
validation study plan for EPA review and comment. For modifications to methods that measure method-
defined parameters, such as oil and grease, a detailed validation study plan must be submitted and agreed
upon prior to conducting the study.
The elements required for a complete application at each tier are presented in Table 2. EPA must
receive all required application information and attachments before the application is considered complete.
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Table 2. Application Requirements
Tier
Level of Use
Application Requirements
TieM
Limited Use
Completed application form
Justification for ATP
Method in EPA format
Method comparison table
Validation study report
Tier 2
Nationwide Use
TierS
Completed application form
Justification for ATP
Method in EPA format
Method comparison table
Validation study report
Method development information and
documentation
2.2.1 Justification for A TP
The entity that proposes an ATP should provide a brief justification for why the ATP is being
proposed. Examples include but are not limited to: the method successfully overcomes some or all of the
interferences associated with the approved method; the ATP significantly reduces the amount of hazardous
wastes generated by the laboratory; or the cost of analyses are significantly reduced when using the ATP.
2.2.2 Standard EPA Method Format
In accordance with the standard EPA format advocated by EPA's Environmental Monitoring
Management Council (EMMC), methods must contain 17 specific topical sections in a designated order.
The 17 sections listed in Appendix C to this document are mandatory for all methods. Additional
numbered sections may be inserted starting with Section 11.0, Procedure, as appropriate for a particular
method. For detailed information on the EPA format for proposed methods, see the Guidelines and Format
document.4
2.2.3 Method Comparison Table
As part of the application, the applicant must perform an in-depth comparison of the proposed
ATP with the EPA approved method that has been modified, and document the comparison in a two-
column method comparison table. The two-column method comparison table shall include the number and
title of each method, the latest revision date of the proposed ATP, and a detailed discussion of each of the
17 topics required by the standard EPA method format. Each topic should be discussed on a separate row
in the method comparison table. The applicant should highlight any differences between the proposed ATP
and the approved method that has been modified. If the proposed method is an automation of a previously
approved manual method, any differences in kinetics and interferences should be presented and a
comparison of the final ratios of the concentrations of the reactants in the proposed and approved methods
included.
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2.2.4 Validation Study Report
The applicant must conduct a validation study and provide a comprehensive validation study report
with the ATP application. The validation study report must include the following elements:
• Background
• Study Design and Objectives
• Study Implementation
• Data Reporting and Validation
• Results
• Data Analysis/Discussion
• Conclusions
• Appendix A - The Method
• Appendix B - Validation Study Plan (optional for Tier 1)
• Appendix C - Supporting Data (Raw Data and Example Calculations)
These elements are described in Section 3.6.
2.2.5 Method Information and Documentation to Facilitate EPA Preparation of Preamble
and Docket
For Tier 2 and 3 applications, the ATP will be approved by the EPA Administrator through
rulemaking. In these cases, the applicant shall provide to EPA information and documentation that will aid
EPA in preparing the preamble and docket for the proposed rule that will be published in the Federal
Register. Information to be provided includes: a detailed background and 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. Specifically, the applicant shall submit information that:
• Defines the purpose and intended use of the method.
• States what the method is based upon, noting any relationship of the method to other existing
analytical methods and indicates whether the method is associated with a sampling method.
• Identifies the matrix(ces) for which the method has been found satisfactory.
• Describes method limitations and indicate any means of recognizing cases where the method may
not be applicable to the specific matrix types.
• Outlines the basic steps involved in performing the test and data analysis.
• Lists options to the method, if applicable.
• Describes and discusses the validation study report, including study design and objectives, study
limitations, study management, technical approach, data reporting and validation, results, data
analysis discussion, and conclusions.
Previous method rules that may serve as examples of the type of information and the appropriate
level of detail necessary 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. In addition to method information, the
applicant must provide copies of all relevant supporting documents used in developing the ATP, for EPA's
inclusion in the rule docket.
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2.3 Proprietary Information in Applications
All information provided to the Federal government is subject to the requirements of the Freedom
of Information Act. Therefore, any proprietary information submitted with the proposed ATP application
should be marked as confidential. EPA staff will handle such information according to the regulations in
subparts A and B of 40 CFR Part 2.
In accordance with 40 CFR §2.203, a business that submits information to EPA may assert a
business confidentiality claim covering the information by placing on (or attaching to) the information at
the time it is submitted to EPA, a cover sheet, stamped or typed legend, or other suitable form of notice
employing language such as trade secret, proprietary, or company confidential. Allegedly confidential
portions of otherwise non-confidential documents should be clearly identified by the business, and may be
submitted separately to facilitate identification and handling by EPA. If the business desires confidential
treatment only until a certain date or until the occurrence of a certain event, the notice should so state.
Please be advised, however, that any methods to be proposed in the Federal Register cannot be claimed as
confidential business information.
If a claim of business confidentiality is not made at the time of submission, EPA will make such
efforts as are administratively practicable to associate a late claim with copies of previously submitted
information in EPA files. However, EPA cannot ensure that such efforts will be effective in light of the
possibility of prior disclosure or widespread prior dissemination of the information.
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3.0 METHOD VALIDATION
3.1 Introduction
Method validation is the process by which a laboratory or vendor substantiates the performance of
a method modification by demonstrating that the modified method can meet the QC acceptance criteria in
the EPA-designated method or other EPA-specified document. Appendix E to this protocol contains the
QC acceptance criteria for inorganic methods. The QC acceptance criteria for organic methods are
contained in the text of the methods (for organic methods that do not contain QC acceptance criteria consult
with EPA). ATPs must be validated to prove that they accurately measure the concentration of an analyte
in an environmental sample. If, during a compliance inspection or audit, it is determined that a regulated
party is using an unvalidated modified method, the data generated by the unvalidated method will be
considered unacceptable for compliance monitoring or reporting. The validation requirements listed below
were developed to reflect the level of intended use of the ATP. This is accomplished through a three-tiered
approach, as shown in Table 3.
Table 3: Tiered Validation Strategy
Tier Level
Tierl
Tier 2
TierS
Laboratory Use
Single Laboratory
(Limited use)
All Laboratories
(Nationwide use)
All Laboratories
(Nationwide use)
Applicable to ...
One or more matrix types
from any industry
One matrix type within one industrial subcategory; or all
PWSs
All matrix types from all industrial subcategories
Under Tier 1, single laboratories will be allowed to validate and use modified test methods without
the burden of conducting an interlaboratory validation study, whereas methods intended for multi-
laboratory use in a given industrial subcategory (Tier 2) or for multi-laboratory use for all industrial
subcategories (Tier 3) require interlaboratory testing.
3.2 Summary of Validation Requirements
EPA has developed a tiered validation approach that coordinates validation requirements with the
level of intended use of the ATP. Tier 1 (LU) represents validation in a single laboratory, Tier 2 (NW)
represents interlaboratory validation in one industrial subcategory, and Tier 3 (NW) represents
interlaboratory validation in multiple matrix types. ATPs may be used after validation at the appropriate
level is performed and formal approval is granted by the appropriate authority. Tier 1 (LU) contains two
levels of validation, depending on whether the individual laboratory will be applying the ATP to a single
matrix type or to multiple matrix types. The Tier 1- Single Matrix Type category allows the laboratory to
apply the ATP to a single matrix type. The Tier 1- Multiple Matrix Type category allows a single
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ATP Protocol for Organic and Inorganic Analytes
laboratory to apply the ATP to an unlimited number of matrix types after the method has been validated on
a minimum of nine matrix types.
Table 4 summarizes the validation requirements for wastewater ATPs. Table 5 summarizes the
validation requirements for drinking water ATPs. Please note that only Tier 2 or Tier 3 (NW) validations
are applicable to drinking water; the Office of Ground Water and Drinking Water (OGWDW) no longer
accepts Tier 1 (LU) ATP applications for drinking (potable) water programs.
Table 4. Summary of Validation Requirements for Wastewater Alternate
Test Procedures'1'
Method Application
Number of
Matrix
Labs types
Number of Analyses Required
IPR-
reagent
water12' MS/MSD MDL(3)
Tier 1-Single-lab
First matrix type 1
Each additional matrix type (8 max.) 1
Tier 2-Multi-lab, single matrix type 3
Tier 3-Multi-lab, multiple matrix types
All matrix types 9(7)
12
36
2<4)
2<4)
6(6)
18(6)
21
63
Notes:
(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. Nine would be the maximum number of matrix types (or facilities) that would be
required to validate a modified wastewater method at Tier 1 or 3.
(2) IPR reagent water analyses would be used to validate a method modification. The required
number of IPR analyses would be four times the number of laboratories required to validate a
method modification because each laboratory would perform a 4-replicate IPR test.
(3) A method detection limit (MDL) test would be performed in each laboratory using the alternate
test procedure. 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
EPA-designated approved method.
(4) The MS/MSD test would demonstrate that the EPA-designated approved method MS/MSD QC
acceptance criteria have been met.
(5) The MDL, reagent water IPR, and sample matrix IPR tests would not have to be repeated after
the first matrix type or facility was validated.
(6) The MS/MSD analyses would demonstrate that MS/MSD recovery and precision criteria
associated with the EPA-designated approved method have been met. The required number of
MS/MSD analyses would be two times the number of facilities or matrix types tested.
(7) The number of laboratories and samples would vary if a conventional interlaboratory study is
used.
10
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Table 5. Summary of Validation Requirements for Drinking Water Alternate
Test Procedures'1'
Method Application
Number of
Labs PWSs
Number of Analyses Required
IPR- reagent
water12' MS/MSD MDL(3)
Tier 2-Multilab 3 3 12 6(4) 21
Notes:
(1) Numbers of analyses in this table do not include background analyses or additional QC tests
such as calibration, blanks, etc.
(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 would be four times
the number of laboratories required to validate a method modification because each laboratory
would perform a 4-replicate IPR test.
(3) A method detection limit (MDL) test would be performed in each laboratory using the alternate
test procedure. 40 CFR part 136 Appendix B requires a minimum of seven analyses per
laboratory to determine an MDL.
(4) For validation of a method modification, the MS/MSD analyses would demonstrate that the EPA-
designated approved method MS/MSD recovery and precision have been met.
All ATPs must be validated to demonstrate that the method is capable of yielding reliable data for
compliance monitoring purposes. Test results from validation of an ATP are used to demonstrate that the
ATP produces results equivalent to results produced by the EPA-designated approved method.
Equivalency is established by demonstrating that the ATP generates results that meet or exceed the QC
acceptance criteria of the EPA-designated approved method. Appendix E to this protocol contains the QC
acceptance criteria for inorganic methods. The QC acceptance criteria for organic methods are contained in
the text of the methods (for organic methods that do not contain QC acceptance criteria consult with EPA).
EPA must approve all ATPs. All validation study results must be documented in accordance with the
requirements outlined below.
3.3 Tier 1, 2, and 3 Validation Studies
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, or 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 studies are expected to be used by vendors, commercial laboratories, water supply laboratories,
dischargers, and state and municipal laboratories repetitively testing samples from multiple sites within the
same industrial subcategory on a routine basis. Tier 3 studies are expected to be used by vendors,
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commercial laboratories, dischargers, and state and municipal laboratories testing a wide variety of sample
matrices from diverse sites.
3.3.1 Tier 1 Validation Studies (for Wastewater Only)
The primary intent of Tier 1 is to allow use of a modified method by a single laboratory. Tier 1
can be applied to one or more matrix types, excluding drinking water matrices; the Office of Ground Water
and Drinking Water (OGWDW) no longer accepts Tier 1, limited-use drinking (potable) water
applications.
Tier 1 - Single Matrix Type
Tier 1-Single Matrix Type validation studies are performed in a single laboratory on a single
matrix type. Results of the validation study and the method modification are applicable in this laboratory
to this matrix type and cannot be used by another laboratory or for another matrix type.
Tier 1 - Multiple Matrix Types
If a laboratory intends to apply the method to more than one matrix type, the laboratory must
validate the method on each matrix type. The maximum number of matrix types to which the ATP must be
applied to demonstrate that it will likely be successful for all other matrix types is nine matrix types for
wastewater ATPs. EPA chose this upper limit of matrix tests for Tier 1- multiple matrix types validation,
because the maximum number of matrices tested should not be greater than the number required for Tier 3
validation of a wastewater method (nine). Therefore, after testing nine different wastewater matrix types,
no subsequent matrix type tests are required, and the method can be used for any matrix type. The specific
tests to be conducted on the first wastewater matrix type or and those for each additional matrix type are
enumerated in Tables 4 and 5. In all cases, the laboratory must try to determine if the measurement result
for the target analyte using a new matrix type differs from the result obtained in a reagent water matrix or
in a previously validated matrix type sample.
Matrices that must be tested for Tier 1- multiple matrix type validation of a wastewater ATP are
given in Table 6. As with a Tier 1- single matrix type validation study, Tier 1- multiple matrix type
validation studies are performed in a single laboratory and, therefore, cannot be transferred to another
laboratory. If a wastewater method is validated by a single laboratory in two to eight discrete matrix types,
the validation is applicable to those matrix types only. However, once a laboratory has validated the
method on nine matrix types, and those matrix types possess the characteristics required in Table 5, the
validation is applicable to all other matrix types.
If results of Tier 1- multiple matrix type validation studies are to be applied to a different medium
(e.g., air, water, soil, sludge), each medium must be represented in the samples tested in the validation
study.
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Table 6. Matrix Types Required for Multiple Matrix Type
Validation Studies
1. Effluent from a POTW
2. ASTM D 5905 - 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 (nationwide-use only)
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
NaCI greater than 120 mg/L
CaCO3 greater than 140 mg/L
3.3.2 Tier 2 Validation Studies for Wastewater and Drinking Water
The primary intent of Tier 2 is to allow all regulated entities and laboratories to apply an ATP 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 modified drinking water method.
EPA believes that implementation of Tier 2 will encourage the development and application of
techniques that overcome matrix interference problems specific to effluents of certain industrial
subcategories, lower detection limits, improve the reliability of results, lower the costs of measurements, or
improve overall laboratory productivity when analyzing samples from a given industry.
Significant industries within Tier 2 are: PWSs, publicly-owned treatment works (POTWs), and
individual industrial subcategories that are defined in the regulations at 40 CFR parts 405 - 503. At
present, there are approximately 650 industrial subcategories defined in the Part 405 - 503 regulations,
each of which constitutes an individual industry under this protocol.
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 one or more
facilities in the same industrial subcategory. In all cases, the laboratory must try to determine if the
measurement result for the target analyte using an ATP differ from the result obtained in a reagent water
matrix or in a previously validated matrix type or PWS sample.
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Drinking water sources tested for Tier 2 validation of a drinking water ATP must include samples
collected from PWSs with water quality characteristics that are sufficiently different so that sample matrix
effects, if any, can be observed. 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 ATP. 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.
For POTWs, if an ATP is validated on final effluent only, that method would be 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 are to be monitored, the method must be validated
separately on these sample matrix types.
In contrast to Tier 1, once an ATP 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 the validated matrix type from within the industrial
subcategory, and as long as the other laboratories meet all of the method's QC acceptance criteria. If the
ATP is to be applied to another matrix type, the modification must be validated separately on that matrix
type.
3.3.3 Tier 3 Validation Studies
The primary intent of Tier 3 is to allow nationwide use of an ATP by all regulated entities and
laboratories for all matrix types. 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 all matrix types.
Tier 3 validation studies are performed in a minimum of nine laboratories, each with a different
matrix type, for a total of nine samples. The minimum requirements for sample matrix types that must be
used in the validation study are given in Table 6. If the method is to be applied to drinking water, at least
one matrix employed in the study should be of the drinking water type. 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 6. For example, if an ATP 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 developer of the ATP in identifying sources for samples of
such discharges.
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3.4 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 and submit a detailed study plan. As noted earlier, for ATPs that measure method-
defined parameters, such as oil and grease, a detailed validation study plan must be submitted and agreed
upon prior to conducting the study. For Tier 1 ATP validations involving analytes which are not method-
defined, development of a validation study plan is not required though it is recommended.
The validation study plan should contain the elements described in Sections 3.4.1 through 3.4.6.
3.4.1 Background
The Background section of the validation study plan should:
• Identify the ATP method as a modification of an approved method
• Identify the program use of the ATP method (drinking water or waste water or both)
• Include a summary of the ATP method
• Cite the organization and method number (given in 40 CFR parts 136, 141, and 405 - 503) for the
approved method
• Describe the reasons for and extent of the modification, the logic behind the technical approach to
the modification, and the result of the modification
• Identify the matrices, matrix types, and/or media to which the ATP method is believed to be
applicable
• List the analytes measured by the ATP method 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; a total metals method must measure total metals.
3.4.2 Objectives
The Objectives section of the validation study plan should describe overall objectives and data
quality objectives of the study.
3.4.3 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
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3.4.4 Technical Approach
The Technical Approach section of the validation study plan should:
• Indicate at which tier the study will be performed
• Describe the approach that will be followed by each organization involved in the study
• 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
3.4.5 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.
3.4.6 Limitations
The Limitations section of the validation study plan should explain any limiting factors related to
the scope of the study.
3.5 Detailed Procedures for Conducting Validation Studies
When validating ATPs, laboratories must adhere to the standardized QC detailed in the EPA-
designated approved method (or other EPA-specified document) and incorporate these criteria into the
ATP. Laboratories must use a reference matrix (usually, reagent water) and field samples for the
validation study.
3.5.1 Method Compilation
Prior to conducting a validation study, the organization responsible for modifying the method
should detail the full method in accordance with EPA's Guidelines and Format document.4 If the
organization that develops an ATP is a consensus standards organization or government organization with
a standardized format, that organization's standard 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.
3.5.2 Method Detection Limit Study
Each laboratory participating in the Tier 1, 2, or 3 validation study shall use the procedures
specified in the modified method and perform a method detection limit (MDL) study in accordance with the
procedure given at 40 CFR part 136, Appendix B.
For validation studies of an ATP, each laboratory participating in the study must demonstrate an
MDL that meets the criteria specified for the EPA-designated approved method. For wastewater methods,
the MDL must be equal to or less than the ML of the EPA-designated approved method or less than 1/10
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the regulatory compliance limit, whichever is greater. The 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 EPA-designated approved method (or other
EPA-specified document) but is potentially more valuable in allowing determination of the analyte(s) of
interest at the regulatory compliance limit in a complex sample matrix. For drinking water ATPs, the
required detection limits are specified for regulated chemical contaminants at 40 CFR part 141. For
unregulated drinking water contaminants, the detection limits in the EPA-designated approved method or
other EPA-specified document should be used.
Each laboratory must perform its MDL study on an instrument that is calibrated at a range that
will encompass the minimum level (ML) for wastewater ATPs or one-half the maximum contaminant level
(MCL) for drinking water ATPs.
3.5.3 Calibration
Following completion of the MDL study, each laboratory participating in the study must perform a
calibration in accordance with the procedures specified in the ATP.
For validation of an ATP, 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 EPA-designated
approved method (or other EPA-specified document), as may often be the case for drinking water methods,
in the applicable regulations.
3.5.4 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. The
IPR consists of analyses of four replicates of reagent water spiked with the analytes of interest.
For validation of an ATP, each laboratory participating in the study must demonstrate that it can
meet the IPR precision and recovery criteria given for the EPA-designated approved method.
3.5.5 Field Sample A nalyses
After laboratories participating in the Tier 1, 2, or 3 validation study have successfully completed
the IPR analyses, the method modification is validated on the matrix type(s) chosen for the validation
study. The numbers of analyses required are described below.
3.5.5.1 Tier 1 - Single Matrix Type Validation Studies
In a Tier 1- single matrix type study performed to validate an ATP, the laboratory must determine
the background concentration of an unspiked sample prior to analyzing an MS/MSD pair for the matrix
type being tested, for a total of three field sample analyses (background, MS, and MSD). The laboratory
performing the validation study must demonstrate that it can meet the MS/MSD precision and recovery QC
acceptance criteria given for the EPA-designated approved method. QC acceptance criteria for most
inorganic analyte-method combinations can be found at Appendix E of this document. QC acceptance
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criteria for other classes of analytes (e.g. pesticides) are often published in the EPA-designated approved
method compilation or in other EPA documents.
3.5.5.2 Tier 1 - Multiple Matrix Type Validation Studies
In Tier 1- multiple matrix type studies performed to validate ATPs, 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 for wastewater. Since three field sample analyses are required for each matrix type
(one background, one MS, and one MSB), and between two and nine matrix types may be tested for
wastewater and between two and three for drinking water, a Tier 1- Multiple matrix type validation study
will require analysis of 6 - 27 samples. The laboratory performing the validation study must demonstrate
that it can meet the MS/MSD precision and recovery QC acceptance criteria given for the EPA-designated
approved method. QC acceptance criteria for most inorganic analyte-method combinations can be found at
Appendix E of this document. QC acceptance criteria for other classes of analytes (e.g. pesticides) are
often published in the EPA-designated approved method compilation or in other EPA documents.
3.5.5.3 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 on the sample it receives. Because there are three
laboratories, each of which performs three analyses (one background, one MS, and one MSD), Tier 2
validation studies will require analysis of 9 samples. Each laboratory participating in the study must
demonstrate that it can meet the MS/MSD precision and recovery QC acceptance criteria given for the
EPA-designated approved method. QC acceptance criteria for most inorganic analyte-method
combinations can be found at Appendix E of this document. QC acceptance criteria for other classes of
analytes (e.g. pesticides) are often published in the EPA-designated approved method compilation or in
other EPA documents.
3.5.5.4 Tier3 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. Each laboratory participating in the
study must demonstrate that it can meet the MS/MSD precision and recovery QC acceptance criteria given
for the EPA-designated approved method. QC acceptance criteria for most inorganic analyte-method
combinations can be found at Appendix E of this document. QC acceptance criteria for other classes of
analytes (e.g. pesticides) are often published in the EPA-designated approved method compilation or in
other EPA documents.
3.5.6 Ongoing Precision and Recovery
Each batch of samples which includes field samples, but not the IPR samples, must include an
OPR sample. Each laboratory participating in the study that analyzes an OPR sample must demonstrate
that it can meet the OPR recovery criteria given in the EPA-designated approved method (or other EPA-
specified document).
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3.5.7 Calibration Verification
The field samples discussed in Section 3.5.5 must be analyzed in a separate batch of instrumental
determinations from the initial calibration sequence, so that calibration verification is performed. Each
laboratory participating in the Tier 1, 2, or 3 validation study must verify calibration as described in the
method.
Each laboratory participating in the study and verifying calibration must demonstrate that it can
meet the acceptance criteria given for the EPA-designated approved method (or other EPA-specified
document) for calibration verification. QC acceptance criteria for most inorganic analyte-method
combinations can be found at Appendix E of this document. QC acceptance criteria for other types of
analytes (e.g. pesticides) are often published in the EPA-designated approved method compilation or in
other EPA documents.
3.5.8 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.
For validation of an ATP, each laboratory participating in the study must demonstrate that it can
meet the QC acceptance criteria for blanks that are specified in the method (or other EPA-specified
document).
3.5.9 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.
For validation of an ATP, each laboratory participating in the study must demonstrate that it can
meet the surrogate or labeled compound recovery criteria specified in the EPA-designated approved method
(or other EPA-specified document).
3.5.10 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.
Each laboratory participating in the study must demonstrate that it can meet the absolute and
relative retention time criteria that are specified in the EPA-designated approved method (or other EPA-
specified document).
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3.5.11 New Analytes
As described in Section 1.3.3, EPA proposes to consider the addition of new analytes to approved
methods as acceptable method modifications under this protocol. Laboratories will be required to
demonstrate equivalency in accordance with the requirements summarized above for other Tier 1, 2, and 3
ATPs. In addition, laboratories are required either to develop QC acceptance criteria for the added analyte;
see Protocol for EPA Approval of New Methods for Organic and Inorganic Analytes in Wastewater and
Drinking Water.
3.6 Validation Study Report
Laboratories or other organizations responsible for developing ATPs at Tiers 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 ATPs which
are not intended for use with method-defined analytes, the completed Checklists®, along with the raw data
and example calculations, are considered adequate to document method equivalency; a full validation study
report is not necessary. In all cases, a copy of all required validation data should be maintained at the
laboratory or other organization responsible for developing the ATP.
The information and supporting data required in the validation study report must be sufficient to
enable EPA to support a claim of equivalent performance of a method modification. If data are collected
by a contract laboratory, the organization responsible for using the method (e.g., 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.
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 3.6.1 through 3.6.10.
3.6.1 Background
The Background section of the validation study report must describe the method modification that
was validated and identify the organization responsible for developing the ATP. The background section of
the validation study report must:
• Include a method summary
• Cite the organization and method number and title for the ATP
• Cite the method number (given in 40 CFR parts 136, 141, and 405 - 503) for the approved method
that is being modified
• Cite the method number (given in 40 CFR parts 136, 141, and 405 - 503) for the EPA-designated
approved method that is being used for demonstrating method equivalency
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• Describe the reasons for and extent of the modification, the logic behind the technical approach to
the modification, and the result of the modification
• Identify the matrices, matrix types, and/or media to which the modified method is believed to be
applicable
• List the analytes measured by the modified method including corresponding CAS Registry or
EMMI numbers (Alternatively, this information may be provided on the data reporting forms in 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
3.6.2 Study Design an d 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
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 3.4 for required elements of the study design).
3.6.3 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
• 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
3.6.4 Data Reporting and Validation
This section of the validation study report must describe the procedures that were used to report
and validate study data. While EPA does not require the use of an standard format for analytical data
submission, a validation study data reporting form may be found in Section 9.3 of this document.
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3.6.5 Results
This section of the validation study report presents the study results. Results must be presented on
the Checklists5, 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 3.6.10).
The Checklists, instructions for their completion, and an example set of completed Checklists are
provided in Appendix D. 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 the modified method met all QC acceptance criteria of the
EPA-designated approved method (or other EPA-specified document), for purposes of assessing method
equivalency.
3.6.6 Data A nalysis/Discussion
This section of the validation study report must provide a statistical analysis and discussion of the
study results. The discussion must address any discrepancies between the results and the QC acceptance
criteria of the EPA-designated approved method.
3.6.7 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).
3.6.8 Appendix A - The Method Compilation
The modified method compilation (or modified portion of the approved method) prepared in
accordance with EPA's Guidelines and Format document4, must be appended to the validation study report.
3.6.9 Appendix B - Validation Study Plan
If a validation study plan was prepared, it must be appended to the validation study report.
3.6.10 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.
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3.6.10.1 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
• Instrument(s) 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)
• 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 EPA-designated approved 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.
3.6.10.2 Example 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.
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4.0 EPA REVIEW AND APPROVAL
4.1 EPA Review of Applications
All requests for approval of proposed ATPs will undergo review and approval by EPA. Limited
use ATPs (Tier 1) will be approved through an EPA letter of approval. ATPs proposed for nationwide use
(Tiers 2 and 3) will be approved through rulemaking. Proposed test procedures prepared under this
protocol should demonstrate an improvement when compared to the existing EPA-approved method that
offers one or more of the following advantages: better method sensitivity or selectivity, lower analytical
costs, fewer matrix interference problems, improvement in laboratory productivity, or reduction in the
amount of hazardous materials used and/or produced in the laboratory.
EPA's Analytical Methods Staff (AMS) at EPA Headquarters will review all nationwide-use ATPs
and will review limited-use applications if requested by the EPA Regional Office or State Agency. AMS
may be assisted in its technical review by contractor personnel. When a formal ATP application is
received, AMS will first check the documentation for completeness. If the documentation is incomplete,
AMS will contact the applicant and request missing documentation before proceeding with its review.
At a minimum, an application must include a completed ATP application form, the proposed test
procedure in EPA standard format, and the method comparison table, before AMS will review the package.
If these elements are present, AMS will assess the application to determine whether a full ATP validation is
required or whether the requested modification falls within the inherent flexibility of the method. In this
case, AMS will notify the applicant whether or not ATP validation is required.
If all elements of the ATP application are present, including the validation study report and
supporting data, AMS will begin an internal review of the ATP for scientific merit, consistency, and
appropriateness. The internal review at EPA may involve multiple programs and workgroups. Should any
problems or questions arise during the review, EPA or its technical support contractor will communicate
with the applicant to resolve outstanding issues. Depending on the circumstances, EPA may return the
application to the applicant for revision. Internal review of proposed ATPs will involve the three steps
briefly described below.
The first step of EPA's technical review will evaluate the description of the proposed method and
method comparison table, and assess the ATP's applicability for approval at 40 CFR 136 or 141. If the
proposed method is not applicable to 40 CFR 136 or 141 and/or the method description or method
comparison table are not acceptable, EPA will recommend rejection of the application. If this information
is acceptable, the evaluation will proceed.
In the second step of EPA's review, the performance of the ATP will be evaluated. The
performance (sensitivity, precision, and accuracy) of the ATP will be compared to the performance of the
EPA-designated approved method used to demonstrate method equivalency. This evaluation is based on
the data provided by the applicant in the Checklists. At a minimum, the results produced using the ATP
must meet the QC acceptance criteria of the EPA-designated approved method. If method performance is
acceptable, the review will continue.
As the third and final step, EPA will perform a detailed audit of the proposed method test data. The
evaluation of test data in applications can be accomplished more quickly if machine-readable files of test
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data (and analysis software where different from EPA software) are provided on floppy disks with the
application. Data files should be in IBM-PC compatible format, suitable for input directly into statistical
analysis software, such as the Trimmed Spearman-Karber, Probit, Dunnett, and ICP programs.
4.2 Approval Recommendation
EPA will complete its review and notify the applicant of its approval recommendation within 90
days of receiving a complete application (see Table 2). For limited-use wastewater applications (Tier 1),
AMS will notify the applicant of EPA's recommendation, and forward the recommendation to the
appropriate Regional Administrator (see Table 1) for action. The Regional Administrator will issue the
formal approval for use of the ATP.
For limited-use drinking water applications and all nationwide-use applications (Tiers 2 or 3),
AMS will notify the applicant of EPA's recommendation, and if the ATP is recommended for approval,
will initiate the rulemaking process through which the ATP is formally approved by the EPA
Administrator.
4.3 Rulemaking Process
Using the method information provided with the ATP application to develop the preamble, EPA
will prepare the proposed rule for approval, compile the rule docket, pass the proposed rule through
internal review at EPA, and submit it to the Office of the Federal Register (OFR) for publication.
Preparation, approval, and publication of a proposed rule generally requires a minimum of four months,
and may take longer depending on the nature of the method. When published, the proposed rule requests
public comment and allows a specified comment period, generally 30 to 60 days. At the end of the
comment period, EPA will forward any significant comments to the method applicant for 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 provided by the applicant and complete the response-to-
comments document for the final rule. EPA will then prepare the final rule, compile the rule docket, 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 effective date, the method is approved by EPA
and will be included in the appropriate table(s) at 40 CFR 136 and/or 141 in the next CFR update. It
generally requires a minimum of eight months after the proposed rule is published to receive and
respond to comments, prepare and process the final rule through internal EPA review, and publish the
final rule in the Federal Register.
If circumstances merit, EPA may issue a letter of approval to authorize use of the ATP during the
rulemaking period.
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ATP Protocol for Organic and Inorganic Analytes
5.0 REFERENCES
1. ASTM, 1994. Standard Practice for Determination of Precision and Bias of Applicable Methods
of Committee D-19 on Water. Designation D-2777-86 (Reapproved 1994). Annual Book
of ASTM Standards,. Vol. 11.04.
2. Youden, W.J. and E.H. Stiener, 1975. Statistical Manual of the AOAC. AOAC- International.
1111 N. 19th Street; Suite 210, Arlington, VA 22209.
3. Wernimont, G.T., 1985. Use of Statistics to Develop and Evaluate Analytical Methods. AOAC-
International.
4. USEPA 1996. Guidelines and Format for Methods to Be Proposed at 40 CFR Part 136 or Part
141 (Guidelines and Format document). U.S. Environmental Protection Agency. Office of Water,
Engineering and Analysis Division. Washington, D.C. EPA- 821-B-96-003.
5. Checklist for Initial Demonstration of Method Performance, Checklist for Continuing
Demonstration of Method Performance, and Certification Statement
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6.0 APPENDIX A - ATP APPLICATION FORM
EPA Office of Water
Alternate Test Procedure Application Form for Chemical Analytes
Applicant Name and Address:
Date Application Submitted:
Alternate Test Procedure:
(Method number & title)
Alternate to Approved Method:
EPA-designated Approved
Method for Equivalency
Demonstration:
Analyte(s):
Type (WW, DW, or WW/DW):
Level of Use:
(LU or NW)
JEPA Use Only
<\TP Case No.
Validation Tier:
(1,2 or 3)
FOR LIMITED-USE APPLICATIONS ONLY:
ID number of existing or pending permit:
Issuing agency:
Type of permit:
Discharge serial number:
ATTACHMENTS:
n Justification for ATP
n Alternate Test Procedure (Method in standard EPA format)
Q Method Comparison Table
n Validation Study Plan (optional)
n Validation Study Report
n Method Information and Documentation for Preamble and Docket
n Other
Submit Application and Attachments in Triplicate
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7.0 APPENDIX B - HEADQUARTERS AND REGIONAL ATP CONTACTS
Headquarters
William Telliard
Director, Analytical Methods Staff (AMS)
Mail Code 4303
Waterside Mall
401 M. Street, S.W.
Washington, DC 20460
Region 1
Arthur Clark
QA Chemist
USEPA Region 1
EQA
60 Westview Street
Lexington, MA 02173
Region 2
Linda M. Mauel
USEPA Region 2
Division of Science and Monitoring
2890 Wood bridge Avenue (MS-220)
Building 10
Edison, NJ 08837-3679
Region 3
Charles Jones
Regional QA Officer
USEPA Region 3
Environmental Assessment and Protection
Division
1650 Arch Street, 3ES-10
Philadelphia, PA 19103-2029
Region 4
Wayne Turnbull
Chemist/ATP Coordinator
USEPA Region 4
Room: SESD
960 College Station Road
Athens, GA 30605-2720
Kenneth Gunter
USEPA Region 5
77 W. Jackson Blvd., WT-15J
Chicago, IL 60604
Region 6
David Stockton
USEPA Region 6 Laboratory
Houston Branch
10625 Fallstone Road (6MD-HI)
Houston, TX 77099
Region 7
Doug Brune
USEPA Region 7
726 Minnesota Avenue, ENSV/QA
Kansas City, KS66101
Region 8
Rick Edmonds
Regional Quality Assurance Officer
USEPA Region 8
999 18th Street - Suite 500 (8TMS-L)
Denver, CO 80202-2466
Region 9
Roseanne Sakamoto
USEPA Region 9
75 Hawthorne Street, PMD-3
San Francisco, CA 94105
Region 10
Bruce Woods
QAO
USEPA Region 10
200 Sixth Avenue, OEA-095
Seattle, WA 98101
Region 5
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8.0 APPENDIX C - STANDARD EPA METHOD FORMAT
The following is a listing of the 17 required method sections. Applicants should consult the Method
Guidelines and Format document4 for a detailed description of the required content for each section and
other formatting guidelines and conventions.
1.0 Scope and application
This section outlines the purpose, range, limitations, and intended use of the method, and identifies
target analytes.
2.0 Summary of Method
This section provides an overview of the method procedure and quality assurance.
3.0 Definitions
This section includes definitions of terms, acronyms, and abbreviations used in the method. If
preferred, definitions may be provided in a glossary at the end of the method or manual. In this
case, the definitions section must still appear in the method, with a notation that definitions are
provided in a glossary at the end of the method. Refer to the specific section number of the
glossary.
4.0 Interferences
This section identifies known or potential interferences that may occur during use of the method,
and describes ways to reduce or eliminate interferences.
5.0 Safety
This section describes special precautions needed to ensure personnel safety during the
performance of the method. Procedures described here should be limited to those which are above
and beyond good laboratory practices. The section must contain information regarding specific
toxicity of analytes or reagents.
6.0 Equipment and Supplies
This section lists and describes all non-consumable supplies and equipment needed to perform the
method.
7.0 Reagents and Standards
This section lists and describes all reagents and standards required to perform the method, and
provides preparation instructions and/or suggested suppliers as appropriate.
8.0 Sample Collection, Preservation, and Storage
This section provides requirements and instructions for collecting, preserving, and storing samples.
9.0 Quality Control
This section cites the procedures and analyses required to fully document the quality of data
generated by the method. The required components of the laboratory's quality assurance (QA)
program and specific quality control (QC) analyses are described in this section. For each QC
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analysis, the complete analytical procedure, the frequency of required analyses, and interpretation
of results are specified.
10.0 Calibration and Standardization
This section describes the method/instrument calibration and standardization process, and required
calibration verification. Corrective actions are described for cases when performance
specifications are not met.
11.0 Procedure
This section describes the sample processing and instrumental analysis steps of the method, and
provides detailed instructions to analysts.
12.0 Data Analysis and Calculations
This section provides instructions for analyzing data, and equations and definitions of constants
used to calculate final sample analysis results.
13.0 Method Performance
This section provides method performance criteria for the method, including precision/bias
statements regarding detection limits and source/limitations of data produced using the method.
14.0 Pollution Prevention
This section describes aspects of the method that minimize or prevent pollution known to be or
potentially attributable to the method.
15.0 Waste Management
This section describes minimization and proper disposal of waste and samples.
16.0 References
This section lists references for source documents and publications that contain ancillary
information. Note: Each method should be a free-standing document, providing all information
necessary for the method user to perform the method may be found. References within a method
should be restricted to associated or source material. Procedural steps or instructions should not
be referenced as being found elsewhere, but should be included in total within the method.
77.0 Tables, Diagrams, Flowcharts, and Validation Data
This section contains all method tables and figures (diagrams and flowcharts), and may contain
validation data referenced in the body of the method.
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9.0 APPENDIX D - EQUIVALENCY CHECKLISTS
9.1 Checklists and Instructions for Use
The Checklist for Initial Demonstration of Method Performance and Certification Statement
(collectively called "Checklists") and instructions for their completion are provided in this appendix
section. The Checklists, 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 ATP approval program; these categories are indicated
as "NA" (not applicable). The EMMC instructions are annotated to clarify each checklist item's
applicability to the ATP approval program. Annotated sections are highlighted within text boxes as shown
below.
ATP Approval Protocol
Annotated instructions.
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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)
8. Sample(s) used in initial demonstration have
recommended preservative, where applicable.
Performance
Criteria (2)
Based on
Measurement Reference
Quality
Method Objective
Results
Obtained
Pert.
Spec.
Achieved
(/)
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Initial Demonstration of Method Performance (1)
Category
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)
27. Bias (analyte by analyte)
28. Detection Limit (w/ units; analyte by analyte)
Performance
Criteria (2)
Based on
Measurement Reference
Quality
Method Objective
Results
Obtained
Pert.
Spec.
Achieved
(/)
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Initial Demonstration of Method Performance (1)
Category
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
Results
Obtained
Pert.
Spec.
Achieved
(/)
1 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):
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 7/13/96
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.
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. The
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.
ATP Approval Protocol:
(1) Under the ATP approval protocol, the term "EPA-designated approved method" is used in place of
EMMC's term "reference method"
(2) EMMC's definition of the term "media" is equivalent to the ATP protocol's definition of "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.
ATP Approval Protocol:
Under the ATP approval protocol, the term "ATP" is used in place of "PBM".
Header:
Each page of the checklist contains six lines of header information, consisting of:
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* Date (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).
* 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).
ATP Approval Protocol:
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 Regulation(enter 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.
ATP Approval Protocol:
Enter the matrix type as defined in the ATP protocol, 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 in 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?7E: UNDER NORMAL
CIRCUMSTANCES, IT WOULD NEVER BE ACCEPTABLE TO ANSWER "NO" TO ANY OF
THESE PERFORMANCE CATEGORIES, OR FAIL TO ATTACH THE REQUESTED
MATERIALS :
ATP Approval Protocol:
Categories that do not apply to ATP method validation are 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 & 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 and project managers/officers.
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ATP Approval Protocol:
See the Guidelines and Format for Methods to be Proposed at 40 CFR Part 136 or Part 141 ( EPA-
821-B-96-003) for detailed guidance on the standard EPA 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 in 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 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).
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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. Samples(s) 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. Samples(s) used in the initial demonstration must be within the recommended holding times,
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.
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.
#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 Oast 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 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.
#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.
#14. Source of reference material.
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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, fluorinated or isotopically labeled compounds, with structural
similarities to the analytes of interest. Also, they are not expected to be present in environmental samples.
Surrogates are often used in the analysis for organic analytes. Enter the names of the surrogate compounds
in 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 attach 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 in 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".
ATP Approval Protocol:
Enter the same matrix type as entered in the header.
41 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
#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 into 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.
ATP Approval Protocol:
Under the ATP protocol, initial spikes, also known as initial precision and recovery (IPR) standards,
shall be performed in reagent water. Using reagent water allows comparison of IPR spike recoveries
determined with the modified method against IPR criteria specified in the EPA-designated approved
method because approved 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.
#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 (analyte by analyte).
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.
42 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
ATP Approval Protocol:
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).
ATP Approval Protocol:
For ATPs, enter the detection limits specified in the EPA-designated approved method.
#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 in 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 (w/ units; analyte by analyte).
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.
#31. Qualitative confirmation.
Enter all relevant criteria used for identification, including such items as: retention time; use of a second
chromatographic 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.
#32. Frequency (initial Demonstration to be performed.
43 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
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 other necessary program/project specific method performance categories.
ATP Approval Protocol:
Under the ATP approval protocol 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.
#34. Matrix Spike/Matrix Spike Duplicate Relative Percent Deviation.
Enter the calculated relative percent deviation between the MS and MSB analyte recoveries.
Signatures:
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.
44 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
9.2 Example of Completed Checklists
This appendix 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 (40 CFR 141.24) and wastewater (62 FR 48394, September 15, 1997), and proposed for
use in 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.
45 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
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: Paper Mill #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 Dioxins 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 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)
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
(/)
•
•
•
N/A
•
•
•
N/A
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ATP Protocol for Organic and Inorganic Analytes
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, 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
Performance
Criteria (2)
Based on
Measurement Reference
Quality
Method Objective
Attach 4
Attach 5
Attach 6&8
Attach 6&8
Attach 6&8
Extraction
Attach 8
volumetric
pipet
Attach 6
at least four
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
four
Pert.
Spec.
Achieved
(/)
•
•
•
•
N/A
N/A
•
•
•
•
N/A
•
•
•
•
•
•
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ATP Protocol for Organic and Inorganic Analytes
Initial Demonstration of Method Performance (1)
Category
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
Attach 7
Attach 9
Attach 5
Annual
Results
Obtained
Attach 7
Attach 9
Attach 5
Annual
Pert.
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.
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
The certification above must accompany this form each time it is submitted.
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ATP Protocol for Organic and Inorganic Analytes
Certification Statement
Date: February 2, 1994 Page _1 of _1
Laboratory Name & Address: ABC Analytical, Inc., Anytown, USA
Facility Name: Paper Mill #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: PolychlorinatedDioxins 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 (1).
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 Manager 2/2/94
Facility Manager's Name and Title Signature Date
John Doe, Chemist 2/2/94
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.
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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ATP Protocol for Organic and Inorganic Analytes
9.3 Data Reporting Form
This appendix provides an example data reporting form. The form illustrates those aspects of data
reporting which are expected, regardless of the specific format used; specifically, data should be presented
in a clear and logical format, and should be labeled clearly.
In addition to using an appropriate data reporting format, submitting electronic versions of data can be
very helpful in expediting the review of an ATP. Data files should be in IBM-PC compatible format,
suitable for input directly into statistical analysis software, such as the Trimmed Spearman-Karber, Probit,
Dunnett, and ICP programs.
50 March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
ATP Data Form1
ATP Method
Title*
Revision „ , ,
Date — —
Include Method Number and Revision Number
Please record all data and quality control (QC) performance results (for comparison against QC
acceptance criteria) from your validation study using this data form. If you have additional data, please
attach it to this form in a tabular format, being sure to label all columns and rows clearly.
For Tier 1 Studies (Single Laboratory Use): Complete 1 form for each matrix type.
For Tier 2 (Nationwide Use; Single Matrix) or Tier 3 (Nationwide Use; Multiple Matrices): Complete 1
form for each participant laboratory.
Units of Concentration:
Linear Calibration Data
Units of Response:
Number of Points:
Analyte Cone.
Response
RF/CF/RR*
'Response Factor/Calibration Factor/Relative Response
Method Detection Limit (MDL) Data
Spiking Concentration used for MDL Study (include units):
MDL Data
Initial Precision Recovery (IPR) Data
Spiking Concentration used for IPR Study (include units):
IPR Data
Matrix Spike / Matrix Spike Duplicate (MS/MSD) Data
Spiking Concentration used for MS/MSP Study
MS Concentration
MSD Concentration
Background Concentration
nclude units):
ATP QC Performance Results
Calibration
Points
Lin
Spike
Cone
IPR Recovery and
Precision
Low
High
Precision
OPR Data
Precision
Low
High
MS/MSD Recovery and
RPD
Low
High
RPD
MDL
ML
f For multi-analyte methods, present additional Data and QC acceptance criteria for each analyte in a tabular format, making
sure to include proper labels, and attach to this form.
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ATP Protocol for Organic and Inorganic Analytes
10.0 APPENDIX E - QUALITY CONTROL ACCEPTANCE CRITERIA
Table IF- Standardized QC and QC Acceptance Criteria for Methods in 40 CFR Part 136, Table 1
Analyte- Reference
No Detector Method
1. Aluminum - Flame 202.1
" -Furnace 202.2
" -ICP 200.7
2. Ammonia -distill
" -Messier 350.2
" -Titr 350.2
" -ISE 350.3
" -Phenate 350.1
3. Antimony - Flame 204.1
Antimony - 204.2
Furnace
Antimony - ICP 200.7
4. Arsenic
" - Hydride 206.3
" - Furnace 206.2
" - ICP 200.7
"- Color (SDDC) 206.4
5. Barium -Flame 208.1
" - Furnace 208.2
" - ICP 200.7
6. Beryllium - Flame 210.1
"-Furnace 210.2
" - ICP 200.7
7. Boron -Color 212.3
" - ICP 200.7
8. Bromide 320.1
9. Cadmium - Flame 213.1
Cadmium - 213.2
Furnace
Cadmium - ICP 200.7
10. Calcium - Flame 215.1
Calcium - ICP 200.7
Calcium -Titr 215.2
11. Chloride - Titr/Hg 325.3
Chloride -Auto 325.1
12. Chlorine -Ampere 330.1
Chlorine - lodo 330.3
Chlorine - Back titr 330.2
Chlorine - 330.4
DPD-FAS
Chlorine - Spectra 330.5
13. Chromium VI - AA 218.4
14. Chromium - Flame 218.1
Chromium - 218.2
Furnace
Chromium - ICP 200.7
15. Cobalt -Flame 219.1
Cobalt - Furnace 219.2
Cobalt - ICP 200.7
16. Copper -Flame 220.1
Copper - Furnace 220.2
Spike
cone.
500 ug/L
500 ug/L
500ug/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
200 ug/L
200 ug/L
100 ug/L
100 ug/L
100 ug/L
40 ug/L
1 mg/L
1 mg/L
1 mg/L
100 ug/L
50 ug/L
100 ug/L
240 ug/L
1 mg/L
2.8 mg/L
100 ug/L
100 ug/L
100 ug/L
200 ug/L
10 mg/L
10 mg/L
100 mg/L
100 mg/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
100 ug/L
100 ug/L
100 ug/L
100 ug/L
500 ug/L
100 ug/L
100 ug/L
100 ug/L
100 ug/L
Specification
Calibr
point
3
5
3
3
3
3
1
1
5
3
3
3
3
3
3
5
3
3
5
3
5
3
3
3
3
3
3
3
3
3
3
3
5
3
3
3
3
3
3
3
3
3
3
3
5
IPR
% Recovery and Precision
lin Low
10% 81
25 % 71
10% 81
10% 81
10% 73
10% 79
87
77
25 % 70
10% 71
10% 71
10% 82
10% 73
10% 72
10% 97
25 % 82
10% 90
10% 85
25 % 79
10% 79
25 % 54
10% 76
10% 70
10% 88
10% 84
10% 84
10% 82
10% 86
10% 84
10% 92
10% 93
10% 79
25 % 78
10% 68
10% 79
10% 82
10% 84
10% 67
10% 83
10% 84
10% 85
10% 85
10% 86
10% 90
25 % 86
High
117
127
121
121
129
127
115
117
118
121
127
118
129
128
101
122
110
109
119
119
146
126
122
110
114
118
120
120
124
108
109
115
116
124
119
120
112
123
117
118
113
113
116
110
112
SD
18
28
20
20
28
24
14
20
24
25
28
18
28
28
2.0
20
10
12
20
20
46
25
26
11
15
17
19
17
20
7.6
8.2
18
19
28
20
19
14
28
17
17
14
14
15
10
13
OPR
% Recovery %
Low
79
68
79
79
70
77
86
75
68
68
68
80
70
69
97
80
89
84
77
77
49
74
67
87
83
83
80
84
82
92
82
77
76
65
77
80
83
64
82
82
84
83
84
89
84
High
119
130
123
123
132
129
116
119
120
124
130
120
132
131
101
124
111
110
121
121
151
128
125
111
115
119
122
122
126
108
110
117
118
127
121
122
113
126
118
119
114
115
118
111
114
Low
79
68
79
79
70
77
86
75
68
68
68
80
70
69
97
80
89
84
77
77
49
74
67
87
83
83
80
84
82
92
82
77
76
65
77
80
83
64
82
82
84
83
84
89
84
MS/MSD
Recovery
High
119
130
123
123
132
129
116
119
120
124
130
120
132
131
101
124
111
110
121
121
151
128
125
111
115
119
122
122
126
108
110
117
118
127
121
122
113
126
118
119
114
115
118
111
114
RPD
20
31
22
22
31
26
15
22
26
28
31
20
31
31
2.2
22
11
13
22
22
51
27
29
12
16
18
21
19
22
8.4
9.0
20
21
31
22
21
15
31
18
18
15
16
17
11
15
ML
15 ug/L
20 ug/L
50 ug/L
50 ug/L
1.0 mg/L
30 ug/L
10 ug/L
1.0 mg/L
20 ug/L
20 ug/L
2.0 ug/L
5.0 ug/L
20 ug/L
10 ug/L
1.0 mg/L
10 ug/L
2 ug/L
50 ug/L
1.0 ug/L
1.0 ug/L
100 ug/L
10 ug/L
2 mg/L
50 ug/L
0.5 ug/L
2 ug/L
200 ug/L
20 ug/L
2 mg/L
...
1mg/L
...
0.1 mg/L
...
0.1 mg/L
0.2 mg/L
10 ug/L
15 ug/L
5 ug/L
10 ug/L
500 ug/L
5 ug/L
5 ug/L
100 ug/L
5 ug/L
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ATP Protocol for Organic and Inorganic Analytes
Table IF- Standardized QC and QC Acceptance Criteria for Methods in 40 CFR Part 136, Table 1
Analyte- Reference
No Detector Method
Copper - ICP 200.7
17. Cyanide - Spectra 335.2
18. Fluoride- 340.2
Elec/man
Fluoride- 340.1
SPADNS
Fluoride - Auto 340.3
19. Hardness- 130.1
Color/auto
Hardness- 130.2
Titr/EDTA
20. pH- Electrode 150.1
21. Iron -Flame 236.1
Iron - Furnace 236.2
Iron - ICP 200.7
22. TKN -Digest 351.3
TKN-Titr 351.3
TKN-Nessler 351.3
TKN - Electrode 351.3
TKN-Phenate 351.1
TKN - Block/color 351.2
23. Lead -Flame 239.1
Lead - Furnace 239.2
Lead - ICP 200.7
24. Magnesium - 242.1
Flame
Magnesium - ICP 200.7
25. Manganese- 243.1
Flame
Manganese - 243.2
Furnace
Manganese - ICP 200.7
26. Mercury - CV/Man 245.1
Mercury - CV/Auto 245.2
27. Molybdenum - 246.1
Flame
Molybdenum - ICP 200.7
28. Nickel -Flame 249.1
Nickel - Furnace 249.2
Nickel - ICP 200.7
29. Nitrate 352.1
30. N02-N03- 353.3
Cd/Man
N02-N03 - 353.2
Cd/Auto
N02-N03- 353.1
Cd/Hydra
31. 0-phosphate- 365.1
Auto
0-phosphate - 365.2
Man1
32. DO-Winkler 360.2
DO -Electrode 360.1
33. Phenol- 420.1
Color/Man
Spike
cone.
100 ug/L
250 ug/L
1 mg/L
1 mg/L
1 mg/L
100 mg/L
100 mg/L
N/A
500 ug/L
100 ug/L
500 ug/L
2 mg/L
5 mg/L
5 mg/L
5 mg/L
5 mg/L
5 mg/L
300 ug/L
100 ug/L
300 ug/L
2 mg/L
2 mg/L
100 ug/L
100 ug/L
100 ug/L
4 ug/L
4 ug/L
300 ug/L
100 ug/L
100 ug/L
100 ug/L
100 ug/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
300 ug/L
300 ug/L
1 mg/L
1 mg/L
500 ug/L
Specification
Calibration
point lin
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
2
3 10%
5 25 %
3 10%
5 25 %
3 10%
5 25 %
5 25 %
5 25 %
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 25 %
3 10%
3 10%
5 25 %
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
5 25 %
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
IPR
% Recovery and Precision
Low
86
65
85
79
87
93
93
87
80
88
49
82
78
69
78
79
87
84
84
83
84
86
83
86
84
77
67
80
83
84
82
77
79
88
88
86
89
98
98
59
High
116
129
115
127
117
109
107
113
124
116
153
118
122
129
122
119
113
116
118
115
120
112
113
114
126
121
131
118
117
116
120
125
119
110
110
112
113
102
102
123
SD
15
32
15
24
15
8.4
7.2
2.2
13
22
14
52
18
22
30
22
20
13
16
17
16
18
13
15
14
26
22
32
19
17
16
19
24
20
11
11
13
12
2.0
2.0
32
OPR
% Recovery %
Low
84
62
84
77
85
92
92
86
78
86
44
80
76
66
76
77
86
82
82
81
82
85
81
84
71
75
64
78
81
83
80
75
77
87
87
84
87
98
98
56
High
118
132
116
129
119
110
108
114
126
118
158
120
124
132
124
121
114
118
120
117
122
113
115
116
129
123
134
120
119
117
122
127
121
111
111
114
115
102
102
126
Low
84
62
84
77
85
92
92
86
78
86
44
80
76
66
76
77
86
82
82
81
82
85
81
84
71
75
64
78
81
83
80
75
77
87
87
84
87
98
98
56
MS/MSD
Recovery
High
118
132
116
129
119
110
108
114
126
118
158
120
124
132
124
121
114
118
120
117
122
113
115
116
129
123
134
120
119
117
122
127
121
111
111
114
115
102
102
126
RPD
17
35
16
26
17
9.2
7.9
2.4
14
24
16
57
20
24
33
24
22
14
18
19
18
20
14
17
16
29
24
35
21
19
17
21
26
22
12
12
15
14
2.2
2.2
35
ML
10 ug/L
60 ug/L
100 ug/L
100 ug/L
50 ug/L
10 mg/L
30 mg/L
N/A
300 ug/L
5 ug/L
100 ug/L
50 ug/L
50 ug/L
50 ug/L
50 ug/L
50 ug/L
100 ug/L
40 ug/L
5 ug/L
20 ug/L
20 ug/L
50 ug/L
100 ug/L
1 ug/L
2 ug/L
0.2 ug/L
0.2 ug/L
300 ug/L
10 ug/L
0.2 ug/L
5 ug/L
20 ug/L
0.1 mg/L
10 ug/L
50 ug/L
10 ug/L
10 ug/L
10 ug/L
50 ug/L
50 ug/L
5 ug/L
53
March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
Table IF- Standardized QC and QC Acceptance Criteria for Methods in 40 CFR Part 136, Table 1
Analyte- Reference
No Detector Method
Phenol - 420.2
Color/Auto
34. Phosphorus - 365.2
Asc/Man
Phosphorus - 365.3
Asc/Man
Phosphorus- 365.1
Asc/Auto
Phosphorus - 365.4
Block
35. Potassium - Flame 258.1
Potassium - ICP 200.7
36. Selenium- 270.2
Furnace
Selenium - ICP 200.7
37. Silica - Color/Man 370.1
Silica -ICP 200.7
38. Silver -Flame 272.1
Silver - Furnace 272.2
Silver -ICP 200.7
39. Sodium -Flame 273.1
Sodium - ICP 200.7
40. Sulfate- 375.1
Color/Auto
Sulfate - Grav 375.3
Sulfate - Turbid 375.4
41. Surfactants 425.1
42. Thallium - Flame 279.1
Thallium - Furnace 279.2
Thallium - ICP 200.7
43. Tin -Flame 282.1
44. Titanium - Flame 283.1
45. Vanadium - Flame 286.1
Vanadium - 286.2
Furnace
Vanadium - ICP 200.7
46. Zinc -Flame 289.1
Zinc - Furnace 289.2
Zinc - ICP 200.7
Spike
cone.
500 ug/L
1mg/L
1mg/L
1mg/L
1mg/L
10 mg/L
10 mg/L
100 ug/L
300 ug/L
5 mg/L
1mg/L
100 ug/L
100 ug/L
100 ug/L
30 ug/L
10 mg/L
50 mg/L
50 mg/L
50 mg/L
3 mg/L
100 ug/L
100 ug/L
100 ug/L
10 mg/L
2 mg/L
2 mg/L
200 ug/L
200 ug/L
100 ug/L
100 ug/L
100 ug/L
Specification
Calibration
point lin
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
5 25 %
3 10%
5 25 %
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
3 10%
IPR
% Recovery and Precision
Low
41
82
79
81
80
84
82
77
80
64
-82
88
83
83
90
86
83
85
83
83
85
81
73
83
85
81
82
87
87
81
83
High
121
112
115
111
112
116
120
117
120
120
190
112
115
117
116
122
115
113
115
119
115
115
127
109
115
121
118
113
113
119
121
SD
40
15
18
15
16
16
19
20
20
28
136
12
16
17
13
18
16
14
16
18
15
17
27
13
15
20
18
13
13
19
19
OPR
% Recovery %
Low
37
81
77
80
79
82
80
75
78
61
-96
86
82
82
88
85
82
83
81
81
83
80
70
32
84
79
80
86
85
79
81
High
125
113
117
112
113
118
122
119
122
123
204
114
116
118
118
123
116
115
117
121
117
116
130
110
116
123
120
114
115
121
123
Low
37
81
77
80
79
82
80
75
78
61
-96
86
82
82
88
85
82
83
81
81
83
80
70
32
84
79
80
86
85
79
81
MS/MSD
Recovery
High
125
113
117
112
113
118
122
119
122
123
204
114
116
118
118
123
116
115
117
121
117
116
130
110
116
123
120
114
115
121
123
RPD
44
16
20
16
17
18
21
22
22
31
150
14
17
18
15
19
17
16
18
20
17
18
30
14
16
22
20
14
15
21
21
ML
2 ug/L
10 ug/L
10 ug/L
10 ug/L
10 ug/L
100 ug/L
1 mg/L
5 ug/L
50 ug/L
2 mg/L
50 ug/L
100 ug/L
1 ug/L
5 ug/L
30 ug/L
100 ug/L
10 mg/L
10 ug/L
1 mg/L
25 ug/L
600 ug/L
5 ug/L
50 ug/L
10 mg/L
2 mg/L
2 mg/L
10 ug/L
10 ug/L
50 ug/L
0.2 ug/L
5 ug/L
Legend for acronyms and abbreviations in Table IF:
Reference Method: QC acceptance criteria are for modifications to the reference method specified in Table IB.
CAL points: the number of points required for calibration
CAL linearity: the relative standard deviation (RSD) of the calibration factor or response factor below which an averaged calibration factor or response factor may be used in place of a
calibration curve. For an averaged response or calibration factor above this number, a calibration curve must be used.
Spike cone. : the concentration at which the QC acceptance criteria were determined.
%Recovery: the amount of analyte recovered expressed as a percent.
SD: the standard deviation of the % recovery.
IPRSD : the upper limit on theQC acceptance criterion for precision of the determination of % recovery expressed as the SD at the spike concentration, it is not an RSD.
IPR recovery (low/high): the lower and upper QC acceptance criteria for % recovery in the initial precision and recovery test.
OPR recovery (low/high): the lower and upper QC acceptance criteria for % recovery in the ongoing precision and recovery test.
MS/MSD recovery (low/high): the lower and upper QC acceptance criteria for % recovery of the matrix spike and matrix spike duplicate.
RPD = relative percent difference (RPD) is the absolute value of the difference between two measurements expressed as a percent. For the MS/MSD test RPD = 100% x [|MS - MSD
/ V2(MS + MSD)].
MS/MSD RPD: the upper limit on the QC acceptance criterion for precision expressed as the RPD for the MS/MSD test.
ML value: The minimum level (ML) as the lowest calibration point
54
March 10, 1999
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ATP Protocol for Organic and Inorganic Analytes
Table I Standardized QC and QC Acceptance Criteria for Modifications to Methods in 40 CFR 141.23(k)(1)
No. Analyte - Detector
1. Antimony -
Antimony -
STGFAA
2. Arsenic - ICP
Arsenic- ICP/MS
Arsenic - STGFAA
3. Barium - ICP
Barium - ICP/MS
4. Beryllium - ICP
Beryllium - ICP/MS
Beryllium -
STGFAA
5. Cadmium - ICP
Cadmium -
ICP/MS
Cadmium -
STGFAA
6. Calcium - ICP
7. Chromium - ICP
Chromium -
ICP/MS
Chromium -
STGFAA
8. Copper - ICP
Copper - ICP/MS
Copper - STGFAA
9. Cyanide -
Spectro/Auto
10. Fluoride- 1C
11. Lead -ICP/MS
Lead - STGFAA
12. Mercury - CV/Man
Mercury - CV/Auto
Mercury - ICP/MS
13. Nickel -ICP
Nickel - ICP/MS
Nickel - STGFAA
14. Nitrate -1C
Nitrate - Cd/Auto
15. Nitrite -1C
Nitrite - Cd/Auto
16. 0-phosphate- 1C
0-phosphate -
Asc/Auto
17. Selenium -
ICP/MS
Selenium -
STGFAA
18. Silica -ICP
19. Sodium -ICP
20. Thallium - ICP/MS
Thallium -
STGFAA
Reference
Method
200.8
200.9
200.7
200.8
200.9
200.7
200.8
200.7
200.8
200.9
200.7
200.8
200.9
200.7
200.7
200.8
200.9
200.7
200.8
200.9
335.4
300.0
200.8
200.9
245.1
245.2
200.8
200.7
200.8
200.9
300.0
353.2
300.0
353.2
300.0
365.1
200.8
200.9
200.7
200.7
200.8
200.9
Spike
cone.
10ug/L
10ug/L
50 ug/L
50 ug/L
50 ug/L
1 mg/L
1 mg/L
4 ug/L
4 ug/L
4 ug/L
5 ug/L
5 ug/L
5 ug/L
100 mg/L
100 ug/L
100 ug/L
50 ug/L
1 mg/L
1 mg/L
100 ug/L
200 ug/L
2 mg/L
15 ug/L
15 ug/L
2 ug/L
2 ug/L
2 ug/L
100 ug/L
100 ug/L
50 ug/L
5 mg/L
5 mg/L
1 mg/L
1 mg/L
1 mg/L
1 mg/L
50 ug/L
50 ug/L
5 mg/L
5 mg/L
5 ug/L
5 ug/L
Specification
Calibration
point lin
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
10%
IPR
% Recovery and Precision %
Low
81
72
87
91
86
91
92
84
87
82
82
89
80
93
90
90
85
93
92
86
66
85
92
84
66
67
54
87
91
85
90
88
83
92
84
90
82
76
87
92
89
68
High
117
132
113
111
114
107
106
112
115
118
118
109
118
110
108
106
115
109
110
114
118
109
111
118
122
119
138
109
107
115
110
114
111
108
114
110
110
112
121
116
115
128
OPR
Recovery
SD Low High
18 80
30 69
13 86
10 90
14 84
7.6 91
7.2 91
14 83
14 85
18 80
18 81
10 88
19 78
8.6 92
9.4 89
8.4 89
15 84
8 92
9.4 91
14 85
26 63
12 84
9.8 91
17 82
28 63
26 64
42 50
11 86
8.4 90
15 83
9.6 89
13 87
14 81
8.0 91
15 83
9.8 89
14 80
18 75
10 84
12 91
13 88
30 65
118
135
114
112
116
107
107
113
117
120
119
110
120
112
109
107
116
110
111
115
121
110
113
120
125
122
142
110
108
117
111
115
113
109
115
111
112
113
124
117
116
131
MS/MSD
/o Recovery
_ow High
80 118
69 135
86 114
90 112
84 116
91 107
91 107
83 113
85 117
80 120
81 119
88 110
78 120
92 112
89 109
89 107
84 116
92 110
91 111
85 115
63 121
84 110
91 113
82 120
63 125
64 122
50 142
86 110
90 108
83 117
89 111
87 115
81 113
91 109
83 115
89 111
80 112
75 113
84 124
91 117
88 116
65 131
RPD
19
33
14
11
16
8.4
7.9
15
16
20
19
11
21
9.5
10
9.2
16
8.8
10
15
29
13
11
19
31
29
46
12
9.2
17
11
14
16
8.8
16
11
16
19
12
13
14
33
MDL
0.4 ug/L
0.8 ug/L
0.008 mg/L
1.4 ug/L
0.5 ug/L
0.001 mg/L
0.8 ug/L
0.0003 mg/L
0.3 ug/L
0.02 ug/L
0.001 mg/L
0.5 ug/L
0.05 ug/L
0.01 mg/L
0.003 mg/L
0.9 ug/L
0.1 ug/L
0.003 mg/L
0.5 ug/L
0.7 ug/L
5 ug/L
0.01 mg/L
0.6 ug/L
0.7 ug/L
0.2 ug/L
0.2 ug/L
0.2 ug/L
0.005 mg/L
0.5 ug/L
0.6 ug/L
0.002 mg/L
10 ug/L
0.004 mg/L
10 ug/L
0.003 mg/L
1 ug/L
7.9 ug/L
0.6 ug/L
0.02 mg/L
0.03 mg/L
0.3 ug/L
0.7 ug/L
55
March 10, 1999
-------
ATP Protocol for Organic and Inorganic Analytes
Legend for acronyms and abbreviations in Table I:
Reference Method: QC acceptance criteria are for modifications to the reference method specified at 141.23(k)(1).
Calibration: the number of points required for calibration and the linearity of the calibration.
Linearity (%): the relative standard deviation (RSD) of the calibration factor or response factor below which an averaged calibration factor or response factor may be used in place
of a calibration curve. For an averaged response or calibration factor above this number, a calibration curve must be used.
Spike cone. : the concentration at which the QC acceptance criteria were determined.
%Recovery: the amount of analyte recovered expressed as a percent.
SD: the standard deviation of the % recovery also expressed as a percent.
IPR SD : the upper limit on theQC acceptance criterion for precision of the determination of % recovery expressed as theSD at the spike concentration, it is not an RSD.
IPR recovery (low/high): the lower and upper QC acceptance criteria for % recovery in the initial precision and recovery test.
OPR recovery (low/high): the lower and upper QC acceptance criteria for % recovery in the ongoing precision and recovery test.
MS/MSD recovery (low/high): the lower and upper QC acceptance criteria for % recovery of the matrix spike and matrix spike duplicate.
RPD: relative percent difference (RPD) is the absolute value of the difference between two measurements expressed as a percent. For the MS/MSD testRPD = 100% x [|MS -
MS/MSD RPD: the upper limit on the QC acceptance criterion for precision expressed as the RPD for the MS/MSD test.
MDL: the method detection limit from table at 1 41 .23(a)(4)(i) or the reference method against which to evaluate the MDL of the modifed method.
Asc/Auto Ascorbic Acid Automated
Cd/Auto Cadmium Automated
CV Man/Auto Cold Vapor Manual/Automated
1C Ion Chromatography
ICP Inductively Coupled Plasma as in ICP Atomic Emission Spectrometry
ICP/MS ICP/Mass Spectrometry
STGFAA Stabilized Temperature Graphite Furnace Atomic Asorption
Spectro/Auto Specrophotometric Semi-Automated
56 March 10, 1999
------- |