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


EPA 821-B-98-002


March 1999

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 threetiered 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 

Pre-decisional draft ATPPRO19.WPD 

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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 EPAspecified 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 

Pre-decisional draft ATPPRO19.WPD 

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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 Adding New Target Analytes 

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.) 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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 LEVEL OF 

USE APPLICANT SUBMIT 

APPLICATION TO1 

APPROVAL 

AUTHORITY 

Tier 1 

Limited Use 

for 

Wastewater 

EPA Regional laboratories EPA Regional 

Administrator 

(Regional ATP 

Coordinator)2 

EPA Regional 

Administrator 

States, commercial 

laboratories, individual 

dischargers, or permitees in 

States that do not have 

authority 

EPA Regional 

Administrator 

(Regional ATP 

Coordinator)2 

States, commercial 

laboratories, individual 

dischargers, or permitees in 

States that have authority 

Director of State 

Agency issuing the 

NPDES permit2 

Tier 2 Nationwide 

Use All applicants 

Director, Analytical 

Methods Staff, EPA 

Headquarters 

EPA 

Administrator 

Tier 3 Nationwide 

Use All applicants 

Director, Analytical 

Methods Staff, EPA 

Headquarters 

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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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 EPAapproved 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-byside 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 methoddefined 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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

Table 2. Application Requirements 

Tier Level of Use Application Requirements 

Tier 1 Limited Use 

• Completed application form 

• Justification for ATP 

• Method in EPA format 

• Method comparison table 

• Validation study report 

Tier 2 

Nationwide Use 

• Completed application form 

• Justification for ATP 

• Method in EPA format 

• Method comparison table 

• Validation study report 

• Method development information and 

documentation 

Tier 3 

2.2.1 Justification for ATP 

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 twocolumn 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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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: 

C Background

C Study Design and Objectives

C Study Implementation

C Data Reporting and Validation

C Results

C Data Analysis/Discussion

C Conclusions

C Appendix A - The Method

C Appendix B - Validation Study Plan (optional for Tier 1)

C 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: 

C Defines the purpose and intended use of the method.

C 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. 

C Identifies the matrix(ces) for which the method has been found satisfactory. 

C Describes method limitations and indicate any means of recognizing cases where the method may 

not be applicable to the specific matrix types. 

C Outlines the basic steps involved in performing the test and data analysis. 

C Lists options to the method, if applicable. 

C 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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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 Laboratory Use Applicable to . . . 

Tier 1 Single Laboratory 

(Limited use) 

One or more matrix types from any industry 

Tier 2 All Laboratories 

(Nationwide use) 

One matrix type within one industrial subcategory; or all 

PWSs 

Tier 3 All Laboratories 

(Nationwide use) 

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 multilaboratory 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 

Pre-decisional draft ATPPRO19.WPD 

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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) 

Number of Number of Analyses Required 

Method Application Labs 

Matrix 

types 

IPRreagent 

water(2) MS/MSD MDL(3) 

Tier 1-Single-lab 

First matrix type 1 1 4 2(4) 7 

Each additional matrix type (8 max.) 1 1 0(5) 2(4) 0(5) 

Tier 2-Multi-lab, single matrix type 3 1 12 6(6) 21 

Tier 3-Multi-lab, multiple matrix types 

All matrix types 9(7) 9 36 18(6) 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. 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

Table 5. Summary of Validation Requirements for Drinking Water Alternate 

Test Procedures(1) 

Number of Number of Analyses Required 

Method Application Labs PWSs 

IPR- reagent 

water(2) 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 EPAdesignated 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 timeconsuming 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, 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 12 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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: 

C Total suspended solids (TSS) greater than 40 mg/L 

C Total dissolved solids (TDS) greater than 100 mg/L 

C Oil and grease greater than 20 mg/L 

C NaCl greater than 120 mg/L 

C 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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 13 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 14 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 methoddefined 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 methoddefined, 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: 

C Identify the ATP method as a modification of an approved method

C Identify the program use of the ATP method (drinking water or waste water or both)

C Include a summary of the ATP method

C Cite the organization and method number (given in 40 CFR parts 136, 141, and 405 - 503) for the

approved method 

C Describe the reasons for and extent of the modification, the logic behind the technical approach to 

the modification, and the result of the modification 

C Identify the matrices, matrix types, and/or media to which the ATP method is believed to be 

applicable 

C List the analytes measured by the ATP method including corresponding CAS Registry or EMMI 

numbers 

C 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: 

C Identify the organization responsible for managing the study

C Identify laboratories, facilities, and other organizations that will participate in the study

C Delineate the study schedule

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 15 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

3.4.4 Technical Approach 

The Technical Approach section of the validation study plan should: 

C Indicate at which tier the study will be performed

C Describe the approach that will be followed by each organization involved in the study

C Describe how sample matrices and participating laboratories will be selected

C Explain how samples will be collected and distributed

C Specify the numbers and types of analyses to be performed by the participating laboratories

C 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 EPAdesignated 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 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 16 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 Analyses 

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 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 17 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 MSD), 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 Tier 3 Validation Studies 

In a Tier 3 validation study, each of the nine laboratories participating in the study will determine 

the background concentration and analyze an MS/MSD pair on the sample it receives. Since there are a 

total of nine laboratories, each performing three field sample analyses (one background, one MS, and one 

MSD), a Tier 3 validation study will require analysis of 27 samples. 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 EPAspecified document). 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 18 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 EPAspecified document). 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 19 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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(5), 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: 

C Include a method summary

C Cite the organization and method number and title for the ATP 

C Cite the method number (given in 40 CFR parts 136, 141, and 405 - 503) for the approved method

that is being modified 

C 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 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 20 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

C Describe the reasons for and extent of the modification, the logic behind the technical approach to 

the modification, and the result of the modification 

C Identify the matrices, matrix types, and/or media to which the modified method is believed to be 

applicable 

C 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.) 

C 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.) 

C State the purpose of the study 

3.6.2 Study Design and Objectives 

The Study Design and Objectives section of the validation study report must describe the study 

design, and identify overall objectives and data quality objectives of the study. Any study limitations must 

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: 

C Identify the organization that was responsible for managing the study 

C 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 

C Indicate at which Tier level the study was performed

C Delineate the study schedule that was followed

C Describe how sample matrices were chosen, including a statement of compliance with Tier

requirements for matrix type selection 

C Explain how samples were collected and distributed 

C Specify the numbers and types of analyses performed by the participating laboratories 

C Describe how analyses were performed 

C 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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 21 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 Analysis/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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 22 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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: 

C Sample numbers or other identifiers used by the both the regulated entity and the laboratory

C Sample preparation (extraction/digestion) dates

C Analysis dates and times

C Sequence of analyses or run logs

C Sample volume

C Extract volume prior to each cleanup step

C Extract volume after each cleanup step

C Final extract volume prior to injection

C Digestion volume

C Titration volume

C Percent solids or percent moisture

C Dilution data, differentiating between dilution of a sample and dilution of an extract or digestate

C Instrument(s) and operating conditions

C 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.) 

C Chromatograms, ion current profiles, bar graph spectra, library search results

C 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) 

C Direct instrument readouts; i.e., strip charts, printer tapes, etc., and other data to support the final results 

C 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. 

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 23 March 10, 1999 
ATP Protocol for Organic and Inorganic Analytes 

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 

Pre-decisional draft ATPPRO19.WPD 

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ATP Protocol for Organic and Inorganic Analytes 

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-tocomments 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. AOACInternational. 

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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ATP Protocol for Organic and Inorganic Analytes 

6.0 APPENDIX A - ATP APPLICATION FORM 

EPA Office of Water 

Alternate Test Procedure Application Form for Chemical Analytes 

Applicant Name and Address: EPA Use Only 

ATP Case No. 

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) 

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: 

Justification for ATP 

Alternate Test Procedure (Method in standard EPA format) 

Method Comparison Table 

Validation Study Plan (optional) 

Validation Study Report 

Method Information and Documentation for Preamble and Docket 

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 Woodbridge 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

Region 5 

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, KS 66101

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

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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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ATP Protocol for Organic and Inorganic Analytes 

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. 

17.0 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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ATP Protocol for Organic and Inorganic Analytes 

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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T

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: Page __of __

Laboratory Name & Address:

Facility Name:

Discharge Point ID:

EPA Program and Applicable Regulation:

Medium:

(e.g., wastewater, drinking water, soil, air, waste solid, leachate, sludge, other)

Analyte or Class of Analytes:

(e.g., barium, trace metals, benzene, volatile organics, etc.)

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

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. 

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ATP Protocol for Organic and Inorganic Analytes 

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

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) 

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ATP Protocol for Organic and Inorganic Analytes 

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

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) 

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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ATP Protocol for Organic and Inorganic Analytes 

Certification Statement 

Date:

Laboratory Name & Address:

Facility Name:

Discharge Point ID:

EPA Program and Applicable Regulation:

Medium:

(e.g., water, soil, air)

Analyte or Class of Analytes:

7/13/96 

Page __of __ 

(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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ATP Protocol for Organic and Inorganic Analytes 

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. 

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: 

(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.” 

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). 

* 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: 

This field is optional. Identify the facility from which the matrix samples were taken. 

ATP Approval Protocol: 

Enter the matrix type as defined in the ATP protocol, instead of the medium. 

* Analyte or Class of Analytes 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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ATP Protocol for Organic and Inorganic Analytes 

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--NOTE: 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 Protocol for Organic and Inorganic Analytes 

ATP Approval Protocol: 

See the Guidelines and Format for Methods to be Proposed at 40 CFR Part 136 or Part 141 ( EPA821-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 (last study 

sponsor and title:; last study number:). 

Several EPA Programs conduct periodic performance evaluation (PE) studies. Organizations outside of the 

Agency also may conduct such studies. Enter the sponsor, title, and date of the most recent study 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”, i.e., 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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ATP Protocol for Organic and Inorganic Analytes 

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. 

Pre-decisional draft ATPPRO19.WPD 

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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. 

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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. 

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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 MSD 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. 

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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 OctaChlorinated 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. 

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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: Polychlorinated Dioxins and Furans

(e.g., barium, trace metals, benzene, volatile organics, etc.; Attach separate list, as

needed.)

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

1. Written method (addressing all elements in the 

EMMC format) attached 

U

2. Title, number and date/rev. of "reference 

method", if applicable (3) 

EPA Method 

1613 Rev. B 

U

3. Copy of the reference method, if applicable, 

maintained at facility 

U

4. Differences between the PBM and reference 

method (if applicable) attached 

N/A 

5. Concentrations of calibration standards Attach 1 Attach 1 U

6. %RSD or correlation coefficient of calibration 

regression 

Attach 2 Attach 2 U

7. Performance range tested (with units) Attach 3 Attach 3 U

8. Sample(s) used in initial demonstration have 

recommended preservative, where applicable. 

N/A 

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ATP Protocol for Organic and Inorganic Analytes 

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

9. Samples(s) used in initial demonstration met 

recommended holding times, where applicable 

U

10. Interferences Attach 4 Attach 4 U

11. Qualitative identification criteria used Attach 5 Attach 5 U

12. Performance Evaluation studies performed for 

analytes of interest, where available: 

Latest study sponsor and title: 

Latest study number: 

John Doe, 

PE Study, 

1234 

U

13. Analysis of external reference material N/A 

14. Source of reference material N/A 

15. Surrogates used, if applicable Attach 6 & 8 Attach 6 & 

8 

U

16. Concentrations of surrogates, if applicable Attach 6 & 8 Attach 6 & 

8 

U

17. Recoveries of surrogates appropriate to the 

proposed use, if applicable 

Attach 6 & 8 Attach 6 & 

8 

U

18. Sample preparation Extraction Extraction U

19. Clean-up procedures N/A 

20. Method Blank Result Attach 8 Attach 8 U

21. Matrix (reagent water, drinking water, sand, 

waste solid, ambient air, etc.) 

Paper Mill 

Effluent 

U

22. Spiking system, appropriate to method and 

application 

volumetric 

pipet 

volumetric 

pipet 

U

23. Spike concentrations (w/ units corresponding to 

final sample concentration) 

Attach 6 Attach 6 U

24. Source of spiking material Acme 

Standards 

lot #105 

cat #41 

U

25. Number of replicate spikes at least four four U

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ATP Protocol for Organic and Inorganic Analytes 

Initial Demonstration of Method Performance (1) 

Category Performance 

Criteria (2) 

Based on 

Measurement Reference 

Quality 

Method Objective 

Results 

Obtained 

Perf. 

Spec. 

Achieved 

(T) 

26. Precision (analyte by analyte) Attach 7 Attach 7 U

27. Bias (analyte by analyte) N/A 

28. Detection Limit (w/ units; analyte by analyte) N/A 

29. Confirmation of Detection Limit, if applicable N/A 

30. Quantitation Limit (w/ units: analyte by analyte) Attach 9 Attach 9 U

31. Qualitative Confirmation Attach 5 Attach 5 U

32. Frequency of performance of the Initial 

Demonstration 

Annual Annual U

33. Other criterion (specify) N/A 

34. Other criterion (specify) N/A 

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 analytespecific performance criteria from the reference method or those needed to satisfy measurement quality 

objectives. 

3 If a reference method is the source of the performance criteria, the reference method should be 

appropriate to the required application, and the listed criteria should be fully consistent with that 

reference method. 

Name and signature of each analyst involved in the initial demonstration of method 

performance (includes all steps in the proposed method/modification): 

John Doe 2/2/94 

Name Signature Date 

________________________ __________________________ _________ 

Name Signature Date 

________________________ __________________________ _________ 

Name Signature Date 

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: Polychlorinated Dioxins 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. 

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ATP Protocol for Organic and Inorganic Analytes 

ATP Data Form† 

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.

Linear Calibration Data 

Units of Concentration:___________ Units of Response: ___________ Number of Points:____________ 

Analyte Conc. 

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/MSD Study (include units): ___________ 

MS Concentration 

MSD Concentration 

Background Concentration 

ATP QC Performance Results 

Calibration Spike IPR Recovery and 

Precision 

OPR Data 

Precision 

MS/MSD Recovery and 

RPD 

MDL/ML 

Points Lin Conc Low High Precision Low High Low High RPD MDL ML 

† 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 

Specification 

IPR OPR MS/MSD 

No 

AnalyteDetector Reference 

Method 

Spike 

conc. 

Calibration 

point 

% Recovery and Precision % Recovery % Recovery 

Low High SD Low High Low High RPD ML

1. Aluminum - Flame 202.1 500 ug/L 3 10 % 81 117 18 79 119 79 119 20 15 

" 202.2 500 ug/L 5 25 % 71 127 28 68 130 68 130 31 20 ug/L 

" 200.7 500ug/L 3 10 % 81 121 20 79 123 79 123 22 50 ug/L 

2. Ammonia - distill 

" 350.2 1 mg/L 3 10 % 81 121 20 79 123 79 123 22 50 ug/L 

" 350.2 1 mg/L 3 10 % 73 129 28 70 132 70 132 31 1.0 mg/L 

" 350.3 1 mg/L 3 10 % 79 127 24 77 129 77 129 26 30 ug/L 

" 350.1 1 mg/L 1 87 115 14 86 116 86 116 15 10 ug/L 

3. Antimony - Flame 204.1 1 1 77 117 20 75 119 75 119 22 1.0 mg/L 

Antimony -

Furnace 

204.2 200 ug/L 5 25 % 70 118 24 68 120 68 120 26 20 ug/L 

Antimony - ICP 200.7 200 ug/L 3 10 % 71 121 25 68 124 68 124 28 20 ug/L 

4. Arsenic 

" - Hydride 206.3 100 ug/L 3 10 % 71 127 28 68 130 68 130 31 2.0 ug/L 

" - Furnace 206.2 100 ug/L 3 10 % 82 118 18 80 120 80 120 20 5.0 ug/L 

" - ICP 200.7 100 ug/L 3 10 % 73 129 28 70 132 70 132 31 20 ug/L 

" - Color (SDDC) 206.4 40 ug/L 3 10 % 72 128 28 69 131 69 131 31 10 ug/L 

5. Barium - Flame 208.1 1 mg/L 3 10 % 97 101 2.0 97 101 97 101 2.2 1.0 mg/L 

" - Furnace 208.2 1 mg/L 5 25 % 82 122 20 80 124 80 124 22 10 ug/L 

" - ICP 200.7 1 mg/L 3 10 % 90 110 10 89 111 89 111 11 2 ug/L 

6. Beryllium - Flame 210.1 100 ug/L 3 10 % 85 109 12 84 110 84 110 13 50 ug/L 

" - Furnace 210.2 50 ug/L 5 25 % 79 119 20 77 121 77 121 22 1.0 ug/L 

" - ICP 200.7 100 ug/L 3 10 % 79 119 20 77 121 77 121 22 1.0 ug/L 

7. Boron - Color 212.3 240 ug/L 5 25 % 54 146 46 49 151 49 151 51 100 ug/L 

" - ICP 200.7 1 mg/L 3 10 % 76 126 25 74 128 74 128 27 10 ug/L 

8. Bromide 320.1 2.8 mg/L 3 10 % 70 122 26 67 125 67 125 29 2 mg/L 

9. Cadmium - Flame 213.1 100 ug/L 3 10 % 88 110 11 87 111 87 111 12 50 ug/L 

Cadmium -

Furnace 

213.2 100 ug/L 3 10 % 84 114 15 83 115 83 115 16 0.5 ug/L 

Cadmium - ICP 200.7 100 ug/L 3 10 % 84 118 17 83 119 83 119 18 2 ug/L 

10. Calcium - Flame 215.1 200 ug/L 3 10 % 82 120 19 80 122 80 122 21 200 ug/L 

Calcium - ICP 200.7 10 mg/L 3 10 % 86 120 17 84 122 84 122 19 20 ug/L 

Calcium - Titr 215.2 10 mg/L 3 10 % 84 124 20 82 126 82 126 22 2 mg/L 

11. Chloride - Titr/Hg 325.3 100 mg/L 3 10 % 92 108 7.6 92 108 92 108 8.4 

Chloride - Auto 325.1 100 mg/L 3 10 % 93 109 8.2 82 110 82 110 9.0 1 mg/L 

12. Chlorine - Ampere 330.1 1 mg/L 3 10 % 79 115 18 77 117 77 117 20 

Chlorine - Iodo 330.3 1 mg/L 5 25 % 78 116 19 76 118 76 118 21 0.1 mg/L 

Chlorine - Back titr 330.2 1 mg/L 3 10 % 68 124 28 65 127 65 127 31 

Chlorine -

DPD-FAS 

330.4 1 mg/L 3 10 % 79 119 20 77 121 77 121 22 0.1 mg/L 

Chlorine - Spectro 330.5 1 mg/L 3 10 % 82 120 19 80 122 80 122 21 0.2 mg/L 

13. Chromium VI - AA 218.4 100 ug/L 3 10 % 84 112 14 83 113 83 113 15 10 ug/L 

14. Chromium - Flame 218.1 100 ug/L 3 10 % 67 123 28 64 126 64 126 31 15 ug/L 

Chromium -

Furnace 

218.2 100 ug/L 3 10 % 83 117 17 82 118 82 118 18 5 ug/L 

Chromium - ICP 200.7 100 ug/L 3 10 % 84 118 17 82 119 82 119 18 10 ug/L 

15. Cobalt - Flame 219.1 500 ug/L 3 10 % 85 113 14 84 114 84 114 15 500 ug/L 

Cobalt - Furnace 219.2 100 ug/L 3 10 % 85 113 14 83 115 83 115 16 5 ug/L 

Cobalt - ICP 200.7 100 ug/L 3 10 % 86 116 15 84 118 84 118 17 5 ug/L 

16. Copper - Flame 220.1 100 ug/L 3 10 % 90 110 10 89 111 89 111 11 100 ug/L 

Copper - Furnace 220.2 100 ug/L 5 25 % 86 112 13 84 114 84 114 15 5 ug/L 

lin 

ug/L 

- Furnace 

- ICP 

- Nessler 

- Titr 

- ISE 

- Phenate 

mg/L 

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Table IF- Standardized QC and QC Acceptance Criteria for Methods in 40 CFR Part 136, Table 1

Specification 

IPR OPR MS/MSD 

No 

AnalyteDetector Reference 

Method 

Spike 

conc. 

Calibration 

point 

% Recovery and Precision % Recovery % Recovery 

Low High SD Low High Low High RPD ML

Copper - ICP 200.7 100 ug/L 3 10 % 86 116 15 84 118 84 118 17 10 ug/L 

17. Cyanide - Spectro 335.2 250 ug/L 3 10 % 65 129 32 62 132 62 132 35 60 ug/L 

18. Fluoride -

Elec/man 

340.2 1 mg/L 3 10 % 85 115 15 84 116 84 116 16 100 ug/L 

Fluoride -

SPADNS 

340.1 1 mg/L 3 10 % 79 127 24 77 129 77 129 26 100 ug/L 

Fluoride - Auto 340.3 1 mg/L 3 10 % 87 117 15 85 119 85 119 17 50 ug/L 

19. Hardness -

Color/auto 

130.1 100 mg/L 3 10 % 93 109 8. 4 92 110 92 110 9.2 10 mg/L 

Hardness -

Titr/EDTA 

130.2 100 mg/L 3 10 % 93 107 7.2 92 108 92 108 7.9 30 mg/L 

20. pH - Electrode 150.1 N/A 2 2.2 2.4 N/A 

21. Iron - Flame 236.1 500 ug/L 3 10 % 87 113 13 86 114 86 114 14 300 ug/L 

Iron - Furnace 236.2 100 ug/L 5 25 % 80 124 22 78 126 78 126 24 5 ug/L 

Iron - ICP 200.7 500 ug/L 3 10 % 88 116 14 86 118 86 118 16 100 ug/L 

22. TKN - Digest 351.3 2 mg/L 5 25 % 49 153 52 44 158 44 158 57 50 ug/L 

TKN - Titr 351.3 5 mg/L 3 10 % 82 118 18 80 120 80 120 20 50 ug/L 

TKN - Nessler 351.3 5 mg/L 5 25 % 78 122 22 76 124 76 124 24 50 ug/L 

TKN - Electrode 351.3 5 mg/L 5 25 % 69 129 30 66 132 66 132 33 50 ug/L 

TKN - Phenate 351.1 5 mg/L 5 25 % 78 122 22 76 124 76 124 24 50 ug/L 

TKN - Block/color 351.2 5 mg/L 3 10 % 79 119 20 77 121 77 121 22 100 ug/L 

23. Lead - Flame 239.1 300 ug/L 3 10 % 87 113 13 86 114 86 114 14 40 ug/L 

Lead - Furnace 239.2 100 ug/L 3 10 % 84 116 16 82 118 82 118 18 5 ug/L 

Lead - ICP 200.7 300 ug/L 3 10 % 84 118 17 82 120 82 120 19 20 ug/L 

24. Magnesium -

Flame 

242.1 2 mg/L 3 10 % 83 115 16 81 117 81 117 18 20 ug/L 

Magnesium - ICP 200.7 2 mg/L 3 10 % 84 120 18 82 122 82 122 20 50 ug/L 

25. Manganese -

Flame 

243.1 100 ug/L 3 25 % 86 112 13 85 113 85 113 14 100 ug/L 

Manganese -

Furnace 

243.2 100 ug/L 3 10 % 83 113 15 81 115 81 115 17 1 ug/L 

Manganese - ICP 200.7 100 ug/L 3 10 % 86 114 14 84 116 84 116 16 2 ug/L 

26. Mercury - CV/Man 245.1 4 ug/L 5 25 % 84 126 26 71 129 71 129 29 0.2 ug/L 

Mercury - CV/Auto 245.2 4 ug/L 3 10 % 77 121 22 75 123 75 123 24 0.2 ug/L 

27. Molybdenum -

Flame 

246.1 300 ug/L 3 10 % 67 131 32 64 134 64 134 35 300 ug/L 

Molybdenum - ICP 200.7 100 ug/L 3 10 % 80 118 19 78 120 78 120 21 10 ug/L 

28. Nickel - Flame 249.1 100 ug/L 3 10 % 83 117 17 81 119 81 119 19 0.2 ug/L 

Nickel - Furnace 249.2 100 ug/L 3 10 % 84 116 16 83 117 83 117 17 5 ug/L 

Nickel - ICP 200.7 100 ug/L 3 10 % 82 120 19 80 122 80 122 21 20 ug/L 

29. Nitrate 352.1 1 mg/L 5 25 % 77 125 24 75 127 75 127 26 0.1 mg/L 

30. NO2-NO3 -

Cd/Man 

353.3 1 mg/L 3 10 % 79 119 20 77 121 77 121 22 10 ug/L 

NO2-NO3 -

Cd/Auto 

353.2 1 mg/L 3 10 % 88 110 11 87 111 87 111 12 50 ug/L 

NO2-NO3 -

Cd/Hydra 

353.1 1 mg/L 3 10 % 88 110 11 87 111 87 111 12 10 ug/L 

31. O-phosphate -

Auto 

365.1 300 ug/L 3 10 % 86 112 13 84 114 84 114 15 10 ug/L 

O-phosphate -

Man 1 

365.2 300 ug/L 3 10 % 89 113 12 87 115 87 115 14 10 ug/L 

32. DO - Winkler 360.2 1 mg/L 3 10 % 98 102 2.0 98 102 98 102 2.2 50 ug/L 

DO - Electrode 360.1 1 mg/L 3 10 % 98 102 2.0 98 102 98 102 2.2 50 ug/L 

33. Phenol -

Color/Man 

420.1 500 ug/L 3 10 % 59 123 32 56 126 56 126 35 5 ug/L 

lin 

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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 

Specification 

IPR OPR MS/MSD 

No 

AnalyteDetector Reference 

Method 

Spike 

conc. 

Calibration 

point 

% Recovery and Precision % Recovery % Recovery 

Low High SD Low High Low High RPD ML

Phenol -

Color/Auto 

420.2 500 ug/L 3 10 % 41 121 40 37 125 37 125 44 2 ug/L 

34. Phosphorus -

Asc/Man 

365.2 1 mg/L 3 10 % 82 112 15 81 113 81 113 16 10 ug/L 

Phosphorus -

Asc/Man 

365.3 1 mg/L 3 10 % 79 115 18 77 117 77 117 20 10 ug/L 

Phosphorus -

Asc/Auto 

365.1 1 mg/L 3 10 % 81 111 15 80 112 80 112 16 10 ug/L 

Phosphorus -

Block 

365.4 1 mg/L 3 10 % 80 112 16 79 113 79 113 17 10 ug/L 

35. Potassium - Flame 258.1 10 mg/L 3 10 % 84 116 16 82 118 82 118 18 100 ug/L 

Potassium - ICP 200.7 10 mg/L 3 10 % 82 120 19 80 122 80 122 21 1 mg/L 

36. Selenium -

Furnace 

270.2 100 ug/L 3 10 % 77 117 20 75 119 75 119 22 5 ug/L 

Selenium - ICP 200.7 300 ug/L 5 25 % 80 120 20 78 122 78 122 22 50 ug/L 

37. Silica - Color/Man 370.1 5 mg/L 3 10 % 64 120 28 61 123 61 123 31 2 mg/L 

Silica - ICP 200.7 1 mg/L 5 25 % -82 190 136 -96 204 -96 204 150 50 ug/L 

38. Silver - Flame 272.1 100 ug/L 3 10 % 88 112 12 86 114 86 114 14 100 ug/L 

Silver - Furnace 272.2 100 ug/L 3 10 % 83 115 16 82 116 82 116 17 1 ug/L 

Silver - ICP 200.7 100 ug/L 3 10 % 83 117 17 82 118 82 118 18 5 ug/L 

39. Sodium - Flame 273.1 30 ug/L 3 10 % 90 116 13 88 118 88 118 15 30 ug/L 

Sodium - ICP 200.7 10 mg/L 3 10 % 86 122 18 85 123 85 123 19 100 ug/L 

40. Sulfate -

Color/Auto 

375.1 50 mg/L 3 10 % 83 115 16 82 116 82 116 17 10 mg/L 

Sulfate - Grav 375.3 50 mg/L 3 10 % 85 113 14 83 115 83 115 16 10 ug/L 

Sulfate - Turbid 375.4 50 mg/L 3 10 % 83 115 16 81 117 81 117 18 1 mg/L 

41. Surfactants 425.1 3 mg/L 3 10 % 83 119 18 81 121 81 121 20 25 ug/L 

42. Thallium - Flame 279.1 100 ug/L 3 10 % 85 115 15 83 117 83 117 17 600 ug/L 

Thallium - Furnace 279.2 100 ug/L 3 10 % 81 115 17 80 116 80 116 18 5 ug/L 

Thallium - ICP 200.7 100 ug/L 3 10 % 73 127 27 70 130 70 130 30 50 ug/L 

43. Tin - Flame 282.1 10 mg/L 3 10 % 83 109 13 32 110 32 110 14 10 mg/L 

44. Titanium - Flame 283.1 2 mg/L 3 10 % 85 115 15 84 116 84 116 16 2 mg/L 

45. Vanadium - Flame 286.1 2 mg/L 3 10 % 81 121 20 79 123 79 123 22 2 mg/L 

Vanadium -

Furnace 

286.2 200 ug/L 3 10 % 82 118 18 80 120 80 120 20 10 ug/L 

Vanadium - ICP 200.7 200 ug/L 3 10 % 87 113 13 86 114 86 114 14 10 ug/L 

46. Zinc - Flame 289.1 100 ug/L 3 10 % 87 113 13 85 115 85 115 15 50 ug/L 

Zinc - Furnace 289.2 100 ug/L 3 10 % 81 119 19 79 121 79 121 21 0.2 ug/L 

Zinc - ICP 200.7 100 ug/L 3 10 % 83 121 19 81 123 81 123 21 5 ug/L 

lin 

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 conc. : 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.

IPR SD : the upper limit on the QC 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*

/ 1/

2(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

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 54 March 10, 1999 
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) 

Specification 

IPR OPR MS/MSD 

Calibration 

point 

% Recovery and Precision % Recovery % 

No. Analyte - Detector Reference 

Method 

Spike 

conc. Low High SD Low High Low High RPD MDL 

1. Antimony - 200.8 10 ug/L 3 10 % 81 117 18 80 118 80 118 19 0.4 ug/L 

Antimony -

STGFAA 

200.9 10 ug/L 3 10 % 72 132 30 69 135 69 135 33 0.8 ug/L 

2. Arsenic - ICP 200.7 50 ug/L 3 10 % 87 113 13 86 114 86 114 14 0.008 mg/L 

Arsenic - ICP/MS 200.8 50 ug/L 3 10 % 91 111 10 90 112 90 112 11 1.4 ug/L 

Arsenic - STGFAA 200.9 50 ug/L 3 10 % 86 114 14 84 116 84 116 16 0.5 ug/L 

3. Barium - ICP 200.7 1 mg/L 3 10 % 91 107 7.6 91 107 91 107 8.4 0.001 mg/L 

Barium - ICP/MS 200.8 1 mg/L 3 10 % 92 106 7.2 91 107 91 107 7.9 0.8 ug/L 

4. Beryllium - ICP 200.7 4 ug/L 3 10 % 84 112 14 83 113 83 113 15 0.0003 mg/L 

Beryllium - ICP/MS 200.8 4 ug/L 3 10 % 87 115 14 85 117 85 117 16 0.3 ug/L 

Beryllium -

STGFAA 

200.9 4 ug/L 3 10 % 82 118 18 80 120 80 120 20 0.02 ug/L 

5. Cadmium - ICP 200.7 5 3 10 % 82 118 18 81 119 81 119 19 0.001 mg/L 

Cadmium -

ICP/MS 

200.8 5 ug/L 3 10 % 89 109 10 88 110 88 110 11 0.5 ug/L 

Cadmium -

STGFAA 

200.9 5 ug/L 3 10 % 80 118 19 78 120 78 120 21 0.05 ug/L 

6. Calcium - ICP 200.7 100 mg/L 3 10 % 93 110 8.6 92 112 92 112 9.5 0.01 mg/L 

7. Chromium - ICP 200.7 100 ug/L 3 10 % 90 108 9.4 89 109 89 109 10 0.003 mg/L 

Chromium -

ICP/MS 

200.8 100 ug/L 3 10 % 90 106 8.4 89 107 89 107 9.2 0.9 ug/L 

Chromium -

STGFAA 

200.9 50 ug/L 3 10 % 85 115 15 84 116 84 116 16 0.1 ug/L 

8. Copper - ICP 200.7 1 mg/L 3 10 % 93 109 8 92 110 92 110 8.8 0.003 mg/L 

Copper - ICP/MS 200.8 1 mg/L 3 10 % 92 110 9.4 91 111 91 111 10 0.5 

Copper - STGFAA 200.9 100 ug/L 3 10 % 86 114 14 85 115 85 115 15 0.7 ug/L 

9. Cyanide -

Spectro/Auto 

335.4 200 ug/L 3 10 % 66 118 26 63 121 63 121 29 5 ug/L 

10. Fluoride - IC 300.0 2 mg/L 3 10 % 85 109 12 84 110 84 110 13 0.01 mg/L 

11. Lead - ICP/MS 200.8 15 ug/L 3 10 % 92 111 9.8 91 113 91 113 11 0.6 ug/L 

Lead - STGFAA 200.9 15 ug/L 3 10 % 84 118 17 82 120 82 120 19 0.7 ug/L 

12. Mercury - CV/Man 245.1 2 ug/L 3 10 % 66 122 28 63 125 63 125 31 0.2 ug/L 

Mercury - CV/Auto 245.2 2 ug/L 3 10 % 67 119 26 64 122 64 122 29 0.2 ug/L 

Mercury - ICP/MS 200.8 2 ug/L 3 10 % 54 138 42 50 142 50 142 46 0.2 ug/L 

13. Nickel - ICP 200.7 100 ug/L 3 10 % 87 109 11 86 110 86 110 12 0.005 mg/L 

Nickel - ICP/MS 200.8 100 ug/L 3 10 % 91 107 8.4 90 108 90 108 9.2 0.5 ug/L 

Nickel - STGFAA 200.9 50 ug/L 3 10 % 85 115 15 83 117 83 117 17 0.6 ug/L 

14. Nitrate - IC 300.0 5 mg/L 3 10 % 90 110 9.6 89 111 89 111 11 0.002 mg/L 

Nitrate - Cd/Auto 353.2 5 mg/L 3 10 % 88 114 13 87 115 87 115 14 10 ug/L 

15. Nitrite - IC 300.0 1 mg/L 3 10 % 83 111 14 81 113 81 113 16 0.004 mg/L 

Nitrite - Cd/Auto 353.2 1 mg/L 3 10 % 92 108 8.0 91 109 91 109 8.8 10 ug/L 

16. O-phosphate - IC 300.0 1 mg/L 3 10 % 84 114 15 83 115 83 115 16 0.003 mg/L 

O-phosphate -

Asc/Auto 

365.1 1 mg/L 3 10 % 90 110 9.8 89 111 89 111 11 1 ug/L 

17. Selenium -

ICP/MS 

200.8 50 ug/L 3 10 % 82 110 14 80 112 80 112 16 7.9 ug/L 

Selenium -

STGFAA 

200.9 50 ug/L 3 10 % 76 112 18 75 113 75 113 19 0.6 ug/L 

18. Silica - ICP 200.7 5 mg/L 3 10 % 87 121 10 84 124 84 124 12 0.02 mg/L 

19. Sodium - ICP 200.7 5 mg/L 3 10 % 92 116 12 91 117 91 117 13 0.03 mg/L 

20. Thallium - ICP/MS 200.8 5 ug/L 3 10 % 89 115 13 88 116 88 116 14 0.3 ug/L 

Thallium -

STGFAA 

200.9 5 3 10 % 68 128 30 65 131 65 131 33 0.7 ug/L 

lin 

Recovery 

ug/L 

ug/L 

ug/L 

Pre-decisional draft ATPPRO19.WPD

Do not cite or quote 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 conc. : 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 the QC 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* /1⁄2 (MS + MSD)].

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 141.23(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

IC 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

Pre-decisional draft ATPPRO19.WPD 

Do not cite or quote 56 March 10, 1999