1

6560-50-P

ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63

[OAR-2004-0080, FRL-7851-9xxxx-x]

RIN 2060-AF00 

National Emission Standards for Hazardous Air Pollutants: 

Appendix A - Test Methods; Method 301 for the

- Field Validation of Pollutant Measurement Methods from 

Various Waste Media

AGENCY: Environmental Protection Agency (EPA).

ACTION: ProposedFinal rule.

SUMMARY: This action proposes to amend procedures for 

validating alternative emissions test methods, to rewrite 

the EPA’s Method 301 in plain language, reorganize the 

method for clarity, correct technical errors, and revise the

technical procedures. The revisions to the technical 

procedures include replacing quantitation limits with 

detection limits, revising the bias acceptance criteria and 

eliminating the correction factors, revising the precision 

acceptance criteria, and allowing analyte spiking as an 

option even when there is an existing test method.amends 
2

EPA’s Method 301, Field Validation of Pollutant Measurement 

Methods from Various Waste Media. We revised the procedures

in Method 301 based on our experience in applying the method

and to correct errors that were brought to our attention. 

This action finalizes amendments to Method 301 after 

considering comments received on the proposed rule published

in the Federal Register on December 22, 2004. Changes made 

to the Method 301 protocol under this action apply only to 

methods submitted to the EPA for approval after the 

effective date of this action.

DATES: Comments. Comments must be received on or before 

[INSERT DATE 60 DAYS AFTER PUBLICATION IN THE FEDERAL 

REGISTER].

Public Hearing. If anyone contacts the EPA requesting a 

public hearing by [INSERT DATE 20 DAYS AFTER PUBLICATION IN 

THE FEDERAL REGISTER], a public hearing will be held on 

[INSERT DATE 30 DAYS AFTERDATES: This final rule is 

effective on [Insert date of publication in the Federal 

Register].

ADDRESSES: Comments. Submit your comments, identified by

EPA has established a docket for this action under Docket ID

No. OAR-2004-0080, by one of the following methods.

· Federal eRulemaking Portal: 
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http:///www.regulations.gov. Follow the on-line 

instructions for submitting comments.

· Agency Website: http://www.epa.gov/edocket. EDOCKET, 

EPA’s electronic public docket and comment system, is 

EPA’s preferred method for receiving comments. Follow 

the on-line instructions for submitting comments.

· Mail: Air and Radiation Docket and Information Center 

(Mail Code 6102T), Attention Docket Number EPA-HQ-OAR2004-0080, Room B108, U.S. EPA, 1301 Constitution 

Avenue, NW., Washington, DC 20460. The EPA requests 

that a separate copy also be sent to the contact person

listed below (see FOR FURTHER INFORMATION CONTACT). 

Send submissions containing such proprietary or 

confidential business information (CBI) directly to the

following address, and not to the public docket, to 

ensure that proprietary or CBI is not inadvertently 

placed in the public docket: Attention: Mr. Roberto 

Morales, U.S. Environmental Protection Agency, OAQPS 

Document Control Officer, 109 TW Alexander Drive, Room 

C404-02, RTP, NC, 27711. 

· Hand Delivery: Air and Radiation Docket and 

Information Center (Mail Code 6102T), Attention Docket 

Number OAR-2004-0080, Room B102, U.S. EPA, 1301 
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Constitution Avenue, NW, Washington, DC 20460. Such 

deliveries are only accepted during the Docket’s normal

hours of operation, and special arrangements should be 

made for deliveries of boxed information. The EPA 

requests a separate copy also be sent to the contact 

person listed below (see FOR FURTHER INFORMATION 

CONTACT). 

Instructions. Direct your comments to Docket ID No. OAR2004-0080. The EPA’s policy is that all comments received 

will be included in the public docket without change and may

be made available online at http://www.epa.gov/edocket, 

including any personal information provided, unless the 

comment includes information claimed to be Confidential 

Business Information (CBI) or other information whose 

disclosure is restricted by statute. Do not submit 

information that you consider to be CBI or otherwise 

protected through EDOCKET, regulations.gov websites, or email. The EPA EDOCKET and the Federal regulations.gov 

websites are “anonymous access” systems, which means the EPA

will not know your identity or contact information unless 

you provide it in the body of your comment. If you send an 

e-mail comment directly to the EPA without going through 

EDOCKET OR regulations.gov, your e-mail address will be 
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automatically captured and included as part of the comment 

that is placed in the public docket and made available on 

the internet. If you submit an electronic comment, the EPA 

recommends that you include your name and other contact 

information in the body of your comment and with any disk or

CD-ROM you submit. If the EPA cannot read your comment due 

to technical difficulties and cannot contact you for 

clarification, the EPA may not be able to consider your 

comment. Electronic files should avoid the use of special 

characters, any form of encryption, and be free of any 

defects or viruses. For additional information about EPA’s 

public docket visit EDOCKET on-line or see the Federal 

Register of May 31, 2002 (67 FR 38102). 

Docket. All documents in the docket are listed in the EDOCKET 

index at http://www.epa.gov/edocketon the http://www.regulations.gov

web site. Although listed in the index, some information is

not publicly available, i.e.g., CBI or other information 

whose disclosure is restricted by statute. Certain other 

material, such as copyrighted material, is not placed on the

Internet and will be publicly available only in hardcopyhard 

copy form. Publicly available docket materials are 

available either electronically in EDOCKETthrough 
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http://www.regulations.gov or in hard copy at the EPA Docket 

Center (Air Docket),, EPA/DC, EPA West, Room B-1083334, 1301 

Constitution Avenue, NW.,, Washington, DC 20004. . The Docket 

Center isFacility and the Public Reading Room are open from 

8:30 a.m. to 4:30 p.m., Monday through Friday, excluding 

legal holidays. The telephone number for the Public Reading

Room is (202) 566-1744, and the telephone number for the Air

Docket is (202) 566-1742.

Public Hearing. People interested in presenting oral 

testimony or inquiring as to whether a hearing is to be held

should contact FOR FURTHER INFORMATION CONTACT: Ms. Corlis 

McCormick, SourceLula H. Melton, Office of Air Quality 

Planning and Standards, Air Quality Assessment Division,

Measurement Technology Group, Emission Measurement Center 

(D243 (E143-02), U.S. Environmental Protection Agency, 

Research Triangle Park, NC,North Carolina 27711,; telephone 

number: (919) 541-5545, at least 2 days in advance of the 

public hearing. People interested in attending the public 

hearing must also call Ms. McCormick to verify the time, 

date, and location of the hearing. The public hearing will 

provide interested parties the opportunity to present data, 

views, or arguments concerning the proposed changes to 

Method 301. If a public hearing is held, it will be held at
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10:00 a.m. in the EPA's Auditorium in Research Triangle 

Park, North Carolina, or at an alternate site nearby.

FOR FURTHER INFORMATION CONTACT: For information concerning

the proposed standards, contact Mr. Gary McAlister, Source 

Measurement Technology Group, Emission Measurement Center 

(D243-02), U.S. Environmental Protection Agency, Research 

Triangle Park, North Carolina 27711, telephone-2910; fax

number: (919) 541-1062, electronic 0516; e-mail address: 

mcalister.garymelton.lula@epa.gov.

SUPPLEMENTARY INFORMATION:

Preamble Outline 

The information in this preamble is organized as 

follows.

Table of Contents

I. General Information

A. Does this Action Apply to Me?

B. What ShouldWhere Can I Consider as I Prepare 

MyObtain a Copy of This Action?

C. Judicial Review

II. Background

III. Summary of the Final Method

IV. Significant Comments for the EPA?

C. Availability of Received on the Proposed Rule
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II. Introduction

III. What changes Are We Proposing?

A. Use Plain Language

B. ReorganizeAmendments to Method 301

C. Correct Technical Errors

D. Make Technical Revisions

IV. What are the Administrative Requirements?

A. Applicability

B. Reference Material

C. Validation Testing Over a Broad Range of 

Concentrations and Extended Period of Time

D. Performance Audit

E. Sample Stability Procedures

F. Bias and Precision

G. Limit of Detection

H. Critical Values of t for the Two-Tailed 95% 

Confidence Limit

I. Paired Sampling Procedure

J. Standard Deviation

V. Statutory and Executive Order Reviews

A. Executive Order 12866 -– Regulatory Planning and 

Review

B. Paperwork Reduction Act
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C. Regulatory Flexibility Act (RFA)

D. Unfunded Mandates Reform Act

E. Executive Order 13132 -– Federalism

F. Executive Order 13175 -– Consultation and 

Coordination with Indian Tribal Governments

G. Executive Order 13045 -– Protection of Children 

from Environmental Health Risks and Safety Risks

H. Executive Order 13211, – Actions Concerning 

Regulations that Significantly Affect Energy 

Supply, Distribution, or Use

I. National Technology Transfer and Advancement Act of 

1995

J. Executive Order 12898 – Federal Actions to Address 

Environmental Justice in Minority Populations and 

Low-income Populations

K. Congressional Review Act

I. General Information

A. Does this Action Apply to Me?

Method 301 affects/applies to you if you want to 

propose a new or alternative test method to meet an EPA 

compliance requirement in absence of a validated method. . 

B. What Should I Consider as I Prepare My Comments for the 

EPAWhere Can I Obtain a Copy of this Action?
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1. Submitting CBI. Do not submit this information to 

the EPA through EDOCKET, regulations.gov, or e-mail. 

Clearly mark the part or all of the information that you 

claim to be CBI. For CBI information in a disk or CD ROM 

that you mail to the EPA, mark the outside of the disk or CD

ROM as CBI and then identify electronically within the disk 

or CD ROM the specific information that is claimed as CBI. 

In addition to one complete version of the comment that 

includes information claimed as CBI, a copy of the comment 

that does not contain the information claimed as CBI must be

submitted for inclusion in the public docket. Information 

so marked will not be disclosed except in accordance with 

procedures set forth in 40 CFR Part 2.

2. Tips for Preparing Your Comments. When submitting 

comments, remember to:

i. Identify the rulemaking by docket number and other 

identifying information (e.g., subject heading, Federal 

Register proposal publication date and reference page 

number(s)).

ii. Follow directions - The EPA may ask you to respond

to specific questions or organize comments by referencing a 

Code of Federal Regulations (CFR) part or section number.

iii. Explain why you agree or disagree; suggest 
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alternatives and provide substitute language for your 

requested changes.

iv. Describe any assumptions and provide any technical

information and/or data that you used.

v. If you estimate potential costs or burdens, explain

how you arrived at your estimate in sufficient detail to 

allow for it to be reproduced.

vi. Provide specific examples to illustrate your 

concerns, and suggest alternatives.

vii. Explain your views as clearly as possible, 

avoiding the use of profanity or personal threats.

viii. Make sure to submit your comments by the 

specified comment period deadline. 

Commenters wishing to submit proprietary information 

for consideration must clearly distinguish such information 

from other comments and clearly label it as CBI. Send 

submissions containing such proprietary information directly

to the following address, and not to the public docket, to 

ensure that proprietary information is not inadvertently 

placed in the docket: Attention: Mr. Roberto Morales, U.S.

Environmental Protection Agency, OAQPS Document Control 

Officer, 109 TW Alexander Drive, Room C404-02, RTP, NC, 

27711. The EPA will disclose information identified as CBI 
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only to the extent allowed by the procedures set forth in 

40 CFR Part 2. If no claim of confidentiality accompanies a

submission when it is received by the EPA, the information 

may be made available to the public without further notice 

to the commenter.

C. Availability of the Proposed Rule

In addition to being available in the docket, an 

electronic copy of the proposed changes to Method 301 is 

this rule will also be available on the InternetWorldwide 

Web (www) through the Technology Transfer Network (TTN). 

Following the Administrator’s signature, a copy of Method 

301the final rule will be postedplaced on the TTN’s policy 

and guidance page for newly proposed or promulgated rules

http://www.epa.gov/ttn/oarpg.at 

http://www.epa.gov/ttn/oarpg. The TTN provides information 

and technology exchange in various areas of air pollution 

control. If more information regarding the TTN is needed, 

call the TTN HELP line at (919) 541-5384.

II. Introduction

Today’s action proposes to amend EPA’s Method 301;C. 

Judicial Review

We are deeming this a 307 rule under section 307(d)(v). 

Under section 307(b)(1) of the Clean Air Act (CAA), judicial
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review of this final rule is available by filing a petition 

for review in the U.S. Court of Appeals for the District of 

Columbia by [Insert date 60 days after publication in the 

Federal Register]. Any such judicial review is limited to 

only those objections that are raised with reasonable 

specificity in timely comments. Under section 307(b)(2) of 

the Act, the requirements of this final action may not be 

challenged later in civil or criminal proceedings brought by

us to enforce these requirements.

II. Background

This action amends EPA’s Method 301, Field Validation 

of Pollutant Measurement Methods from Various Waste Media.

Method 301 can be foundwas originally promulgated in 

Appendix A of 40 CFR, Part 63 (Test Methods). Method 301 

was promulgated with 40 CFR, Part 63, Subpart D (Regulations

Governing Compliance Extensions for Early Reductions of 

Hazardous Air Pollutants)(58 FR 27338,on June 133, 1991) 

pursuant to Section 112 of the Clean Air Act (as amended in 

1990). . We proposed amendments to Method 301 on December 

22, 2004 (69 FR 76642). This action responds to comments 

received on that proposal and corrects errors found in the 

method. 

III. Summary of the Final Method
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You would use Method 301 whenever you propose to use a 

test method to meet an EPA compliance requirement in absence

ofother than a validated method that is required under a 40 

CFR Part 63 rule. The method specifies procedures for 

determining and documenting the precision and bias of 

measured concentrations from various media (e.g., sludge, 

exhaust gas, wastewater) at the level of an applicable 

standard for a source. Bias (or systemic error) is 

established by comparing your proposed method against a 

reference value. 

A correction factor is employed to eliminate/minimize 

bias. This correction factor is established from data 

obtained during your validation test. Methods that have bias

correction factors outside a specified range are considered 

unacceptable. Method precision (or random error) at the 

level of the standard must be demonstrated to be as precise 

as the validated method for acceptance.

Today’s action proposes to amend those provisions by 

correcting technical errors, and simplifying and clarifying

procedures. Section II of this preamble discusses the 

proposed Method 301 rule, and Section III presents the 

administrative requirements for this action. 
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III. What Changes Are We Proposing?

A. Use Plain Language

In compliance with President Clinton’s June 1, 1998, 

Executive Memorandum on Plain Language in government 

writing, Method 301 has been rewritten in plain language. 

The use of plain language clarifies the requirements of 

Method 301, thus, reducing the burden (time) associated with

understanding the Method. When Method 301 refers to “you,” 

it means the owner or operator of the affected source.

B. Reorganize Method 301

We have reorganized the information in Method 301 to 

make it easier to follow the requirements and to understand 

the relationships among the various requirements. The 

reorganization did not create new requirements, but it does 

incorporate various corrections to technical errors and 

technical revisions. These corrections and revisions, as 

well as the rationale for the changes, are discussed in 

Sections III C and D of this preamble.

Section 17.0 of today’s rule (What detection limits 

must I use?) shall apply instead of Section 9.0 (Practical 

Quantitation Limits) of the promulgated Method 301 rule. We

have retained all other sections from the promulgated Method

301, but you will find them in new places. Where necessary
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for clarity, we have put the information from one section of

Promulgated Method 301 into several new sections. Some 

information has been put into tables at the end of the 

Method. Section 2.0 presents new information. It has been 

added to explain when you must use Method 301 and to 

identify the requirement for receiving written approval from

the Administrator before using the alternative test method. 

Table 1 of this preamble specifies where the sections in 

the promulgated Method 301 are found in the proposed Method 

301 rule. 

The equations of the promulgated Method 301 have also 

been amended. Some of the promulgated equations have been 

modified; some have been replaced by other equations, and 

some have simply been renumbered or reordered. The 

technical reasons for the changes to the equations are 

discussed in Section III. D of this preamble. Table 2 

indicates whether each equation in the proposed amended rule

has changed from the promulgated rule. Equations 301-5 and 

301-10 (correction factors when using isotopic spiking and 

paired sampling systems with a validated test method 

comparison) of promulgated Method 301 rule have been removed

for the reasons discussed in Section III D of this preamble.
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Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.

Proposed New Section Promulgated Method Section

Using Method 301

1.0 What is the purpose of 

Method 301?

1.1 Applicability

2.0 When must I use Method 301? None

3.0 What does Method 301 

include?

1.1.2

4.0 How do I perform Method 

301?

1.2 Principle

Reference Materials and 

Performance Audits

5.0 What reference materials 

must I use?

3.0 Reference Materials

6.0 How do I conduct the 

performance audit?

4.0 EPA Performance Audit 

Materials

Sampling Procedures

7.0 What sampling procedures 

must I use?

5.0 Procedure for 

Determination of Bias and 

Precision in the Field
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Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.

Proposed New Section Promulgated Method Section

8.0 How do I ensure sample 

stability?

8 Procedure for Sample 

Stability in Bias and 

Precision Evaluations

Bias and Precision

9.0 What are the requirements 

for bias?

1.2.1 Bias

10.0 What are the requirements 

for precision?

1.2.2 Precision

11.0 What calculations must I 

perform for isotopic 

sampling?

6.1 Isotopic Sampling

12.0 What calculations must I 

perform for comparison with 

a validated method if I am 

using paired sampling 

systems?

6.2.1 Comparison with a 

validated method: Paired 

Sampling Systems

13.0 What calculations must I 

perform for comparison with 

a validated method if I am 

using quadruplet replicate 

6.2.2 Comparison with a 

validated method: 

Quadruplet Replicate 

Sampling Systems
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Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.

Proposed New Section Promulgated Method Section

sampling systems?

14.0 What calculations must I 

perform for analyte 

spiking?

6.3 Analyte Spiking

15.0 How do I conduct followup 

tests?

11 Followup Testing

Optional Requirements

16.0 How do I use and conduct 

ruggedness testing?

7 Ruggedness Testing

17.0 What detection limits must 

I use?

9 Practical Limit of 

Quantitation

Other Requirements and 

Information

18.0 How do I apply for approval 

to use an alternative 

method?

10 Field Validation Report 

Requirements

19.0 How do I request a waiver? 1.1.1 

and 

12

Procedure for Obtaining a 

Waiver
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Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.

Proposed New Section Promulgated Method Section

20.0 What definitions apply to 

this method?

2 Definitions

21.0 Where can I find additional 

information?

13 Bibliography
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Table 2. Equations in Proposed Method 301

The following equation in proposed 

Method 301. . .

is... The 

following 

equation in 

promulgated 

Method 

301...

301-1 Difference in Sample Results new

301-7 Relative Magnitude of Bias new

301-9 Relative Magnitude of Bias 

for Comparing Against 

Validated Methods Using 

Paired Sampling Systems

new

Equations When Using Isotopic Spiking

301-4 Numerical Value of Bias a revision of 301-1

301-5 Standard Deviation the same as 301-2

301-6 t Test a replacement

for

301-3 and 

301-4

301-8 Relative Standard Deviation a revision of 301-6

Equations When Comparing Against Validated Method Using Paired 
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Sampling Systems

301-2 Standard Deviation for paired 

sampling 

systems, a 

replacement 

for

301-2

301-3 t Test the same as 301-9

301-10 Variance a replacement

for

301-7

301-11 Pooled Variance new

301-12 Alternative Test Method Variance a replacement

for

301-9a

301-13 F test the same as 301-8

Equations When Comparing Against Validated Method Using Quadruplet 

Replicate Sampling Systems

301-14 Bias the same as 301-12

301-15 Alternative Test Method Variance the same as 301-11

Equations When Using Analyte Spiking

301-16 Bias the same as 301-14

301-17 t Test a replacement

for

301-4
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301-18 Standard Deviation for Spiked 

Samples

a revision of 301-13

301-19 Standard Deviation for Unspiked 

Samples

a replacement

for

301-13 and 

301-6

301-20 F test new

301-21 Pooled Standard Deviation a replacement

for

301-15
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C. Correct Technical Errors

Some of the equations in promulgated Method 301 are 

incorrect. We are proposing to correct these equations with

today’s action. For a discussion of new equations due to 

technical revisions, see Section III D of this preamble. We

revised several equations to clarify their intent. Under the

new numbering system, the revised equations are 301-4 

(numerical value of bias), 301-6 (t Test), 301-8 (relative 

standard deviation), 301-18 (standard deviation for spiked 

samples), and 301-19 (standard deviation for unspiked 

samples). These changes were editorial/defining changes and

not technical changes. For example, we added or changed 

subscripts or redefined a variable. 

We added Equations 301-1, 301-7, and 301-9. Equation 

301-1 is used to calculate the difference in minimum and 

maximum storage times under the new sample stability 

procedures. Equation 301-7 is used to calculate relative 

magnitude of bias for isotopic spiking. This new equation 

was needed when we dropped the use of correction factors. 

Likewise, Equation 301-9 was needed for calculating relative

magnitude of bias when comparing against a validated method 

using paired sampling systems. 

We also added Equation 301-11 and changed Equations 
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301-12, 301-17, 301-18, and 301-19 to correct technical 

errors in promulgated Method 301. Equations 301-11 (Pooled 

Variance) and 301-12 (Alternative Test Method Variance) are 

being proposed to correct a technical error in the 

promulgated method. Addition and subtraction can only be 

performed on the variance. It cannot be performed on the 

standard deviation. The proposed Equation 301-11 is a new 

equation that calculates the pooled variance of both methods

when comparing against validated methods using paired 

sampling systems. The proposed Equation 301-12 replaces the

standard deviation with the variance.

Equations 301-17 (calculation of the test “tstatistic”) and 301-21 (calculation of the pooled standard 

deviation) were changed because the divisor was wrong. 

Equation 301-20 (F test) was added so that the tester could 

determine if the spiked and unspiked samples had the same 

precision, thereby allowing them to be pooled to calculate 

the overall precision.

The proposed Equation 301-2 (Standard Deviation) 

replaces the promulgated Equation 301-2 when comparing 

against validated methods using paired sampling systems. 

The text in promulgated 6.2.1.4 directs the analyst to 

determine the mean of the paired sample differences by 
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substituting dm (mean of the paired sample differences) and 

di (standard deviation of the differences) for Si and Sm in 

the proposed Equation 301-2. We created the proposed 

Equation 301-2 to incorporate these changes. 

D. Make Technical Revisions

We are proposing five major technical changes to Method 

301. These technical changes include the following:IV.

Significant Comments Received on the Proposed 

Amendments to Method 301

We proposed five major technical changes to Method 301. 

These technical changes include the following:

(1) Replacing the Practical Limit of Quantitation 

(PLQ) with a procedure to determine the Limit of Detection,

(LOD),

(2) Revising the bias acceptance criteria and 

eliminating correction factors,

(3) Revising precision acceptance criteria when using 

analyte spiking, 

(4) Allowing analyte spiking even when there is an 

existing test method, and 

(5) Establishing new procedures for ensuring sample 

stability.
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1. Practical Limit of Quantitation. We are proposing 

to replace the determination of the PLQ with a procedure to 

determine the Limit of detection (LOD). The purpose of 

establishing a measurement limit is to ensure that a test 

method is appropriate for its intended use. The LOD is a 

better parameter for this purpose. 

The PLQ is defined as the level or concentration at 

which the precision of a test method reaches an acceptable 

value. There are several problems with this concept. The 

first is the idea that there is an absolute value for 

acceptable precision. To a certain extent, a tester can 

compensate for imprecision by collecting additional data so 

there is no absolute level at which the imprecision of a 

test method becomes so great that the method is no longer 

useful. This concept works best when the precision of the 

test method is independent of the concentration of the 

analyte being measured. As the concentration of the analyte

increases, the imprecision of the method as a percentage of 

the measured quantity decreases. In this case, the relative

imprecision will actually decrease as the quantity measured 

increases. 

However, for most environmental measurements, it appears 

that the precision is a function of the concentration of the
28

analyte being measured. The following section provides 

our response to significant comments received on the 

proposed technical changes and some inadvertant errors that 

occurred with the restructuring of, and addition of, 

components to the method. 

A. Applicability

A couple of commenters requested clarification that the 

final rule changes made to Method 301 only apply to methods 

submitted to EPA after promulgation of the changes and that 

Method 301 can be used whether or not a validated method 

exists. We are clarifying in this final rule that 

amendments to Method 301 do not apply to methods submitted 

for approval prior to promulgation. Also, Method 301 can be

used whether or not a validated method exists. This action

clarifies the effective date of the amended Method 301, and 

Section 1.0 of the final method clarifies that Method 301 

can be used whether or not a validated method exists.

B. Reference Material

One commenter provided that, as written, reference 

material is analogous to analyte. Inadvertantly, in Section

5 of Method 301, “reference materials” was followed by 

“(analytes).” This paranthetical was modified for 

clarification purposes as noted below.
29

A few commenters expressed concern that the standard 

against which precision and bias are compared is not 

required to be compared against a true value, usually a 

traceable standard (e.g., NIST). We agree that the 

reference material should be compared to a traceable 

standard. 

We have amended Section 5 of the final method to state 

the following:

You must use reference materials (a material or 

substance whose one or more properties are sufficiently

homogenous to the analyte) that are traceable to a 

national standards body (e.g., National Institute of 

Standards and Technology (NIST)) at the level of the 

applicable emission limitation or standard that the 

subpart in 40 CFR Part 63 requires. 

C. Validation Testing Over a Broad Range of Concentrations 

and Extended Period of Time

One commenter requested that validation testing over a 

broad range of concentrations and/or over an extended period

of time be allowed and mentioned that they had developed 

technology that could test over a broad range of 

concentrations for an extended time-period. The commenter 

argued that if the accuracy and precision requirements can 

be demonstrated with sequential sampling procedures, the EPA

should allow it. We agree with the commenter. In fact, we 

have approved methods demonstrated with sequential sampling 
30

to determine the precision of a proposed alternative method 

in the past. The final method explicitly states that 

sequential sampling procedures are allowed. 

D. Performance Audit

One commenter stated that they do not agree that the 

performance audit requirements in Section 6 of the proposed 

rule should be included in Method 301. The commenter 

supported their position by stating that the audit material 

may not correspond to the matrix for which the alternate 

test method was designed, and it is similar to having to ask

EPA permission to use a method that has passed Method 301 

validation criteria. In addition, the commenter stated that

the 30-day lead time for requesting the performance audit 

material reduces an affected parties’ flexibility in meeting

performance testing timing requirements. 

The function of an audit sample is to allow a tester to

demonstrate that their measurement system using a wellestablished measurement method is operating within 

established quality assurance limits. If the alternative 

method is being compared to a validated test method as part 

of the Method 301 validation and an audit sample for the 

validated method exists, then an audit should be used for 

the validated method. Since the amendments to Method 301 
31

were proposed on December 22, 2004, we promulgated a rule on

September 13, 2010 that moves all discussion of audits from 

the individual rules to the General Provisions of Part 63. 

Therefore, we have removed the proposed Section 6 which 

discussed performance audits.

EThus, the relative imprecision will not decrease as 

the quantity measured increases. In this case, the PLQ has 

no meaning. 

The LOD is the minimum level or concentration of an 

analyte that produces a signal or response that is 

distinguishable from the signal or response produced when no

analyte is present. This is a measurable quantity that can 

be determined regardless of the method’s precision or 

whether that precision varies with the level of the analyte.

For all of these reasons, we believe that the LOD is a more

useful parameter to characterize a test method’s 

performance. 

2. Bias Acceptance Criteria. We are also proposing to

change the acceptance criteria for the bias in a proposed 

alternative method from + 30% to + 10% and concurrently to 

eliminate the requirement for correcting all data collected 

with the method. We believe that twelve pairs of results

from a single source are not sufficient to allow us to 
32

establish a correction factor that can or should be applied 

to all future uses of the method. In addition, keeping 

track of correction factors to ensure that they are applied 

to future uses of the method is a huge administrative burden

both for the users of the method and the regulatory agencies

who oversee its use. If we do not use correction factors, 

method biases of up to 30 percent are undesirably large. 

Therefore, we are proposing to reduce the acceptable bias to

+ 10% and eliminate the requirement to correct the data. 

With this change, the bias of alternative methods will be 

acceptable; the criteria for using the alternative test 

method at similar sources will be clear, and the 

administrative burden will be reduced. 

3. Precision Acceptance Criteria. We are proposing to

change the acceptance criteria for method precision when 

using analyte spiking from + 50% to + 20%. In addition, we 

are proposing to eliminate the requirement for different 

numbers of replicate samples depending on the method’s 

relative precision. All future testing using an alternative

test method at similar sources will require only three 

replicate samples. The requirement in the existing 

procedure was an attempt to compensate for the poorer 

precision of some candidate alternative test methods by 
33

increasing the amount of data that the user was required to 

collect. While more data does compensate for the 

imprecision of any future data collected with the method, 

allowing candidate alternative test methods with poor 

precision creates other problems. One problem is that poor 

precision makes it more difficult to detect potential bias 

in a test method. For this reason, we are proposing to 

tighten the acceptance criteria for the precision of 

candidate alternative test methods.

4. Analyte Spiking. We are also proposing to allow 

the tester to use analyte spiking to evaluate an alternative

test method even when there is an existing compliance test 

method. If the NESHAP specifies a test method, promulgated 

Method 301 requires the tester to evaluate an alternative 

method by direct comparison. We believe that this is too 

restrictive in some cases. For example, a change in process

technology may cause a previously unbiased test method to 

develop an interference that biases its results. If the 

tester is required to compare the alternative test method to

the existing test method, the alternative method could never

demonstrate acceptable performance if it were unbiased. We 

believe that it is sufficient for an alternative method to 

demonstrate acceptable performance by using the analyte 
34

spiking procedure and that this is a reasonable alternative 

to direct comparison. 

5. Sample Stability. Finally, we are proposing Procedures

We proposed procedures for sample stability. Method 

301 previously lacked specific procedures for ensuring that 

samples collected under proposed alternative methods were 

analyzed within an appropriate time. NewWe revised Section 

87.4 includesto include a requirement to calculate the 

difference in the sampling results at the minimum and 

maximum storage times, determine the standard deviation of 

the differences, and test the difference in the results for 

statistical significance by calculating the t-statistic and 

determining if the mean of the differences between the 

initial results and the results after storage is significant

at the 95 percent confidence level. We have also added 

Table 1 to compare the calculated t-statistic with the 

critical value of the t-statistic. These procedures are 

necessary to ensure sample stability and should have been 

included in promulgated Method 301. 

Several commenters provided comments on the minimum and 

maximum storage holding time limits specified in Section 7.0

of Method 301. Commenters recommended that either the 

minimum and maximum holding times be removed and that 
35

holding times should be defined by the data or that they be 

liberalized (e.g., increase the minimum hold time to 48 to 

72 hours from 24 hours). We agree with the commenters and 

are revising the minimum hold time to be seven days. The 

method will also require that the samples be analyzed again

at the proposed maximum storage time or two weeks after the 

initial analysis.

F. Bias and Precision

We proposed to change the acceptance criteria for the 

bias in a proposed alternative method from ± 30% to ± 10% 

and concurrently to eliminate the requirement for correcting

all data collected with the method. We provided that we 

believe that twelve pairs of results from a single source 

are not sufficient to allow us to establish a correction 

factor that can or should be applied to all future uses of 

the method. 

One commenter stated that they did not believe that 

bias acceptance criteria should be changed unless 

uncertainties in the reference value are included in 

determining the significance of differences.

One commenter provided that the proposed reduction of 

bias from ± 30 to ± 10 percent is too stringent. One 

commenter suggested allowing a bias of ± 15 percent with no 
36

correction factors, while continuing to allow a bias of ± 30

percent with the use of correction factors for bias values 

between 15 and 30 percent. The commenter provided a summary

of EPA Method 301 validations of several methods to support 

their position. 

We agree that reducing the acceptable bias to ± 10

percent may be too stringent because there may be testing 

situations that are so difficult that there are no methods 

readily available that could meet this requirement. We 

believe that a reasonable solution is to allow methods that 

have a bias greater than 10 percent if the results from 

these methods are corrected to account for that bias. 

However, we believe that we should not approve the use of 

methods with greater than 30 percent bias even if the user 

were willing to correct the results. We have changed the 

final method to allow a bias of ± 10 percent with no 

correction factors and allow a bias of ± 30 percent with the

use of correction factors for bias values between 10 and 30 

percent.

We proposed to change the acceptance criteria for 

method precision when using analyte spiking from ± 50% to 

± 20%. In addition, we proposed to eliminate the 

requirement for different numbers of replicate samples 
37

depending on the method’s relative precision. We also 

proposed to tighten the acceptance criteria for the 

precision of candidate alternative test methods.

One commenter stated that the proposed reduction of 

precision criteria from ± 50 percent to ± 20 percent is too 

stringent. The commenter suggested allowing a precision of 

± 30 percent with no use of replicate runs and the continued

allowance of a precision of ± 50 percent with the use of 

additional sample runs for precision values between 30 and 

50 percent. The commenter provided a summary of EPA Method 

301 validations of several methods to support their 

position. 

Based on our evaluation of the summary provided by the 

commenter and their suggestion, we have changed the final 

method. The method will continue to require a precision of 

± 20 percent when only the required three runs per test are 

performed. However, we have added an option to allow test 

methods with a precision greater than ± 20 percent but less 

than ± 50 percent provided that the user collect nine sample

runs per test during any compliance testing where the method

is used. 

G. Limit of Detection

We proposed to replace the determination of the 
38

practical limit of quantitation (PLQ) with a procedure to 

determine the limit of detection (LOD). The purpose of 

establishing a measurement limit is to ensure that a test 

method is appropriate for its intended use. The LOD is a 

better parameter for this purpose. We provided that for 

most environmental measurements, it appears that precision 

is a function of the concentration of the analyte being 

measured. Thus, the relative imprecision will not decrease 

as the quantity measured increases. III. What Are The 

Administrative Requirements?

In this case, we stated that the PLQ has no meaning. 

Several commenters disagreed that the PLQ is a meaningless 

concept and that there are instances that substituting the 

LOD for the PLQ is not always appropriate. Some of these 

commenters stated that the Office of Water formed a FACA to 

consider alternative approaches to similar procedures they 

proposed (40 CFR 136 Appendix B) and that Method 301 should 

be deferred until after those discussions have concluded and

that consistent application be applied across the Agency 

based on those discussions.

The PLQ is a limit determined by the standard deviation

of an estimate of a concentration; if the standard deviation
39

of the estimate exceeds a threshold, then that estimate is 

unacceptable. The LOD is a limit determined by the estimate

of the concentration itself. If this estimate possesses a 

value that cannot be distinguished from an estimate 

resulting from a blank sample with a stated level of 

confidence, then this estimate is unacceptable. The LOD is 

clearly a threshold that should be used in Method 301 since 

an estimate that cannot be distinguished from one resulting 

from a blank sample is unlikely to provide meaningful 

results. 

The PLQ does not appear to have any relevance for 

Method 301. There does not appear to be a good reason for a

method that produces a standard deviation that exceeds an 

established threshold not to go through the full rigor of 

the bias and precision tests prescribed in Method 301. For 

these reasons, Method 301 retains the use of the LOD in lieu

of the PLQ.

One commenter provided that the proposed LOD 

determination does not appear appropriate for radiochemical 

methods and suggested that the content of the Multi-Agency 

Radiological Laboratory Analytical Protocols Manual (MARLAP)

be used. We agree with the commenter and have amended 

Method 301 to allow for the use of the MARLAP for 
40

radiochemical methods.

A few commenters requested that the calulation of the 

LOD be better defined and clarified in Table 4 of the 

method. One commenter expressed that the description of the

procedures used for estimating S0 in Table 4 need to be 

clarified.

The LOD is defined as the lowest quantity of a 

substance that can be distinguished from the absence of that

substance (i.e., blank value) with a stated level of 

confidence. For example, suppose blank samples are normally

distributed, and S0 represents the standard deviation of the 

blank samples (i.e., the standard deviation of pure 

“noise”). Then a sample value larger than 3S0 will have a 

probability of not being a blank of at least 99% if S0 is 

estimated with at least 14 degrees of freedom (or at least 7

degrees of freedom if a 1-sided alternative hypothesis is 

assumed). If S0 is “known”, then the probability will be 

99.74%, but this is often truncated to 99%.

The method for obtaining S0 has been clarified to 

proceed as follows:

(1) Pick a concentration level that you think should 

approximate the LOD and call this level LOD1. Prepare seven

samples of a standard set at a concentration of LOD1. 
41

Estimate the standard deviation of these seven samples, and 

call it S1.

(2) Define LOD0 = 3S1.

(3) If LOD1 ≤ 2LOD0, then define S0 = S1.

(4) If LOD1 > 2LOD0, then proceed as follows:

a. Prepare two additional standards at 

concentrations lower than LOD1, and call these LOD2

and LOD3. Prepare seven samples of each of these 

two standards and estimate their standard deviations 

and call them S2 and S3, respectively.

b. Plot S1, S2, and S3 as a function of 

concentration, draw a best-fit straight line through 

them, and extrapolate to zero concentration.

c. Define S0 as the extrapolation of the standard 

deviation at zero concentration.

H. Critical Values of t for the Two-Tailed 95% Confidence 

Limit

A couple of commenters provided that the values of t 

for the two-tailed 95% confidence limit are wrong since they

reflected an 80% confidence limit and there are some 

apparent typesetting errors. We corrected these values to 

reflect the 95% confidence limit and eliminated the

typesetting errors in the final method. 
42

I. Paired Sampling Procedure

A couple of commenters pointed out several errors and 

expressed concerns with the methods to ascertain and test 

precision in Section 12. 

Upon evaluation, we have decided to revise Section 12.2 

in Method 301. We are deleting the comparison of the 

precision of the alternative method to that of the validated

method. This decision was made because the paired sampling 

method described in it does not allow for the estimation of 

the within-sample standard deviation for either the 

alternative or validated methods.

J. Standard Deviation 

One commenter expressed that the precision is a 

function of concentration; in other words, as the 

concentration level increases, so does the standard 

deviation of the estimate of that concentration. This could

render the relative standard deviation (Eq. 301-8 in Section

10.4) meaningless.

A second commenter also expressed that the standard 

deviation is a function of concentration. This commenter 

noted that pollutant concentrations from an emission source 

are variable, resulting in a range of possible concentration

values being measured. The commenter suggested that the 
43

appropriate procedure to compare two methods under these 

circumstances is to compare the regression lines of the two 

methods across a range of concentrations. 

We agree that this could be a potentially serious 

concern, if there is little control over the concentrations 

being measured. However, if there is an appropriate level 

of control, then the procedures given in Method 301 are 

sufficient. In most situations, we believe that an 

appropriate level of control exists. For example, consider 

the case where an alternative method is compared against a 

validated method, using quadruple samples. We believe that 

an appropriate level of control exists if the following four

conditions are met: (1) there is positive correlation 

between the estimates within both alternative and validated 

pairs in the quadruple samples, and the respective 

correlation coefficients are reasonably constant as a 

function of concentration, (2) there is positive correlation

between the alternative and validated estimates in the 

quadruple samples and the correlation coefficient is 

reasonably constant as a function of concentration, (3) the 

within-quadruple sample concentrations are reasonably 

similar; and (4) if the between-quadruple sample 

concentrations vary greatly, then the functional 
44

relationship between the standard deviation and 

concentration is reasonably similar for both the alternative

and validated methods. We believe that these four 

conditions hold for most cases, and an appropriate level of 

control exists. If one or more of these conditions is 

violated, then the user may request that they be allowed to 

compare the regression lines resulting from the alternative 

and validated estimates as a function of concentration as 

an alternative to the requirements in Method 301. 

V. Statutory and Executive Order Reviews 

A. Executive Order 12866 - Regulatory Planning and Review

Under Executive Order 12866 (58 FR 51735, October 4, 

1993), the EPA must determine whether the regulatory action 

is "significant" and, therefore, subject to review by the 

Office of Management and Budget (OMB) and the requirements 

of the Executive Order. The Executive Order defines 

"significant regulatory action" as one that is likely to 

result in a rule that may:

(1) Have an annual effect on the economy of $100 

million or more or adversely affect in a material way the 

economy, a sector of the economy, productivity, competition,

jobs, the environment, public health or safety, or State, 
45

local, or tribal governments or communities;

(2) Create a serious inconsistency or otherwise 

interfere with an action taken or planned by another agency;

(3) Materially alter the budgetary impact of 

entitlements, grants, user fees, or loan programs, or the 

rights and obligation of recipients thereof; or

(4) Raise novel legal or policy issues arising out of 

legal mandates, the President's priorities, or the 

principles set forth in the Executive Order.

It has been determined that this proposed 

regulatoryThis action is not a "significant regulatory 

action" under the terms of Executive Order (EO)12866 (58 FR 

51735, October 4, 1993) and is, therefore, not subject to 

OMB review. under the EO. 

B. Paperwork Reduction Act 

This action does not impose or change the an 

information collection burden under the provisions of the 

Paperwork Reduction Act, 44 U.S.C. 3501, et seq. Burden 

means the total time, effort, or financial resources 

expended by persons to generate, maintain, retain, or 

disclose or provide information to or for a Federal agency. 

This includes the time needed to review instructions; 

develop, acquire, install, and utilize technology and 
46

systems for the purposes of collecting, validating, and 

verifying information, processing and maintaining 

information, and disclosing and providing information; 

adjust the existing ways to comply with any previously 

applicable instructions and is defined at 5 CFR 1320.3(b). 

We are not promulgating any new paperwork requirements; 

train personnel to be able to respond to a collection of 

information; search data sources; complete and review the 

collection of information; and transmit or otherwise 

disclose the collection of information. 

An agency may not conduct or sponsor, and a person is 

not required to respond to a collection of information 

unless it displays a currently valid OMB control number. 

The OMB control numbers for EPA’s (e.g., monitoring, 

reporting, recordkeeping) as part of today’s final action. 

This final rule amends Method 301 which may be used to 

validate test data or a new test method. Method 301 has 

been part of our regulations are listed in 40 CFR Part 9 and

48 CFR Chapter 15. for many years, and the amendments that 

we are making would not add any new paper work requirements.

C. Regulatory Flexibility Act (RFA)Analysis 

The RFA generally requires an agency to prepare a 

regulatory flexibility analysis of any rule subject to 
47

notice and comment rulemaking requirements under the 

Administrative Procedure Act or any other statutestatue

unless the agency certifies that the rule will not have a 

significant economic impact on a substantial number of small

entities. Small entities include small businesses, small 

organizations, and small governmental jurisdictions. 

For the purposes of assessing the impacts of today's 

proposed rulethis action on small entities, a small entity 

is defined as: (1) a small business that meets the 

definitions foris a small business based on theindustrial 

entity as defined in the U.S. Small Business 

AssociationAdministration (SBA) size standards which, for 

this proposed action, are operations that have fewer than 

1,000 employees;(see 13 CFR 121.201); (2) a small 

governmental jurisdiction that is a government of a city, 

county, town, school district, or special district with a 

population of less than 50,000; andor (3) a small 

organization that is any not-for-profit enterprise whichthat

is independently owned and operated and is not dominant in 

its field. 

After considering the economic impacts of today’s 

proposedfinal rule on small entities, I certify that this 

proposed action will not have a significant economic impact 
48

on a substantial number of small entities. In determining 

whether a rule has significant economic impact on a 

substantial number of small entities, the impact of concern 

is any significant adverse economic impact on small entities

since the primary purpose of the regulatory flexibility 

analysis is to identify and address regulatory alternatives 

“which minimize any significant economic impact of the 

proposed rule on small entities,” (5 U.S.C. 603 and 604). 

Thus, an agency may certify that a rule will not have a 

significant economic impact on a substantial number of small

entities if the rule relieves regulatory burden, or 

otherwise has a positive economic effect on all of the small

entities subject to the rule. This proposed rule will not 

This final rule does not impose any requirements on small 

entities. This rule establishes procedures for using 

alternative methods. As such, Small entities and other 

sourcesmay chose to use this regulatory option of validating

their own new or alternative compliance test method, but 

they are not required to comply withchoose this proposed 

rule, but may elect to useoption. Method 301. The proposed

rule offers additional flexibility to all sources, including

will not impose any significant impact on small entities

that may be subject. Any small entity choosing to use 
49

Method 301 to requirements under the CAA. Additionally, 

this proposed amended rule clarifies and simplifies the 

procedures for usingvalidate a new or alternative methods. 

We continue to be interestedtest method would likely do so because 

this option is less burdensome than the original method in 

the potential impacts of the proposed rule on small entities and welcome comments on 

issues related to such impacts. regulations.

D. Unfunded Mandates Reform Act 

This action contains no Federal mandates under the 

provisions of Title II of the Unfunded Mandates Reform Act 

of 1995 (UMRA), Public Law 1044, establishes requirements2 

U.S.C. 1531-1538 for Federal agencies to assess the effects 

of their regulatory actions on State, local, andor tribal 

governments andor the private sector. Under Section 202 of 

the UMRA, the EPA generally must prepare a written 

statement, including cost-benefit analysis, for proposed and

final rules with "Federal mandates" that may result in 

expenditures to This action imposes no enforceable duty on 

any State, local, and tribal governments, in the aggregate, 

or to the private sector, of $100 million or more in any one

year. Before promulgating an EPA rule for which a written 

statement is needed, Section 205 of the UMRA generally 

requires the EPA to identify and consider a reasonable 
50

number of regulatory alternatives and adopt the least 

costly, most cost-effective, or least burdensome alternative

if the Administrator publishes with the final rule an 

explanation why that alternative was not adopted. Before 

EPA establishes any regulatory requirements that may 

significantly or uniquely affect small governments, 

including tribal governments, it must have developed under 

Section 203 of the UMRA a small government agency plan. The

plan must provide for notifying potentially affected small 

governments, enabling official of affected small governments

to have meaningful and timely input in the development of 

EPA regulatory proposals with significant Federal 

intergovernmental mandates, and informing, educating, and 

advising small governments on compliance with the regulatory

requirements. 

We have determined that today’s proposed amended rule 

does not contain Federal mandates for State, local, or 

tribal governments or the private sector. Therefore, this 

proposed amended ruleaction is not subject to the 

requirements of sections 202 and 205 of the UMRA. or 

205 of the UMRA. This action is also not subject to the 

requirements of section 203 of UMRA because it contains no 

regulatory requirements that might significantly or uniquely
51

affect small governments. Any small entity that chooses to 

use Method 301 would likely do so because this option is 

less burdensome.

E. Executive Order 13132 - Federalism 

Executive Order 13132, entitled "Federalism" (64 FR 

43255, August 10, 1999), requires the EPA to develop an 

accountable process to ensure “meaningful and timely input 

by State and local officials in the development of 

regulatory policies that have federalism implications." 

"Policies that have federalism implications" is defined in 

the Executive Order to include regulations that have 

"substantial direct effects on the States, on the 

relationship between the national government and the States,

or on the distribution of power and responsibilities among 

the various levels of government." 

Under Executive Order 13132, the EPA may not issue a 

regulation that has federalism implications, that imposes 

substantial direct compliance costs, and that is not 

required by statute, unless the Federal government provides 

the funds necessary to pay the direct compliance costs 

incurred by State and local governments, or the EPA consults

with State and local officials early in the process of 

developing the proposed regulation. The EPA also may not 
52

issue a regulation that has federalism implications and that

preempts State law unless the Agency consults with State and

local officials early in the process of developing the 

proposed regulation. 

Today’s proposed amended rule will not have federalism 

implications. TheyThis action does not have federalism 

implications. It will not have substantial direct effects 

on the States, on the relationship between the national 

government and the States, or on the distribution of power 

and responsibilities among the various levels of government,

as specified in Executive Order 13132. Today’s proposed 

amended rule clarifies and simplifies the procedures for 

using alternative methods. Thus, the requirements of 

Section 6 of the Executive Order do not apply This final 

rule simply amends Method 301 which may be used to validate 

test data or a new test method.

F. Executive Order 13175 - Consultation and Coordination 

with Indian Tribal Governments 

Executive Order 13175, entitled “Consultation and 

Coordination with Indian Tribal Governments” (65 FR 67249, 

November 9, 2000), requires EPA to develop an accountable 

process to ensure “meaningful and timely input by tribal 

officials in the development of regulatory policies that 
53

have tribal implications.” The proposed amended ruleThis 

action does not have tribal implications, as specified in 

Executive Order 13175. The proposed action serves to 

clarify and simplify procedures for using (65 FR 67429, 

November 9, 2000). This final rule amends Method 301 which 

can be used to validate a new or alternative methods. 

Therefore, Executive Ordercompliance test method. It does 

not add any new requirements and does not affect pollutant 

emissions or air quality. Thus, Executive Order 13175 does 

not apply to this action.

Although EO 13175 does not apply to the proposed 

amended rule. this proposed rule, EPA specifically solicited

comment on the proposed rule from tribal officials. No 

comments were received.

G. Executive Order 13045 - Protection of Children from 

Environmental Health Risks and Safety Risks 

Executive Order EPA interprets EO 13045, 

“Protection of Children from Environmental Health Risks and 

Safety Risks” (62 FRF.R. 19885, April 23, 1997), applies to 

any rule that the EPA determines is: (1) "economically 

significant" as defined under E.O. 12866; and (2) concerns 

an environmental health or safety risk that the EPA has 

reason to believe may have a disproportionate effect on 
54

children. If the regulatory action meets both criteria, the

EPA must evaluate the environmental health or safety effects

of the planned rule on children and explain why the planned 

regulation is preferable to other potentially effective and 

reasonable alternatives considered by the EPA.

The EPA interprets Executive Order 13045) as applying 

only to those regulatory actions that are based 

onconcern health or safety risks, such that the 

analysis required under section 5-501 of the Executive 

OrderEO has the potential to influence the regulation. 

The proposed amended ruleThis action is not subject to

Executive OrderEO 13045 because it isdoes not 

economically significant as defined in Executive Order 

12866, and because this proposed amended rule is not 

based onestablish an environmental standard intended to

mitigate health or safety risks. Thus, Executive Order

13045 does not apply to this proposed amended rule.

H. Executive Order 13211, - Actions Concerning Regulations 

That Significantly Affect Energy Supply, Distribution, or 

Use 

This ruleaction is not subject to Executive Order 

13211, “Actions Concerning Regulations That Significantly 

Affect Energy Supply, Distribution, or Use” 
55

(66FR28355(May22(66 FR 28355 (May 22, 2001)) because it is 

not a significant regulatory action under Executive Order 

12866.

I. National Technology Transfer and Advancement Act of 1995

Section 112I. National Technology Transfer and Advancement 

Act 

Section 12(d) of the National Technology Transfer and 

Advancement Act of 1995 (NTTAA), Public Law No. 104-113, 

Section 12(d)915 (15 U.S.C. 272 note),) directs all Federal 

agenciesEPA to use voluntary consensus standards instead of 

government unique 

Method 301 - Page 24 of 62

standards in theirits regulatory activities unless to 

do so would be inconsistent with applicable law or otherwise

impractical. Voluntary consensus standards are technical 

standards (for example, materials specifications, test 

methods, sampling procedures, and business practices) that 

are developed or adopted by voluntary consensus standards 

bodies. The NTTAA directs EPA to provide Congress, through 

OMB, explanations when the Agency decides not to use 

available and applicable voluntary consensus standards.

Voluntary consensus standards are technical standards 
56

(e.g., materials specifications, test methods, sampling 

procedures, and business practices, etc.) that are developed

or adopted by one or more voluntary consensus standards 

bodies. Examples of organizations, generally regarded as 

voluntary consensus standards bodies, include the American 

Society for Testing and Materials (ASTM), the National Fire 

Protection Association (NFPA), and the Society of Automotive

Engineers (SAE). The NTTAA requires Federal agencies like 

EPA to provide Congress through OMB with explanations when 

an agency decides not to use available and applicable 

voluntary consensus standards. This proposed amended rule 

clarifies and simplifies, already promulgated, procedures 

for use of alternative standards. The intent of the Method 

301 is to allow owners and operators of sources regulated by

Part 63 standards the flexibility and option to use 

alternative standards. Today’s proposed amended rule is 
57

intended to simplify and clarify the procedures for using 

alternative standards. Therefore, the EPA is not 

considering the use of any voluntary consensus standards 

with today’s proposed action. 

This rulemaking involves technical standards. While 

the Agency has identified ASTM D4855-97 as being potentially

applicable, we have decided not to use it in this 

rulemaking. The use of this voluntary consensus standard 

would have been impractical as the ASTM standard is less 

prescriptive than Method 301 for many procedures. For 

example, the ASTM standard does not require the use of a t-
58

test explicitly to test the precision of an alternative 

method, but instead states than a t-test or F-test should be

used, as appropriate. The primary difference between the 

ASTM standard and EPA Method 301 is that the ASTM standard 

addresses the testing of “materials” rather than 

environmental samples. Therefore, we believe the ASTM is 

impractical as an alternative to Method 301. 

J. Executive Order 12898 - Federal Actions to Address 

Environmental Justice in Minority Populations and Low-income

Populations

Executive Order (EO) 12898 (59 FR 7629 (Feb. 16, 1994) 

establishes federal executive policy on environmental 

justice. Its main provision directs Federal agencies, to 

the greatest extent practicable and permitted by law, to 

make environmental justice part of their mission by 

identifying and addressing, as appropriate, 

disproportionately high and adverse human health or 

environmental effects of their programs, policies, and 

activities on minority populations and low-income 

populations in the United States. 

EPA has determined that this final rule will not have 

disproportionately high and adverse human health or 

environmental effects on minority or low-income populations 
59

because it does not affect the level of protection provided 

to human health or the environment. This action amends a 

method for validating new or alternative compliance test 

methods. It does not change any existing rules that limit 

air pollution emission limits.

K. Congressional Review Act

The Congressional Review Act, 5 U.S.C. 801 et seq., as 

added by the Small Business Regulatory Enforcement Fairness 

Act of 1996, generally provides that before a rule may take 

effect, the agency promulgating the rule must submit a rule 

report, which includes a copy of the rule, to each House of 

the Congress and to the Comptroller General of the United 

States. EPA will submit a report containing this rule and 

other required information to the U.S. Senate, the U.S. 

House of Representatives, and the Comptroller General of the

United States prior to publication of the rule in the 

Federal Register. A major rule cannot take effect until 60 

days after it is published in the Federal Register. This 

action is not a “major rule” as defined by 5 U.S.C. 804(2).

This rule will be effective [Insert date of publication in 

the Federal Register].
60

Method 301 - Field Validation of Pollutant Measurement 

Methods from Various Waste Media

List of Subjects in 40 CFR Part 63

Environmental protection, Alternative test method, Air 

pollution control, Field validation, Hazardous air 

pollutants, Method 301. 

________________________

Dated: December 16, 2004.

 

 

Michael O. Leavitt,

_________________________ 

Lisa P. Jackson, 

Administrator. 
61

For the reasons stated in the preamble, title 40, 

chapter I, Part 63, of the Code of the Federal Regulations 

is proposed to be amended as follows:

PART 63--[AMENDED]

1. The authority citation for Part 63 continues to read as 

follows:

Authority: 42 U.S.C. 7401, et seq.

2. Part 63Appendix A is amended by revising Appendix AMethod

301 to read as follows:

Appendix A to Part 6263 - Test Methods

* * * * *

Method 301--Field Validation of Pollutant Measurement 

Methods From Various Waste Media

Sec.

Using Method 301

1.0 What is the purpose of Method 301?

2.0 When must I use Method 301?

3.0 What does Method 301 include?

4.0 How do I perform Method 301?

Reference Materials and Performance Audits

5.0 What reference materials must I use?

6.0 How do I conduct the performance audit?

Sampling Procedures
62

76.0 What sampling procedures must I use?

87.0 How do I ensure sample stability?

Bias and Precision

8.0 What are the requirements for bias?

9.0 What are the requirements for biasprecision?

10.0 What are the requirements for precision?

11.0 What calculations must I perform for isotopic spiking?

12.0 What calculations must I perform for comparison with a

validated method if I am using paired sampling systems?

1311.0 What calculations must I perform for comparison with

a validated method if I am using quadruplet replicate 

sampling systems?

1412.0 What calculations must I perform for analyte 

spiking?

1513.0 How do I conduct tests at similar sources?

Optional Requirements

1614.0 How do I use and conduct ruggedness testing? 

17.0 What detection limits must I use?

15.0 How do I determine the Limit of Detection (LOD) for 

the alternative method?

Other Requirements and Information

1816.0 How do I apply for approval to use an alternative 

test method?
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1917.0 How do I request a waiver? 

20.0 What definitions apply to this method? 

2118.0 Where can I find additional information?

Using Method 301

1.0 What is the purpose of Method 301?

This method describes the minimumThe purpose of Method 

301 is to provide a set of procedures that you, the owner or

operator of an affected source subject to requirements under

40 CFR Part 63, must can use to validate an alternative test

method to a test method required in 40 CFR part 63. , or to 

validate a stand-alone alternative test method based on 

established precision and bias criteria. If you use Method 

301 to validate your proposed alternative method, you must 

use the procedures described in this method. This method 

describes the minimum procedures that you must use to 

validate an alternative test method to meet 40 CFR Part 63 

compliance requirements. If you choose to propose a 

validation method other than Method 301, you must submit and

obtain the Administrator’s approval for the alternative 

validation method.

2.0 When must I use Method 301?

If you want to request to use an alternative test 

method to meet requirements in a subpart of 40 CFR Part 63, 
64

you mustcan use Method 301 to validate the alternative test 

method. You must request approval to use thethis

alternative test method according to the procedures in 

Section 18Sections 16 and §63.7(f). You must receive the 

Administrator’s written approval to use the alternative test

method before you use the alternative test method to meet 

requirements under 40 CFR Part 63. In some cases, the 

Administrator may decide to waive the requirement to use 

Method 301. for alternative test methods. Section 1917

describes the requirements for obtaining a waiver.

3.0 What does Method 301 include?

3.1 Procedures. This method includes minimum 

procedures to determine and document systematic error (bias)

and random error (precision) of measured concentrations from

exhaust gases, wastewater, sludge, and other media. It 

contains procedures for ensuring sample stability if such 

procedures are not included in the test method. This method

also includes optional procedures for ruggedness and 

detection limits.

3.2 Definitions.

Affected source means affected source as defined in 40 

CFR 63.2 and in the relevant subpart under 40 CFR Part 63.

Alternative test method means the sampling and 
65

analytical methodology selected for field validation using 

the method described in this appendix.

Paired sampling system means a sampling system capable 

of obtaining two replicate samples that were collected as 

closely as possible in sampling time and sampling location.

Quadruplet sampling system means a sampling system 

capable of obtaining four replicate samples that were 

collected as closely as possible in sampling time and 

sampling location.

Surrogate compound means a compound that serves as a 

model for the types of compounds being analyzed (i.e., 

similar chemical structure, properties, behavior). The 

model can be distinguished by the method from the compounds 

being analyzed.

4.0 How do I perform Method 301?

First, you introduce a known concentration of an 

analyte or compare the alternative test method against a 

validated test method to determine the alternative test 

method's bias. Then, you collect multiple, collocated 

simultaneous samples to determine the alternative test 

method's precision. Alternatively, though it is not 

required, we allow validation testing over a broad range of 

concentrations over an extended time period to determine 
66

precision of a proposed alternative method. Sections 5.0 

through 17.0 describe thesethe procedures in detail.

Reference Materials and Performance Audits

5.0 What reference materials must I use?

You must use reference materials (a material or 

substance whose one or more properties are sufficiently 

homogenous to the analyte) that is, analytes)are traceable 

to a national standards body (e.g., National Institute of 

Standards and Technology (NIST)) at the level of the 

applicable emission limitation or standard that the subpart 

in 40 CFR Part 63 requires. If you want to expand the 

applicable range of the method, you must conduct additional 

runs with higher and lower analyte concentrations. The 

additional runs must be conducted according to the 

ruggedness procedures in 16.0. You must use the analytes 

You must obtain information about your analyte according to 

the procedures in 5.1 through 5.4.

5.1 Exhaust Gas Tests Concentration. You must get a 

known concentration of each analyte from an independent 

source such as a speciality gas manufacturer, specialty 

chemical company, or chemical laboratory. You must also get

the manufacturer’s stability datacertification for the 

analyte concentration and recommendations for 
67

recertificationstability.

5.2 Tests for Other Waste Media. You must get the 

pure liquid components of each analyte from an independent 

manufacturer. The manufacturer must certify the purity and 

shelf life of the pure liquid components. You must dilute 

the pure liquid components in the same type medium as the 

waste from the affected source. You must verify the 

accuracy of the concentration of each diluted analyte by 

comparing its response to the pure liquid components.

5.3 Surrogate Analytes. If you demonstrate to the 

Administrator’s satisfaction that a surrogate compound 

behaves as the analyte does, then you may use surrogate 

compounds for highly toxic or reactive compounds. A 

surrogate may be an isotope or one that contains a unique 

element (for example, chlorine) that is not present in the 

source or a derivation of the toxic or reactive compound, if

the derivative formation is part of the method’s procedure. 

You may use laboratory experiments or literature data to 

show behavioral acceptability.

5.4 Isotopically Labeled Materials. Isotope mixtures 

may contain the isotope and the natural analyte. The 

isotope labeled analyte concentration must be more than five

times the natural concentration of the analyte.
68

6.0 How do I conduct the performance audit?

6.1 Getting Performance Audit Material. If EPA has 

performance audit material for the analytes that you are 

testing, you must use it to assess method bias. You can get

a list of performance audit materials at 

http://www.epa.gov/ttn/emc/email.html#audit or by contacting

EMC at (919) 541-5545. You must request the performance 

audit material at least 30 days before the validation test. 

6.2 Sampling and Analyzing Performance Audit Material.

You must sample and analyze the performance audit material 

three times according to the instructions provided with the 

audit sample. You must submit the three results with the 

field validation report. Although there are no acceptance 

criteria for these performance audit results, you and the 

Administrator may use them to assess the relative error of 

sample recovery, sample preparation, and analytical 

procedures and then consider the relative error in 

evaluating the measured emissions.
69

Sampling Procedures

76.0 What sampling procedures must I use?

You may determine bias and precision by comparing 

against a validated test method, using isotopic sampling, or

using analyte spiking. (or the equivalent). Isotopic 

sampling can only be used for procedures requiring mass 

spectrometry or radiological procedures. You must collect 

samples according to the requirements in Table 1. You must 

perform the sampling according to the procedures in Sections

76.1 through 7.56.4.

7.1 Comparison Against a Validated Test Method. If 

you are comparing the results from the validated test 

method, it is recommended that you conduct a performance 

audit according to the procedures in Section 6.

7.2 Isotopic Spiking.6.1 Isotopic Spiking. Spike all

12 samples with the analyte at the concentration in the 

applicable emission limitation or standard in the subpart of

40 CFR Part 63. If there is no applicable emission 

limitation or standard, spike at the expected level of the 

samples. Follow the appropriate spiking procedures in 

7.46.3.1 through 7.46.3.2 for the applicable waste medium.

7.36.2 Analyte Spiking. In each quadruplet set, spike

half of the samples (two out of the four) with the analyte 
70

according to the applicable procedure in Section 7.46.3. 

7.46.3 Spiking Procedure. 

7.46.3.1 Gaseous Analyte with Sorbent or Impinger 

Sampling Trains. Sample the analyte (in the laboratory or 

in the field) at a concentration that is close to the 

concentration in the applicable emission limitation or 

standard in the subpart of 40 CFR Part 63 (or the expected 

sample concentration where there is no standard) for the 

time required by the method, and then sample the gas stream 

for an equal amount of time. The time for sampling both the

analyte and gas stream should be equal; however, the time 

should be adjusted to avoid sorbent breakthrough. The stack

gas and the gaseous analyte may be sampled at the same time.

The analyte must be introduced as close to the tip of the 

sampling train as possible. 

7.46.3.2 Gaseous Analyte with Sample Container (Bag or

Canister). Spike the sample containers after completion of 

each test run with an amount equal to the concentration in 

the applicable emission limitation or standard in the 

subpart of 40 CFR Part 63 (or the expected sample 

concentration where there is no standard). The final 

concentration of the analyte shall approximatewould be 

approximately equal to the level of the emission analyte 
71

concentration in the stack. plus the applicable emission 

standard (corrected for spike volume). The volume amount of

analyte shall be less than 10 percent of the sample volume.

7.46.3.3 Liquid and Solid Analyte with Sorbent or 

Impinger Trains. Spike the trains with an amount equal to 

the concentration in the applicable emission limitation or 

standard in the subpart of 40 CFR Part 63 (or the expected 

sample concentration where there is no standard) before 

sampling the stack gas. If possible, do the spiking in the 

field. If it is not possible to do the spiking in the 

field, you can do it in the laboratory.

7.46.3.4 Liquid and Solid Analyte with Sample 

Container (Bag or Canister). Spike the containers at the 

completion of each test run with an amount equal to the 

concentration in the applicable emission limitation or 

standard in the subpart of 40 CFR Part 63 (or the expected 

sample concentration where there is no standard).

7.56.4 Probe Placement and Arrangement for Stationary 

Source Stack or Duct Sampling. To sample a stationary 

source as defined in 40 CFR 63.2, you must place the probe 

according to the procedures in 7.5.this subsection. You must

place the probes in the same horizontal plane. 

7.56.4.1 Paired Sampling Probes. For paired 
72

Samplesampling probes, the sample probe tip should be 2.5 cm

from the outside edge of the other sample probe, with a 

pitot tube on the outside of each probe. The 

Administrator may approve a validation request where other 

paired arrangements for the pitot tube (where required) are 

used. 

7.5.26.4.2 Quadruplet Sampling Probes. For quadruplet

sampling probes, the tips should be in a 6.0 cm x 6.0 cm 

square area measured from the center line of the opening of 

the probe tip with a single pitot tube, where required, in 

the center or two pitot tubes, where required, with their 

location on either side of the probe tip configuration. You

must propose an alternative arrangement whenever the crosssectional area of the probe tip configuration is 

approximately 5 percent or more of the stack or duct crosssectional area. 

87.0 How do I ensure sample stability?

87.1 Developing Storage and Analysis Procedures. If 

the alternative test method includes well-established 

procedures supported by experimental data for sample storage

and the time within which the collected samples must be 

analyzed, you must store the samples according to the 

procedures in the alternative test method. You are not 
73

required to conduct the procedures in Section 87.2 or 87.3. 

If the alternative test method does not include such 

procedures, you must propose procedures for storing and 

analyzing samples to ensure sample stability. At a minimum,

your proposed procedures must meet the requirements in 

Section 87.2 or 87.3. The minimum storage time should be as

soon as possible, but no longer than 2472 hours after 

collection of the sample. The maximum storage time should 

be fourno longer than two weeks or less. 

87.2 Storage and Sampling Procedures for Stack Test 

Emissions. You must store and analyze samples of stack test

emissions according to Table 3. If you are using analyte 

spiking procedures, you must include equal numbers of spiked

and unspiked samples.

87.3 Storage and Sampling Procedures for Testing Other

Waste Media. (e.g., Soil/Sediment, Solid Waste, 

Water/Liquid). You must analyze half of the replicate 

samples at the proposed minimum storage time and the other 

half at the proposed maximum storage time or within two 

weeks of the initial analysis to identify the effect of 

storage times on analyte samples. The minimum storage time 

should be as soon as possible, but no longer than 24 

hoursseven days after collection of the sample. The 
74

maximum storage time should be two weeks or less.

87.4 Sample Stability. After you have conducted 

sampling and analysis according to 87.2 or 87.3, compare the

results at the minimum and maximum storage times. Calculate

the difference in the results using Equation 301-1.

di = Rmini - Rmaxi Eq. 301-1

Where:

di = difference between the results of the ith 

sample.

Rmini = results from the ith sample at the minimum 

storage time

Rmaxi = results from the ith sample at the maximum 

storage time.

87.4.1 Standard Deviation. Determine the standard 

deviation, SDd, of the differences, di's, of the paired 

samples using Equation 301-2. SDd= 

N

i

(di-dm)

2

n-1

n -1

( d - d )

SD =

i m

2

n

i

d Eq. 301-2

Where:

Vm = validated method

Field Code Changed
75

Pm = proposed alternative test method

di = The difference between the i-th pair of 

samples, Vm - Pmresults of the ith sample, 

Rmini - Rmaxi

dm = The mean of the paired sample differences.,

n = total number of paired samples

87.4.2 T Test. Test the difference in the results for

statistical significance by calculating the t-statistic and 

determining if the mean of the differences between the 

initial results and the results after storage is significant

at the 95 percent confidence level. and n – 1 degrees of 

freedom. Calculate the value of the t-statistic using 

Equation 301-3.

t = 

dm

SDd

n

n

SD

| d |

t=

d

m

Eq. 301-3

Where:

n is the total number of paired samples. 

Compare the calculated t-statistic with the critical 

value of the t-statistic from Table 2. If the calculated tvalue is less than the critical value, the difference is not

Field Code Changed
76

statistically significant, thus, the sampling and analysis 

procedure ensures stability, and you may submit a request 

for validation of the proposed alternative test method. If 

the calculated t-value is greater than the critical value, 

the difference is statistically significant, and you must 

repeat the procedures in 87.2 or 87.3 with new samples using

shorter proposed maximum storage times. 

Bias and Precision

98.0 What are the requirements for bias?

You must establish bias by comparing the results of the

sampling using the alternative test method against a 

reference value. The bias must be no more than +/-± 10%

without the use of correction factors, and no more than ±

30% with the use of correction factors for bias values 

between 10 and 30 percent for the alternative test method to

be acceptable.

109.0 What are the requirements for precision?

At a minimum, you must use paired sampling systems to 

establish precision. If you are using analyte spiking, 

including isotopic samples, the precision expressed as the 

relative standard deviation (RSD),) of the alternative test 

method at the level of the applicable emission limitation or

standard in the subpart of 40 CFR Part 63 must be less than 
77

or equal to 20 percent. For samples with a precision

greater than 20 percent but less than 50 percent, a minimum 

of nine sample runs will be required. If you are comparing 

to a validated test method, the alternative test method must

be at least as precise as the validated method at the level 

of the applicable emission limitation or standard in the 

subpart of 40 CFR Part 63 as determined by an F test.

(Section 11.2.2). 

1110.0 What calculations must I perform for isotopic 

spiking?

You must analyze the bias, precision, relative standard

deviation, and data acceptance for isotopic spiking tests 

according to the provisions in Sections 1110.1 through 

1110.3.

1110.1. Numerical Bias. Calculate the numerical value

of the bias using the results from the analysis of the 

isotopically spiked field samples and the calculated value 

of the isotopically labeled spike according to Equation 301-

4.

B = Sm- CS

B= Sm -CS

Eq. 301-4 Field Code Changed
78

Where:

B = Bias at the spike level.

Sm = Mean of the measured values of the isotopically 

spiked samples.

CS = Calculated value of the isotopically labeled 

spike.

1110.2. Standard Deviation. Calculate the standard 

deviation of the Si values according to Equation 301-5.

SD = 

(Si-Sm)

2

(n-1)

(n -1)

( S - S )

SD=

n

i

2

i m

Eq. 301-5

Where:

Si = Measured value of the isotopically labeled analyte 

in the i-th field sample,

n = Number of isotopically spiked samples, 12.

1110.3 T Test. Test the bias for statistical 

significance by calculating the t--statistic using Equation 

301-6. Use the standard deviation determined in section 

1110.2 and the numerical bias determined in section 1110.1.

t= 

B

SD

n

Field Code Changed
79

n

SD

B

t =

| |

Eq. 301-6

Compare the calculated t-value with the critical value 

of the two--sided t--distribution at the 95 percent 

confidence level and n--1 degrees of freedom. When spiking 

is conducted according to the procedures specified in 

sections 7 6.2 and 76.4 as required, this critical value is 

2.201 for the eleven degrees of freedom. If the calculated 

t-value is less than the critical value, the bias is not 

statistically significant, and the data arebias of the 

candidate test method is acceptable. If the calculated tvalue is greater than the critical value, the bias is 

statistically significant and you must evaluate the relative

magnitude of the bias using Equation 301-7.

100%

CS

B

BR =

Eq. 301-7

Where:

BR = Relative bias.

If the relative bias is less than or equal to 10 

percent, then the data are the bias of the candidate test 

method is acceptable. and no correction factors are 

Field Code Changed
80

required. If the relative bias is greater than 10 percent 

but less than 30 percent, and if you correct all future data

collected with the method for the magnitude of the bias, the

bias of the candidate test method is acceptable. If either 

of the preceding two cases applies, you may proceedcontinue

to evaluate the method by calculating its precision. If 

not, the candidate method will not meet the requirements of 

Method 301.

1110.4 Relative Standard Deviation. Calculate the RSD

according to Equation 301-8

RSD = 

SD

Sm

100

where 

x 100

S

SD RSD=

m

Eq. 301-8

Where:

Sm is= the measured mean of the isotopically labeled 

spiked samples. 

The data and alternative test method are unacceptable 

if the RSD is greater than 20 percent.

1211.0 What calculations must I perform for comparison with

a validated method if I am using pairedquadruplet replicate

sampling systems?

If you are using quadruplet replicate sampling systems 

Field Code Changed
81

to compare an alternative test method to a validated method,

then you must analyze the data according to the provisions 

in this section. If the data from the alternative test 

method fail either the bias or precision test, the data and 

the alternative test method are unacceptable. If the 

Administrator determines that the affected source has highly

variable emission rates, the Administrator may require 

additional precision checks.

You must analyze the data for comparison with a 

validated method according to Section 12. Conduct these 

procedures to determine if an alternative test method 

produces results equivalent to a validated method. If the 

data from the alternative test method fail either the bias 

or precision test, the data and the alternative test method 

are unacceptable.

1211.1 Bias Analysis. 

12.1.1 Standard Deviation. Determine the standard 

deviation, SDd, of the differences, di's, of the paired 

samples using Equation 301-2. 

12.1.2 t Test. Test the bias for statistical 

significance at the 95 percent confidence level by 

calculating the t-statistic and determine if the . 

11.1.1 Bias. Determine the bias, which is defined as 
82

the mean of the differences between the alternative test 

method and the validated method is significant at the 95 

percent confidence level.(dm). Calculate the di according 

to Equation 301-9.

2

( P + P )

-

2

(V +V )

d =

1 2 1 2

i

i i i i Eq. 301-9

Where:

V1i = First measured value with the validated 

method in the i-th sample.

V2i = Second measured value with the 

validated method in the i-th sample.

P1i = First measured value with the 

alternative test method in the i-th 

sample.

P2i = Second measured value with the 

alternative test method in the i-th 

sample.

11.1.2 Standard Deviation of the Differences. 

Calculate the standard deviation of the differences, SDd, 

using Equation 301-2.

11.1.3 T Test. Calculate the t-statistic using 

Equation 301-3., where n is the total number of test sample 

differences (di). For the spikingquadruplet sampling system

Field Code Changed
83

procedure for paired sampling systems, according toin

Section 76.1 and Table 1, n equals nine. 

four. Compare the calculated t-statistic with the 

critical value of the t-statistic. , and determine if the 

bias is significant at the 95 percent confidence level. 

When ninefour runs are conducted, as specified in Section 

7.16.2 and Table 1, the critical value of the t--statistic 

is 1.3973.182 for eightthree degrees of freedom. If the 

calculated t-value is less than the critical value, the bias

is not statistically significant and the data are 

acceptable. If the calculated t-value is greater than the 

critical value, the bias is statistically significant, and 

you must evaluate the relative magnitude of the bias using 

Equation 301-9. If the relative bias is less than or equal 

to 10 percent, then the data are acceptable. Proceed to 

evaluate precision.. 

BR = 

VS

B

X 100% Eq. 301-910

Where:

B = Bias =– mean of the di’s.

VS = mean measured by the validated method. 

12 If the relative bias is less than or equal to 10 
84

percent, the bias of the candidate test method is acceptable

and no correction factors are required. If the relative 

bias is greater than 10 percent but less than 30 percent and

if you correct all future data collected with the method for

the magnitude of the bias, the bias of the candidate test 

method is acceptable. If either of the preceding two cases 

applies, you may continue to evaluate the method by 

calculating its precision. If not, the candidate method 

will not meet the requirements of Method 301.

11.2. Precision. Compare the estimated variance (or 

standard deviation) of the alternative test method to that 

of the validated method. If a significant difference is 

determined using the F test, the alternative test method and

the results are rejected. If the F test does not show a 

significant difference, then the alternative test method has

acceptable precision. This procedure requires that you know

the standard deviation of the validated method, SDv. Use 

the value furnished with the method. IfCalculate the 

standard deviationestimated variance of the validated method

is not available, the paired replicate sampling procedure 

may not be used.using Equation 301-11. 

1211.2.1 Alternative Test Method Variance. Calculate 

the estimated variance of the validatedalternative test
85

method, Sv

2, using Equation 301-10.

S

2

v

= SD2

v

Where:

SDv = Standard deviation provided with the 

validated method.

12.2.2 Pooled Variance. Calculate the pooled variance

of both methods, S2

pooledSp

2, according to Equation 301-11.

S

2

pooled = 

N

i

di

2

2(n-1)

2n

d

S =

2

i

n

2 i

p

Eq. 301-11

Where:

di = The difference between the i-th pair of 

validated and alternative method samples.

n = The number of pairs of samples.

12.2.3 Alternative Test Method Variance. 

Calculate the variance of the collected with the 

alternative test method, S2

p, from the S2pooled using

Equation 301-12. S

2

p

= S

2

pooled - S

2

v

.

(If S2

v > S2pooled, let S2p = S2pooled/2). 

12.2.4n = number of samples and the degrees of 

freedom.

Field Code Changed
86

11.2.2 The F test. Determine if the estimated 

variance of the alternative test method is significantly 

different fromgreater than that of the validated method by 

performingcalculating the F test. Calculate the 

experimental F-value using Equation 301-13.12. 

F = 

Sp

2

Sv

2

Eq. 301-12

Where:

Sp

2 = The estimated variance of the alternative method.

Sv

2 = The estimated variance of the validated method.

Compare the experimental F value with the critical 

range of F at a 95 percentone-sided confidence level. for 

F. The one-sided confidence level of 95% for F is 6.388

when the procedure specified in Section 76.1 and Table 1 for

pairedquadruplet trains is followed as required, the 

critical range is 0.291 to 3.44.. If the calculated F is 

outside the critical range, the difference in precision is 

significant, and the data and alternativethe candidate test 

method are unacceptable.

1312.0 What calculations must I perform for comparison with

S

S

v

p F 2

2
87

a validated method if I am using quadruplet replicate 

sampling systemsanalyte spiking?

If you are using quadruplet replicate sampling systems 

to compare an alternative test method to a validated method,

then you must analyze the data according to the provisions 

in 13.0. If the data from the alternative test method fail 

either the bias or precision test, the data and the 

alternative test method are unacceptable. If the 

Administrator determines that the affected source has highly

variable emission rates, the Administrator may require 

additional precision checks.

13You must analyze the data for analyte spike testing 

according to this section.

12.1 Bias Analysis. Test the bias for statistical 

significance at the 95 percent confidence level by 

calculating the t-statistic. 

1312.1.1 Bias. Determine the bias, which is defined 

as using the meanresults from the analysis of the 

differences between the alternative test methodspiked field 

samples, the unspiked field samples, and the validated 

method (dm). Calculate di according tocalculated value of 

the spike using Equation 301-1413.
88

di= 

(V1

i

+ V2

i

)

2

-

(P1

i

+ P2

i

)

2

CS

2

( M + M )

-

2

( S +S )

d =

1 2 i 2

i

i i 1 i

Eq. 301-13 

Where: V1i =

S1i = First measured value withof the 

validated method in the i-thith spiked

sample.

V2i = S2i = Second measured value with the 

validated method inof the i-thith 

spiked sample.

P1i = M1i = First measured value withof the 

alternative test method in the i-thith 

unspiked sample.

P2i = Second measured value with the 

alternative test method in the i-th 

sample.

13M2i = Second measured of the ith unspiked 

sample.

CS = Calculted value of the spiked level.

12.1.2 Standard Deviation of the Differences. 

Calculate the standard deviation of the differences, SDd, 

using Equation 301-2.

Field Code Changed
89

13 12.1.3 T Test. Calculate the t-statistic using 

Equation 301-3, where n is the total number of test sample 

differences (di). For the quadruplet sampling system 

procedure in Section 7.1 and Table 1, n equals foursix. 

Compare the calculated t-statistic with the critical value 

from of the t-statistic, and determine if the bias is 

significant at the 95 percent confidence level. When 

foursix runs are conducted, as specified in Section 7.2 and 

Table 1, the 2-sided confidence level critical value of the 

t-statistic is 1.6382.571 for threethe five degrees of 

freedom. If the calculated t-value is less than the 

critical value, the bias is not statistically significant 

and the data are acceptable. If the calculated t-value is 

greater than the critical value, the bias is statistically 

significant and you must evaluate the relative magnitude of 

the bias using Equation 301-9. If the relative bias is less

than or equal to 10 percent with no correction factors, or 

the bias is greater than 10 percent but less than 30 percent

with the use of correction factors, then the data are 

acceptable. Proceed to evaluate precision of the 

alternativecandidate test method.

13.2 Precision. Compare the variance of the 

alternative test method to that of the validated method. If
90

a significant difference is determined using the F test, the

alternative test method and the results are rejected. If 

the F test does not show a significant difference, then the 

alternative test method has acceptable precision. This 

procedure requires the standard deviation of the validated 

method, SDv, to be known. Use the value furnished with the 

method. If there are no published values, calculate the 

variance of the validated method using Equation 301-15. 

13.2.1 Alternative Test Method Variance. Calculate 

the variance of the alternative test method, Sp

2, according 

to Equation 301-15.

S

2

p

= 

d

2

i

2n

Where:

di = The difference between the i-th pair of 

samples collected with the alternative test 

method.

13.2.2 The F test. Determine if the variance of the 

alternative test method is greater than that of the 

validated method by calculating the F-value using Equation 

301-13. Compare the experimental F value with the critical 

range of F. The critical range is 0.264 to 3.79 for the 95 

percent confidence level when the procedure specified in 
91

Section 7.1 and Table 1 for quadruplet trains is followed. 

If the calculated F is outside the critical range, the 

difference in precision is significant, and the data and the

alternative test method are unacceptable.

14.0 What calculations must I perform for analyte spiking?

You must analyze the data for analyte spike testing 

according to Section 14.

14.1 Bias Analysis. 

14.1.1 Bias. Calculate the numerical value of the 

bias using the results from the analysis of the spiked field

samples, the unspiked field samples, and the calculated 

value of the spike using Equation 301-16.

B = Sm- Mm- CS

Where:

B = Bias at the spike level.

Sm = Mean of the spiked samples.

Mm = Mean of the unspiked samples.

CS = Calculated value of the spiked level.

14.1.2 T Test. Test the bias for statistical 

significance by calculating the t-statistic using Equation 

301-17 and comparing it with the critical value of the 

two-sided t-distribution at the 95 percent confidence level 

and n-2 degrees of freedom. This critical value is 2.228 
92

for the ten degrees of freedom.

t = 

B

S

2

u

+ S

2

s

12

BR = 

VS

B

X 100% Eq. 301-10

Where:

S

2

u = (SDu)

2, SDu is calculated in Equation 301-19.

S

2

s = (SDs)

2, SDs is calculated in Equation 301-18.

If the calculated t-value is less than the critical value, 

the bias is not statistically significant and the data are 

acceptable. If the calculated t-value is greater than the 

critical value, the bias is statistically significant and 

you must evaluate the relative magnitude of the bias using 

Equation 301-7. If the relative bias is less than or equal 

to 10 percent, then the data are acceptable. You may 

proceed to evaluate precision. 

14 B = Bias – mean of the di’s. 

VS = mean measured by the validated method.

12.2 Precision. Calculate the standard deviation and 

the RSD relative standard deviation of the 

alternativecandidate test method.

14.2.1 Spiked Samples. Calculate the difference, di, 

Field Code Changed
93

between the pairs of the spiked alternative test method 

measurements for each replicate sample set. Determine the 

standard deviation (SDs) of the spiked values using Equation 

301-18.

SDs= 

dis

2

2n

Where: dis = Difference between the i-th pair of spiked 

 samples. 

n = Number of paired samples.

14.2.2 Unspiked Samples. Calculate the The relative

standard deviation of the unspiked values using Equation 

301-19. 

SDu= 

diu

2

2n

Where: diu = Difference between the i-th 

pair of unspiked samples.

n = Number of paired samples.

14.2.3 Pooled Standard Deviation. Calculate the 

pooled standard deviation of the spiked and unspiked samples

if the standard deviations are not significantly different. 

Test for this difference using Equation 301-20.

F = 

Su

2

Ss

2

Where Su

2 and Ss2 are defined in Equation 301-17.
94

For the case where n = 6 and a 95 percent confidence level, 

the standard deviations may be pooled if the calculated F 

lies between 0.139 and 7.146. Calculate the pooled standard

deviation (SDpooled) using Equation 301-21.

SDpooled = 

Ss

2+Su2

2

If the variances are significantly different and cannot be 

pooled, use the standard deviation of the spiked samples for

the bias analysis in Section 14.1.2. 

14.2.4 Relative Standard Deviation. Calculate the RSD

of the alternativecandidate test method can be calculated 

using Equation 301-8 and the pooled standard deviation 

determined from Section 14.2.3. If the pooled standard 

deviation or the standard deviation from the unspiked 

samples is used, Sm is the mean of the unspiked samples. If

the standard deviation of the spiked samples is used, Sm is 

the mean of the spiked samples. The data and alternative 

test method are unacceptable if the RSD is greater than 20 

percent.. 

1513.0 How do I conduct tests at similar sources?

If the Administrator has approved the use of an 

alternative test method to a test method required in 40 CFR 

Part 63 for an affected source, and the Administrator has 
95

approved the use of the alternative test method at your 

similar source according to the procedures in 1917.1.1, you 

must meet the requirements in this section. You must have 

at least three replicate samples for each test that you 

conduct at the similar source. You must average the results

of the samples to determine the pollutant concentration. 

Optional Requirements

1614.0 How do I use and conduct ruggedness testing?

If you want to use a validated test method at a 

concentration that is different from the concentration in 

the applicable emission limitation in the subpart of 40 CFR 

Part 63 or for a source category that is different from the 

source category that the test method specifies, then you 

must conduct ruggedness testing according to the procedures 

in Citation 1018.16 of Section 18.0 and submit a request for

a waiver according to 1917.1.1. 

Ruggedness testing is a laboratory study to determine 

the sensitivity of a method to parameters such as sample 

collection rate, interferant concentration, collecting 

medium temperature, and sample recovery temperature. You 

conduct ruggedness testing by changing several variables 

simultaneously instead of changing one variable at a time. 

For example, you can determine the effect of seven variables
96

in eight experiments instead of one. (W.J. Youden, 

Statistical Manual of the Association of Official Analytical

Chemists, Association of Official Analytical Chemists, 

Washington, DC, 1975, pp. 33-36).

1715.0 How do I determine the Limit of Detection for the 

alternative method?

17 15.1 Limit of Detection. The Limit of Detection (LOD) 

is the lowest level above which you may obtain quantitative 

results with an acceptable degree of confidence. For this 

protocol, the LOD is defined as 3three times the standard 

deviation, So, at the blank level. This LOD corresponds 

to an uncertainty of ±30% at the 99 percent confidence 

level.

 17 15.2 Purpose. The LOD will be used to establish 

the lower limit of the test method. If the estimated LOD is

no more than twice the calculated LOD, use Procedure I in 

Table 4 to determine So. If the LOD is greater than twice 

the calculated LOD, use Procedure II in Table 4 to determine

So. For radiochemical methods, use the Multi-Agency 

Radiological Laboratory Analytical Protocols (MARLAP) Manual

(i.e., uses the minimum detectable concentration (MDC) and 

not the LOD) available at

http://www.epa.gov/radiation/docs/marlap/402-b-04-001c-
97

20_final.pdf. 

Other Requirements and Information

1816.0 How do I apply for approval ofto use an alternative 

test method?

1816.1 Submitting Requests. You must request to use 

an alternative test method according to the procedures in 

§Section 63.7(f). You may not use an alternative test 

method to meet any requirement under 40 CFR Part 63 until 

the Administrator has approved your request. The request 

must include a field validation reportingreport containing 

the information in 18Section 16.2. The request must be 

submitted to the Director, Emissions Monitoring and 

AnalysisAir Quality Assessment Division, U.S. Environmental 

Protection Agency, C304-02, Research Triangle Park, NC 

27711.

1816.2 Field Validation Report. The field validation 

report must contain the information in 1816.2.1 through 

1816.2.98. 

1816.2.1 Regulatory objectives for the testing, 

including a description of the reasons for the test, 

applicable emission limits, and a description of the source.

1816.2.2 Summary of the results and calculations shown

in Sections 76.0 through 1716, as applicable.
98

1816.2.3 Analyte certification and value(s).

1816.2.4 Laboratory demonstration of the quality of 

the spiking system.

18.2.5 Discussion of laboratory evaluations.

1816.2.5 Discussion of field sampling.

16.2.6 Discussion of field sampling.

18.2.7 Discussion of sample preparations and analysis.

1816.2.87 Storage times of samples (and extracts, if 

applicable).

1816.2.98 Reasons for eliminating any results.

1917.0 How do I request a waiver?

1917.1 Conditions for Waivers. If you meet one of the

criteria in 1917.1.1 through 1917.1.32, the Administrator 

may waive the requirement to use the procedures in this 

method to validate an alternative test method. In addition,

if the EPA currently recognizes an appropriate test method 

or considers the analyst’s test method to be satisfactory 

for a particular source, the Administrator may waive the use

of this protocol or may specify a less rigorous validation 

procedure.

1917.1.1 Similar Sources. If the alternative test 

method that you want to use has been validated at another 

source and you can demonstrate to the 
99

Administrator’sAdministrator=s satisfaction that your 

affected source is similar to that source, then the 

Administrator may waive the requirement for you to validate 

the alternative test method. One procedure you may use to 

demonstrate the applicability of the method to your affected

source is by conducting a ruggedness test as described in 

1614.0.

1917.1.2 Documented Methods. If the bias and 

precision of the alternative test method that you are 

proposing have been demonstrated through laboratory tests or

protocols different from this method, and you can 

demonstrate to the Administrator’s satisfaction that the 

bias and precision apply to your application, then the 

Administrator may waive the requirement to use this method 

or to use part of this method. 

19.1.3 Conditional Test Methods. If the alternative 

test method has been demonstrated to be valid at several 

sources, you may ask the Administrator to designate the 

alternative test method as a conditional test method. If 

the Administrator has designated a test method as a 

conditional test method and you are using the conditional 

method within its stated applicability, you do not have to 

validate it according to the procedures in this method. You
100

can find a list of conditional test methods at 

http://www.epa.gov/ttn/emc/ctm.html.

1917.2 Submitting Applications for Waivers. You must 

sign and submit each request for a waiver from the 

requirements in this method in writing. The request must be

submitted to the Director, Emissions Monitoring and 

AnalysisAir Quality Assessment Division, U.S. Environmental 

Protection Agency, C304-02, Research Triangle Park, NC 

27711. 

1917.3 Information Application for Waiver. The 

request for a waiver must contain a thorough description of 

the test method, the intended application, and results of 

any validation or other supporting documents. The request 

for a waiver must contain, at a minimum, the information in 

1917.3.1 through 1917.3.4. The Administrator may request 

additional information if necessary to determine whether 

this method can be waived for a particular application. 

1917.3.1 A Clearly Written Test Method. The method 

should be written preferably in the format of 40 CFR Part 

60, Appendix A Test Methods. It must include an 

applicability statement, concentration range, precision, 

bias (accuracy), and minimum and maximum storage time in 

which samples must be analyzed.
101

1917.3.2 Summaries (see Section 18.3) of previous 

validation tests or other supporting documents. If a 

different procedure from that described in this method was 

used, you must submit documents substantiating the bias and 

precision values to the Administrator’s satisfaction.

1917.3.3 Ruggedness Testing Results. You must submit 

results of ruggedness testing conducted according to Section

1614.0, sample stability conducted according to Section 

87.0, and detection limits conducted according to Section 

1715.0, as applicable. For example, you would not need to 

submit ruggedness testing results if you will be using the 

method at the same concentration level as the concentration 

level at which it was validated. 

1917.3.4 Applicability Statement and ArgumentsBasis

for Waiver Approval. Discussion of the applicability 

statement and argumentsbasis for approval of the waiver. 

This discussion should address as applicable the following: 

applicable regulation, emission standards, effluent 

characteristics, and process operations.

20.0 What definitions apply to this method?

Affected source means affected source as defined in 40 

CFR 63.2 and in the relevant subpart under 40 CFR Part 63.

Alternative test method means the sampling and 
102

analytical methodology selected for field validation using 

the method described in this appendix.

Paired sampling system means a sampling system capable 

of obtaining two replicate samples that were collected as 

closely as possible in sampling time and sampling location.

Quadruplet sampling system means a sampling system capable 

of obtaining four replicate samples that were collected as 

closely as possible in sampling time and sampling location.

Surrogate compound means a compound that serves as a 

model for the types of compounds being analyzed (i.e., 

similar chemical structure, properties, behavior). The 

model can be distinguished by the method from the compounds 

being analyzed.

2118.0 Where can I find additional information?

You can find additional information in the references 

in paragraphs 21Sections 18.1 through 21.1218.16.

 21 18.1 Albritton, J.R., G.B. Howe, S.B. Tompkins, 

R.K.M. Jayanty, and C.E. Decker. 1989. Stability of PartsPer-Million Organic Cylinder Gases and Results of Source 

Test Analysis Audits, Status Report No. 11. Environmental 

Protection Agency Contract 68-02-4125. Research Triangle 

Institute, Research Triangle Park, NC. September.

 21.2 18.2 ASTM Standard E 1169-89 (current version), 
103

“Standard Guide for Conducting Ruggedness Tests,” available 

from ASTM, 100 Barr Harbor Drive, West Conshohoken, PA 

19428.

18.3 DeWees, W.G., P.M. Grohse, K.K. Luk, and F.E. 

Butler. 1989. Laboratory and Field Evaluation of a 

Methodology for Speciating Nickel Emissions from Stationary 

Sources. EPA Contract 68-02-4442. Prepared for Atmospheric

Research and Environmental Assessment Laboratory, Office of 

Research and Development, U.S. Environmental Protection 

Agency, Research Triangle Park, NC 27711. January.

 21.3 18.4 International Conference on Harmonization of 

Technical Requirements for the Registration of 

Pharmaceuticals for Human Use, ICH-Q2A, “Text on Validation 

of Analytical Procedures,” 60 FR 11260 (March 1995).

18.5 International Conference on Harmonization of 

Technical Requirements for the Registration of 

Pharmaceuticals for Human Use, ICH-Q2b, “Validation of 

Analytical Procedures: Methodology,” 62 FR 27464 (May 1997)

18.6 Keith, L.H., W. Crummer, J. Deegan Jr., R.A. 

Libby, J.K. Taylor, and G. Wentler. 1983. Principles of 

Environmental Analysis. American Chemical Society, 

Washington, DC.

 21.4 18.7 Maxwell, E.A. 1974. Estimating variances 
104

from one or two measurements on each sample. Amer. 

Statistician 28:96-97.

 21.5 18.8 Midgett, M.R. 1977. How EPA Validates NSPS 

Methodology. Environ. Sci. & Technol. 11(7):655-659.

 21.6 18.9 Mitchell, W.J., and M.R. Midgett. 1976. 

Means to evaluate performance of stationary source test 

methods. Environ. Sci. & Technol. 10:85-88.

 21.7 18.10 Plackett, R.L., and J.P. Burman. 1946. 

The design of optimum multifactorial experiments. 

Biometrika, 33:305.

 21.8 18.11 Taylor, J.K. 1987. Quality Assurance of 

Chemical Measurements. Lewis Publishers, Inc., pp. 79-81.

 21.9 18.12 U.S. Environmental Protection Agency. 

1978. Quality Assurance Handbook for Air Pollution 

Measurement Systems: Volume III. Stationary Source 

Specific Methods. Publication No. EPA-600/4-77-027b. 

Office of Research and Development Publications, 26 West St.

Clair St., Cincinnati, OH 45268.
 21.10 18.13 U.S. Environmental Protection Agency. 

1981. A Procedure for Establishing Traceability of Gas 

Mixtures to Certain National Bureau of Standards Standard 

Reference Materials. Publication No. EPA-600/7-81-010. 

Available from the U.S. EPA, Quality Assurance Division (MD77), Research Triangle Park, NC 27711.

 21.11 18.14 U.S. Environmental Protection Agency. 

1991. Protocol for The Field Validation of Emission 

Concentrations From Stationary Sources. Publication No. 

450/4-90-015. Available from the U.S. EPA, Emission 

Measurement Technical Information Center, Technical Support 

Division (MD-14), Research Triangle Park, NC 27711. 

 21.12 18.15 Wernimont, G.T., “Use of Statistics to 

Develop and Evaluate Analytical Methods,” AOAC, 1111 North 

19th Street, Suite 210, Arlington, VA 22209. USA, 78-82 

(1987).

18.16 Youden, W.J. Statistical techniques for 

collaborative tests. In: Statistical Manual of the 

Association of Official Analytical Chemists, Association of 

Official Analytical Chemists, Washington, DC, 1975, pp. 33--

36.
Page 106 of 111

Table 1 of Appendix A. Sampling Procedures

If you are... You must collect...

comparing against a 

validated method

nine sets of replicate samples 

using a paired sampling system 

(a total of 18 samples) or four 

sets of replicate samples using 

a quadruplet sampling system (a 

total of 16 samples). In each 

sample set, you must use the 

validated test method to collect 

and analyze half of the samples.

using isotopic spiking 

(can only be used for 

procedures requiring 

mass spectrometry)

a total of 12 replicate samples. 

You may collect the samples 

either by obtaining six sets of 

paired samples or three sets of 

quadruplet samples.

using analyte spiking a total of 24 samples using the 

quadruplet sampling system (a 

total of 6 sets of replicate 

samples).

Formatted Table
Page 107 of 111

Table 2. of Appendix A. Critical Values of t for the Two 

Tailed 95 Percent Confidence Limit

Degrees of freedom t95

1 3=07812.706

2 1=8864.303

3 1=6383.182

4 1=5332.776

5 1=4762.571

6 1=442.447

7 1=4152.365

8 1=3972.306

9 1=3832.262

10 1=3722.228
Page 108 of 111

Table 3 of Appendix A. Storage and Sampling Procedures 

for Stack Test Emissions

If you are... With... Then you must...

using isotopic 

or analyte 

spiking 

procedures

sample 

container (bag 

or canister) 

and impinger 

sampling 

systems

analyze six of the 

samples at the proposed 

minimum storage timewithin 

seven days and then 

analyze the same six 

samples at the proposed 

maximum storage time or 

two weeks after the 

initial analysis.

sorbent and 

impinger 

sampling 

systems that 

require 

extraction or 

digestion

extract or digest six 

of the samples at the 

proposed minimum storage 

timewithin seven days

and extract or digest 

six other samples at 

the proposed maximum 

storage time. or two 

weeks after the first 

extraction or 

digestion. Analyze an 

aliquot of the first 

six extracts 

(digestates) at both the 

proposed minimumwithin 

seven days and proposed 

maximum storage times.

or two weeks after the 

initial analysis. This 

will allow analysis of 

extract storage 

impacts.

Formatted Table
Page 109 of 111

Table 3 of Appendix A. Storage and Sampling Procedures 

for Stack Test Emissions

If you are... With... Then you must...

sorbent 

sampling 

systems that 

require thermal 

desorption

analyze six samples at 

the proposed minimum storage 

time.within seven days.

Analyze another set of 

six samples at the 

proposed maximum 

storage time or within 

two weeks of the 

initial analysis.

comparing an 

alternative 

test method 

against a 

validated test 

method

sampling method 

that does not

include sorbent 

and impinger 

sampling 

systems that 

require 

extraction or 

digestion

analyze half of the 

samples (8 or 9) at the 

proposed minimum storage 

timewithin seven days

and half of the samples 

(8 or 9) at the 

proposed maximum 

storage time or within 

two weeks of the 

initial analysis.

Formatted Table
Page 110 of 111

Table 3 of Appendix A. Storage and Sampling Procedures 

for Stack Test Emissions

If you are... With... Then you must...

sorbent and 

impinger 

sampling 

systems that 

require 

extraction or 

digestion

extract or digest six 

of the samples at the 

proposed minimum storage 

timewithin seven days

and extract or digest 

six other samples at 

the proposed maximum 

storage time. or within 

two weeks of the first 

extraction or 

digestion. Analyze an 

aliquot of the first 

six extracts 

(digestates) at both the 

proposed minimumwithin 

seven days and at the 

proposed maximum 

storage times or within 

two weeks of the 

initial analysis. This 

will allow analysis of 

extract storage 

impacts.

Formatted Table
Page 111 of 111

Table 4. to of Appendix A. Procedures for Estimating So

If the estimated LOD (LOD1, 

expected approximate LOD 

concentration level) is no 

more than twice the 

calculated LOD, use 

Procedure I as follows.

If the LODestimated LOD 

(LOD1, expected approximate 

LOD concentration level) is 

greater than twice the 

calculated LOD, use 

Procedure II as follows.

Estimate the LOD (LOD1) and 

prepare a test standard at 

this level. The test 

standard could consist of a 

dilution of the analyte 

described in Section 5.0.

Prepare two additional 

standards (LOD2 and LOD3) at 

concentration levels lower 

than the standard used in 

Procedure I. (LOD1). 

Using the normal sampling 

and analytical procedures 

for the method, sample and 

analyze this standard at 

least seven times in the 

laboratory.

Sample and analyze each of 

these standards (LOD2and 

LOD3)at least seven times.

Calculate the standard 

deviation, SoS1, of the 

measured values.

Calculate the standard 

deviation (S2 and S3) for 

each concentration level.

Calculate the LODLOD0

(referred to as the 

calculated LOD)as 3 times 

SoS1, where S0 = S1.

Plot the standard deviations 

of the three test standards 

(S1, S2 and S3) as a function 

of the standard 

concentrationsconcentration.

Draw a best--fit straight 

line through the data points 

and extrapolate to zero 

concentration. The standard 

deviation at zero 

concentration is So.

Calculate the LODLOD0

(referred to as the 

calculated LOD)as 3 times 

So.