6560-50-P

ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63

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

RIN 2060-AF00 

Method 301 - Field Validation of Pollutant Measurement 

Methods from Various Waste Media

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule.

SUMMARY: This action amends 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: This final rule is effective on [Insert date of
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publication in the Federal Register].

ADDRESSES: EPA has established a docket for this action 

under Docket ID No. EPA-HQ-OAR-2004-0080. All documents in 

the docket are listed on the http://www.regulations.gov web 

site. Although listed in the index, some information is not

publicly available, 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 hard copy

form. Publicly available docket materials are available 

either electronically through http://www.regulations.gov or 

in hard copy at the Air Docket, EPA/DC, EPA West, Room 3334, 

1301 Constitution Avenue, NW, Washington, DC. The Docket 

Facility 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.

FOR FURTHER INFORMATION CONTACT: Ms. Lula H. Melton, Office 

of Air Quality Planning and Standards, Air Quality 

Assessment Division, Measurement Technology Group (E143-02), 

U.S. Environmental Protection Agency, Research Triangle 
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Park, North Carolina 27711; telephone number: (919) 541-

2910; fax number: (919) 541-0516; e-mail address: 

melton.lula@epa.gov.

SUPPLEMENTARY INFORMATION:

Table of Contents

I. General Information

A. Does this Action Apply to Me?

B. Where Can I Obtain a Copy of This Action?

C. Judicial Review

II. Background

III. Summary of the Final Method

IV. Significant Comments Received on the Proposed 

Amendments to Method 301

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% 
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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

C. Regulatory Flexibility Act

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

J. Executive Order 12898 – Federal Actions to Address 

Environmental Justice in Minority Populations and 

Low-income Populations

K. Congressional Review Act

I. General Information
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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. 

B. Where Can I Obtain a Copy of this Action?

In addition to being available in the docket, an 

electronic copy of this rule will also be available on the 

Worldwide Web (www) through the Technology Transfer Network 

(TTN). Following the Administrator’s signature, a copy of 

the final rule will be placed on the TTN’s policy and 

guidance page for newly proposed or promulgated rules at 

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

and technology exchange in various areas of air pollution 

control. 

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

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 
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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 was originally promulgated in Appendix A of 40 

CFR, Part 63 on June 3, 1991. 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

You would use Method 301 whenever you propose to use a 

test method to meet an EPA compliance requirement other than

a 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 
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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.

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.

The following section provides our response to 
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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.

A few commenters expressed concern that the standard 

against which precision and bias are compared is not 
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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 

to determine the precision of a proposed alternative method 
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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 

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

E. Sample Stability 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. We revised Section 7.4 

to 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 also added Table 1 to compare 

the calculated t-statistic with the critical value of the tstatistic. These procedures are necessary to ensure sample 

stability and should have been included in 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 
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minimum and maximum holding times be removed and that 

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 
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commenter suggested allowing a bias of ± 15 percent with no 

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 
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requirement for different numbers of replicate samples 

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
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We proposed to replace the determination of the 

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. 

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

of the estimate exceeds a threshold, then that estimate is 
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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 

radiochemical methods.
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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. 
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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. 
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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 
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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 
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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

This 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 review

under the EO. 

B. Paperwork Reduction Act 

This action does not impose an information collection 

burden under the provisions of the Paperwork Reduction Act,

44 U.S.C. 3501 et seq. Burden is defined at 5 CFR 1320.3(b). 

We are not promulgating any new paperwork requirements

(e.g., monitoring, reporting, recordkeeping) as part of 
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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 for 

many years, and the amendments that we are making would not 

add any new paper work requirements. 

C. Regulatory Flexibility Analysis 

The RFA generally requires an agency to prepare a 

regulatory flexibility analysis of any rule subject to 

notice and comment rulemaking requirements under the 

Administrative Procedure Act or any other statue 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 purposes of assessing the impacts of this action on 

small entities, a small entity is defined as: (1) a small 

business that is a small industrial entity as defined in the 

U.S. Small Business Administration (SBA) size standards (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; or

(3) a small organization that is any not-for-profit 

enterprise that is independently owned and operated and is 
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not dominant in its field. 

After considering the economic impacts of today’s final

rule on small entities, I certify that this action will not 

have a significant economic impact on a substantial number 

of small entities. This final rule does not impose any 

requirements on small entities. Small entities may chose to 

use this regulatory option of validating their own new or 

alternative compliance test method, but they are not 

required to choose this option. Method 301 will not impose 

any significant impact on small entities. Any small entity 

choosing to use Method 301 to validate a new or alternative 

test method would likely do so because this option is less 

burdensome than the original method in the 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), 2 U.S.C. 1531-1538 for State, local, or

tribal governments or the private sector. This action 

imposes no enforceable duty on any State, local or tribal 

governments or the private sector. Therefore, this action

is not subject to the requirements of sections 202 or 205 of 

the UMRA. This action is also not subject to the 

requirements of section 203 of UMRA because it contains no 
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regulatory requirements that might significantly or uniquely

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 

This 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. 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 

This action does not have tribal implications, as 

specified in Executive Order 13175 (65 FR 67429, November 9, 

2000). This final rule amends Method 301 which can be used 

to validate a new or alternative compliance 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 this proposed rule, 
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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 

EPA interprets EO 13045 (62 F.R. 19885, April 23, 

1997) as applying only to those regulatory actions that 

concern health or safety risks, such that the analysis 

required under section 5-501 of the EO has the 

potential to influence the regulation. This action is 

not subject to EO 13045 because it does not establish 

an environmental standard intended to mitigate health 

or safety risks.

H. Executive Order 13211 - Actions Concerning Regulations 

That Significantly Affect Energy Supply, Distribution, or 

Use 

This action is not subject to Executive Order 13211, 

(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 

Section 12(d) of the National Technology Transfer and 

Advancement Act of 1995 (NTTAA), Public Law 104-113, 12(d)

(15 U.S.C. 272 note) directs EPA to use voluntary consensus 

standards in its regulatory activities unless to do so would 
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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.

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 ttest 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 
Page 27 of 68

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 

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 
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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].
Page 29 of 68

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: 

_________________________ 

Lisa P. Jackson, 

Administrator. 
Page 30 of 68

For the reasons stated in the preamble, title 40, 

chapter I of the Code of the Federal Regulations is 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. Appendix A is amended by revising Method 301 to read as 

follows:

Appendix A to Part 63 - 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

5.0 What reference materials must I use?

Sampling Procedures
Page 31 of 68

6.0 What sampling procedures must I use?

7.0 How do I ensure sample stability?

Bias and Precision

8.0 What are the requirements for bias?

9.0 What are the requirements for precision?

10.0 What calculations must I perform for isotopic spiking?

11.0 What calculations must I perform for comparison with a

validated method if I am using quadruplet replicate sampling

systems?

12.0 What calculations must I perform for analyte spiking?

13.0 How do I conduct tests at similar sources?

Optional Requirements

14.0 How do I use and conduct ruggedness testing? 

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

the alternative method?

Other Requirements and Information

16.0 How do I apply for approval to use an alternative test

method?

17.0 How do I request a waiver? 

18.0 Where can I find additional information?

Using Method 301

1.0 What is the purpose of Method 301?
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The 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 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 use an alternative test method to meet 

requirements in a subpart of 40 CFR Part 63, you can use 

Method 301 to validate the alternative test method. You 

must request approval to use this alternative test method 

according to the procedures in Sections 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 
Page 33 of 68

cases, the Administrator may decide to waive the requirement

to use Method 301 for alternative test methods. Section 17

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 

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 
Page 34 of 68

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 

precision of a proposed alternative method. Sections 5.0 

through 17.0 describe the procedures in detail.

Reference Materials 

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 are traceable to a national 
Page 35 of 68

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. 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 certification for the analyte 

concentration and stability.

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.

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 
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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.

Sampling Procedures

6.0 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

6.1 through 6.4.

6.1 Isotopic Spiking. Spike all 12 samples with the 

analyte at the concentration in the applicable emission 
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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 6.3.1 through 6.3.2 for 

the applicable waste medium.

6.2 Analyte Spiking. In each quadruplet set, spike 

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

according to the applicable procedure in Section 6.3. 

6.3 Spiking Procedure. 

6.3.1 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. 

6.3.2 Gaseous Analyte with Sample Container (Bag or 
Page 38 of 68

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 would be approximately equal to

the analyte 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.

6.3.3 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.

6.3.4 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 
Page 39 of 68

concentration where there is no standard).

6.4 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 this subsection. You must 

place the probes in the same horizontal plane. 

6.4.1 Paired Sampling Probes. For paired sampling

probes, the 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. 

6.4.2 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. 

7.0 How do I ensure sample stability?
Page 40 of 68

7.1 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 

required to conduct the procedures in Section 7.2 or 7.3. 

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 7.2 or 7.3. The minimum storage time should be as 

soon as possible, but no longer than 72 hours after 

collection of the sample. The maximum storage time should 

be no longer than two weeks. 

7.2 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.

7.3 Storage and Sampling Procedures for Testing Other 

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

Water/Liquid). You must analyze half of the replicate 
Page 41 of 68

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 seven days

after collection of the sample. 

7.4 Sample Stability. After you have conducted 

sampling and analysis according to 7.2 or 7.3, 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.

7.4.1 Standard Deviation. Determine the standard 

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

samples using Equation 301-2.
Page 42 of 68

n -1

( d - d )

SD =

i m

2

n

i

d



 Eq. 301-2

Where:

di = The difference between the results of the ith 

sample, Rmini - Rmaxi

dm = The mean of the paired sample differences,

n = total number of paired samples

7.4.2 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.

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

statistically significant, thus, the sampling and analysis 
Page 43 of 68

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 7.2 or 7.3 with new samples using 

shorter proposed maximum storage times. 

Bias and Precision

8.0 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.

9.0 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 

or equal to 20 percent. For samples with a precision
Page 44 of 68

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). 

10.0 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 10.1 through 10.3.

10.1 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= S m - CS Eq. 301-4

Where:

B = Bias at the spike level.

Sm = Mean of the measured values of the isotopically 

spiked samples.
Page 45 of 68

CS = Calculated value of the isotopically labeled 

spike.

10.2 Standard Deviation. Calculate the standard 

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

(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.

10.3 T Test. Test the bias for statistical 

significance by calculating the t-statistic using Equation 

301-6. Use the standard deviation determined in section 

10.2 and the numerical bias determined in section 10.1.

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 6.2 and 

6.4 as required, this critical value is 2.201 for the eleven

degrees of freedom. If the calculated t-value is less than 
Page 46 of 68

the critical value, the bias is not statistically 

significant, and the bias of the candidate test method is

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.

100%

CS

B

BR = Eq. 301-7

Where:

BR = Relative bias.

If the relative bias is less than or equal to 10 

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.

10.4 Relative Standard Deviation. Calculate the RSD 

according to Equation 301-8
Page 47 of 68

x 100

S

SD RSD=

m

















Eq. 301-8

Where:

Sm = 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.

11.0 What calculations must I perform for comparison with a

validated method if I am using quadruplet replicate sampling 

systems?

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 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.

11.1 Bias Analysis. Test the bias for statistical 

significance at the 95 percent confidence level by 

calculating the t-statistic. 

11.1.1 Bias. Determine the bias, which is defined as 
Page 48 of 68

the mean of the differences between the alternative test 

method and the validated method (dm). Calculate 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 quadruplet sampling system

procedure in Section 6.1 and Table 1, n equals four. 
Page 49 of 68

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 four runs are 

conducted, as specified in Section 6.2 and Table 1, the 

critical value of the t-statistic is 3.182 for three 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 301-10. 

BR = 

VS

B

X 100% Eq. 301-10

Where:

B = Bias – mean of the di’s.

VS = mean measured by the validated method. 

If the relative bias is less than or equal to 10 

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 
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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. Use the value furnished with the 

method. Calculate the estimated variance of the validated 

method using Equation 301-11. 

11.2.1 Alternative Test Method Variance. Calculate 

the estimated variance of the alternative test method, Sp

2, 

according to Equation 301-11.

2n

d

S =

2

i

n

2 i

p



Eq. 301-11

Where:

di = The difference between the i-th pair of 

samples collected with the alternative test 

method.

n = number of samples and the degrees of freedom.
Page 51 of 68

11.2.2 The F test. Determine if the estimated 

variance of the alternative test method is greater than that 

of the validated method by calculating the F-value using 

Equation 301-12. 

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 one-sided

confidence level for F. The one-sided confidence level of 

95% for F is 6.388 when the procedure specified in Section 

6.1 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 candidate

test method are unacceptable.

12.0 What calculations must I perform for analyte spiking?

You 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 

S

S

v

p

F 2

2


Page 52 of 68

calculating the t-statistic. 

12.1.1 Bias. Determine 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 301-13.

CS

2

( M + M )

-

2

( S + S )

d =

1 2 i 2

i

i i i 

1

Eq. 301-13 

Where:

S1i = First measured value of the ith spiked

sample.

S2i = Second measured value of the ith spiked

sample.

M1i = First measured value of the ith 

unspiked sample.

M2i = 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.

12.1.3 T Test. Calculate the t-statistic using 

Equation 301-3, where n is the total number of test sample 
Page 53 of 68

differences (di). For the quadruplet sampling system 

procedure in Table 1, n equals six. 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 six runs are conducted, as specified 

in Table 1, the 2-sided confidence level critical value is 

2.571 for the five degrees of freedom. 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 

candidate test method.

BR = 

VS

B

X 100% Eq. 301-10

Where:

B = Bias – mean of the di’s. 

VS = mean measured by the validated method.

12.2 Precision. Calculate the standard deviation and 

the relative standard deviation of the candidate test 

method. The relative standard deviation of the candidate

test method can be calculated using Equation 301-8. 

13.0 How do I conduct tests at similar sources?

If the Administrator has approved the use of an 
Page 54 of 68

alternative test method to a test method required in 40 CFR 

Part 63 for an affected source, and the Administrator has 

approved the use of the alternative test method at your 

similar source according to the procedures in 17.1.1, 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

14.0 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 18.16 of Section 18.0 and submit a request for a 

waiver according to 17.1.1. 

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 
Page 55 of 68

simultaneously instead of changing one variable at a time. 

For example, you can determine the effect of seven variables

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).

15.0 How do I determine the Limit of Detection for the 

alternative method?

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 three times the standard 

deviation, So, at the blank level. 

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-b04-001c-20_final.pdf. 
Page 56 of 68

Other Requirements and Information

16.0 How do I apply for approval to use an alternative test 

method?

16.1 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 report containing the information 

in Section 16.2. The request must be submitted to the 

Director, Air Quality Assessment Division, U.S. 

Environmental Protection Agency, C304-02, Research Triangle 

Park, NC 27711.

16.2 Field Validation Report. The field validation 

report must contain the information in 16.2.1 through 

16.2.8. 

16.2.1 Regulatory objectives for the testing, 

including a description of the reasons for the test, 

applicable emission limits, and a description of the source.

16.2.2 Summary of the results and calculations shown 

in Sections 6.0 through 16, as applicable.

16.2.3 Analyte certification and value(s).

16.2.4 Discussion of laboratory evaluations.
Page 57 of 68

16.2.5 Discussion of field sampling.

16.2.6 Discussion of sample preparations and analysis.

16.2.7 Storage times of samples (and extracts, if 

applicable).

16.2.8 Reasons for eliminating any results.

17.0 How do I request a waiver?

17.1 Conditions for Waivers. If you meet one of the 

criteria in 17.1.1 through 17.1.2, 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.

17.1.1 Similar Sources. If the alternative test 

method that you want to use has been validated at another 

source and you can demonstrate to the Administrator=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 
Page 58 of 68

as described in 14.0.

17.1.2 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. 

17.2 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, Air Quality Assessment Division, 

U.S. Environmental Protection Agency, C304-02, Research 

Triangle Park, NC 27711. 

17.3 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 17.3.1 

through 17.3.4. The Administrator may request additional 

information if necessary to determine whether this method 

can be waived for a particular application. 
Page 59 of 68

17.3.1 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.

17.3.2 Summaries 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.

17.3.3 Ruggedness Testing Results. You must submit 

results of ruggedness testing conducted according to Section

14.0, sample stability conducted according to Section 7.0, 

and detection limits conducted according to Section 15.0, 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. 

17.3.4 Applicability Statement and Basis for Waiver 

Approval. Discussion of the applicability statement and 

basis for approval of the waiver. This discussion should 

address as applicable the following: applicable regulation, 
Page 60 of 68

emission standards, effluent characteristics, and process 

operations.

18.0 Where can I find additional information?

You can find additional information in the references 

in Sections 18.1 through 18.16.

18.1 Albritton, J.R., G.B. Howe, S.B. Tompkins, R.K.M. 

Jayanty, and C.E. Decker. 1989. Stability of Parts-PerMillion 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.

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

“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 
Page 61 of 68

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.

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.

18.7 Maxwell, E.A. 1974. Estimating variances from 

one or two measurements on each sample. Amer. Statistician 

28:96-97.

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

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

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

to evaluate performance of stationary source test methods. 
Page 62 of 68

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

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

design of optimum multifactorial experiments. Biometrika, 

33:305.

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

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

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.

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 (MD-77), 

Research Triangle Park, NC 27711.

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), 
Page 63 of 68

Research Triangle Park, NC 27711. 

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 64 of 68

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).
Page 65 of 68

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

Tailed 95 Percent Confidence Limit

Degrees of freedom t95

1 12.706

2 4.303

3 3.182

4 2.776

5 2.571

6 2.447

7 2.365

8 2.306

9 2.262

10 2.228
Page 66 of 68

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 within 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 within 

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) within 

seven days and proposed 

maximum storage times

or two weeks after the 

initial analysis. This 

will allow analysis of 

extract storage 

impacts.

sorbent 

sampling 

systems that 

require thermal 

desorption

analyze six samples 

within seven days. 

Analyze another set of 

six samples at the 

proposed maximum 

storage time or within 

two weeks of the 

initial analysis.
Page 67 of 68

Table 3 of Appendix A. Storage and Sampling Procedures 

for Stack Test Emissions

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

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) within 

seven days and half of 

the samples (8 or 9) at 

the proposed maximum 

storage time or within 

two weeks of the 

initial analysis.

sorbent and 

impinger 

sampling 

systems that 

require 

extraction or 

digestion

extract or digest six 

of the samples within 

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) within 

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.
Page 68 of 68

Table 4 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 estimated 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, S1, of the 

measured values.

Calculate the standard 

deviation (S2 and S3) for 

each concentration level.

Calculate the LOD0 (referred 

to as the calculated LOD)as 

3 times S1, where S0 = S1.

Plot the standard deviations 

of the three test standards 

(S1, S2 and S3) as a function 

of concentration.

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 LOD0 (referred 

to as the calculated LOD)as 

3 times So.