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[Federal Register Volume 76, Number 96 (Wednesday, May 18, 2011)]
[Rules and Regulations]
[Pages 28664-28675]
From the Federal Register Online via the Government Printing Office [www.gpo.gov]
[FR Doc No: 2011-12058]

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ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63

[OAR-2004-0080, FRL-9306-8]
RIN 2060-AF00

Method 301--Field Validation of Pollutant Measurement Methods 
From Various Waste Media

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule.

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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. The revised 
Method 301 is more flexible, less expensive, and easier to use. This 
action finalizes amendments to Method 301 after considering comments 
received on the proposed rule published in the Federal Register on 
December 22, 2004.

DATES: This final rule is effective on May 18, 2011.

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 in the 
http://www.regulations.gov index. Although listed in the index, some 
information is not publicly available, e.g., confidential business 
information (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 at 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 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 Percent Confidence 
Limit
    I. Paired Sampling Procedure
    J. Standard Deviation
V. Statutory and Executive Order Reviews
    A. Executive Order 12866--Regulatory Planning and Review and 
Executive Order 13563--Improving Regulation and Regulatory 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

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. A redline strikeout

[[Page 28665]]

document that compares this final rule to the proposed rule has also 
been added to the docket.

C. Judicial Review

    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 
United States Court of Appeals for the District of Columbia Circuit by 
July 18, 2011. Under section 307(d)(7)(B) of the CAA, only an objection 
to this final rule that was raised with reasonable specificity during 
the period for public comment can be raised during judicial review. 
Moreover, under section 307(b)(2) of the CAA, the requirements 
established by this action may not be challenged separately in civil or 
criminal proceedings brought by EPA 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 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.

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 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

    Two 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 required to be compared against 
a true value, usually a traceable standard. 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, EPA should allow it. 
We agree with the commenter. We have approved methods demonstrated with 
sequential sampling 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 
party's 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 well-established 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, 
EPA promulgated a rule on September 13, 2010 (75 FR 55636), 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

[[Page 28666]]

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 t-statistic. 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 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 from 
24 hours to 48 to 72 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 percent to  10 percent and concurrently to eliminate the requirement for 
correcting all data collected with the method. We provided that we 
believe that 12 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 percent to  10 percent is too stringent. 
One 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 percent 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 was 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 percent and 30 percent.
    We proposed to change the acceptance criteria for method precision 
when using analyte spiking from  50 percent to  
20 percent. In addition, we proposed to eliminate the 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 percent 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 PLQ with a 
procedure to determine the 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 Federal Advisory Committee Act (FACA) Committee to consider 
alternative approaches to similar procedures they proposed (40 CFR part 
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 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 to not 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.
    A few commenters requested that the calculation 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 
the standard deviation at zero concentration (S0) in Table 4 
needs 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

[[Page 28667]]

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 percent 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 percent, but this is often truncated to 99 percent.
    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. Estimate the 
standard deviation of these seven samples, and call it S1.
    (2) Define LOD0 = 3S1.
    (3) If LOD10, 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 Percent Confidence Limit

    Two commenters provided that the values of t for the two-tailed 95 
percent confidence limit are wrong since they reflected an 80 percent 
confidence limit and there are some apparent typesetting errors. We 
corrected these values to reflect the 95 percent confidence limit and 
eliminated the typesetting errors in the final method.

I. Paired Sampling Procedure

    Two 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 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 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 and Executive 
Order 13563--Improving Regulation and Regulatory Review

    This action is not a ``significant regulatory action'' under the 
terms of Executive Order 12866 (58 FR 51735, October 4, 1993) and is 
therefore not subject to review under Executive Orders 12866 and 13563 
(76 FR 3821, January 21, 2011).

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 this final action. This final rule amends Method 301 which may 
be used to validate test data or a new test method.

C. Regulatory Flexibility Analysis

    The Regulatory Flexibility Act (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 statute 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 as defined 
by the Small Business Administration's (SBA) regulations at 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; and (3) a small organization that is 
any not-for-profit enterprise that is independently owned and operated 
and is not dominant in its field.
    After considering the economic impacts of this 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 will 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. Any small entity choosing to use Method 301 to validate a 
new or

[[Page 28668]]

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 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 final 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

    EPA interprets EO 13045 (62 FR 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 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 action involves technical standards. While EPA 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-test explicitly to test the precision 
of an alternative method, but instead states that 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 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 May 18, 2011.

List of Subjects in 40 CFR Part 63

    Environmental protection, Alternative test method, Air pollution 
control, Field validation, Hazardous air pollutants, Method 301.

    Dated: May 10, 2011.
Lisa P. Jackson,
Administrator.
    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]

0
1. The authority citation for part 63 continues to read as follows:

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

0
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.

[[Page 28669]]

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

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?

    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 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 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 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 Sections 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 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 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 Sections 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

[[Page 28670]]

introduced as close to the tip of the sampling train as possible.
    6.3.2 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 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 
must 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 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 cross-sectional area of the probe tip configuration is 
approximately five percent or more of the stack or duct cross-
sectional area.

7.0 How do I ensure sample stability?

    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 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 Section 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.002

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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.003

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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.004

Where:

n = 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 t-value is less than the 
critical value, the difference is not 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 Section 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 percent without the use of 
correction factors, and no more than  30 percent 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 
greater than 20 percent but less than 50

[[Page 28671]]

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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.005

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.

    10.2 Standard Deviation. Calculate the standard deviation of the 
Si values according to Equation 301-5.
[GRAPHIC] [TIFF OMITTED] TR18MY11.006

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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.007

    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 11 degrees of freedom. If the calculated t-value is less 
than 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.008

Where:

BR = Relative bias.

    If the relative bias is less than or equal to ten 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.009

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 the mean of 
the differences between the alternative test method and the validated 
method (dm). Calculate di according to Equation 
301-9.
[GRAPHIC] [TIFF OMITTED] TR18MY11.010

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.
2i = 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. Compare the calculated t-statistic with the critical 
value of the t-

[[Page 28672]]

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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.011

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 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.012

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.

    11.2.2 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.013

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 percent 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 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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.014

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 value 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 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 two-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.
[GRAPHIC] [TIFF OMITTED] TR18MY11.015

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 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 Section 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 Section 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

[[Page 28673]]

by changing several variables 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., use the minimum 
detectable concentration (MDC) and not the LOD) available at http://www.epa.gov/radiation/docs/marlap/402-b-04-001c-20_final.pdf.

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 Sections 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.
    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 
Sections 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 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 as 
described in Section 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 Sections 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.
    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. 
Your discussion of the applicability statement and basis for 
approval of the waiver should address the following as applicable: 
Applicable regulation, 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-Per-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.
    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 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. 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

[[Page 28674]]

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), 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. Statistical Manual of the Association of Official Analytical 
Chemists, Association of Official Analytical Chemists, Washington, 
DC, 1975, pp. 33-36.

               Table 1 of Appendix A--Sampling Procedures
------------------------------------------------------------------------
       If you are . . .                  You must collect . . .
------------------------------------------------------------------------
comparing against a validated  9 sets of replicate samples using a
 method.                        paired sampling system (a total of 18
                                samples) or 4 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    a total of 12 replicate samples. You may
 only be used for procedures    collect the samples either by obtaining
 requiring mass spectrometry).  6 sets of paired samples or 3 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).
------------------------------------------------------------------------

    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
------------------------------------------------------------------------

  Table 3 of Appendix A--Storage and Sampling Procedures for Stack Test
                                Emissions
------------------------------------------------------------------------
      If you are . . .             With . . .        Then you must . . .
------------------------------------------------------------------------
using isotopic or analyte     sample container      analyze 6 of the
 spiking procedures.           (bag or canister)     samples within 7
                               and impinger          days and then
                               sampling systems.     analyze the same 6
                                                     samples at the
                                                     proposed maximum
                                                     storage time or 2
                                                     weeks after the
                                                     initial analysis.
                              sorbent and impinger  extract or digest 6
                               sampling systems      of the samples
                               that require          within 7 days and
                               extraction or         extract or digest 6
                               digestion.            other samples at
                                                     the proposed
                                                     maximum storage
                                                     time or 2 weeks
                                                     after the first
                                                     extraction or
                                                     digestion. Analyze
                                                     an aliquot of the
                                                     first 6 extracts
                                                     (digestates) within
                                                     7 days and proposed
                                                     maximum storage
                                                     times or 2 weeks
                                                     after the initial
                                                     analysis. This will
                                                     allow analysis of
                                                     extract storage
                                                     impacts.
                              sorbent sampling      analyze 6 samples
                               systems that          within 7 days.
                               require thermal       Analyze another set
                               desorption.           of 6 samples at the
                                                     proposed maximum
                                                     storage time or
                                                     within 2 weeks of
                                                     the initial
                                                     analysis.
comparing an alternative      sampling method that  analyze half of the
 test method against a         does not include      samples (8 or 9)
 validated test method.        sorbent and           within 7 days and
                               impinger sampling     half of the samples
                               systems that          (8 or 9) at the
                               require extraction    proposed maximum
                               or digestion.         storage time or
                                                     within 2 weeks of
                                                     the initial
                                                     analysis.
                              sorbent and impinger  extract or digest 6
                               sampling systems      of the samples
                               that require          within 7 days and
                               extraction or         extract or digest 6
                               digestion.            other samples at
                                                     the proposed
                                                     maximum storage
                                                     time or within 2
                                                     weeks of the first
                                                     extraction or
                                                     digestion. Analyze
                                                     an aliquot of the
                                                     first 6 extracts
                                                     (digestates) within
                                                     7 days and at the
                                                     proposed maximum
                                                     storage times or
                                                     within 2 weeks of
                                                     the initial
                                                     analysis. This will
                                                     allow analysis of
                                                     extract storage
                                                     impacts.
------------------------------------------------------------------------

[[Page 28675]]

                               Table 4 of Appendix A--Procedures for Estimating So
----------------------------------------------------------------------------------------------------------------
 
----------------------------------------------------------------------------------------------------------------
If the estimated LOD (LOD1, expected approximate LOD     If the estimated LOD (LOD1, expected approximate LOD
 concentration level) is no more than twice the           concentration level) is greater than twice the
 calculated LOD, use Procedure I as follows. Estimate     calculated LOD, use Procedure II as follows. Prepare
 the LOD (LOD1) and prepare a test standard at this       two additional standards (LOD2 and LOD3) at
 level. The test standard could consist of a dilution     concentration levels lower than the standard used in
 of the analyte described in Section 5.0.                 Procedure I (LOD1).
Using the normal sampling and analytical procedures for  Sample and analyze each of these standards (LOD2 and
 the method, sample and analyze this standard at least    LOD3) at least 7 times.
 7 times in the laboratory.
Calculate the standard deviation, S1, of the measured    Calculate the standard deviation (S2 and S3) for each
 values.                                                  concentration level.
Calculate the LOD0 (referred to as the calculated LOD)   Plot the standard deviations of the three test
 as 3 times S1, where S0 = S1.                            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.
----------------------------------------------------------------------------------------------------------------

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[FR Doc. 2011-12058 Filed 5-17-11; 8:45 am]
BILLING CODE 6560-50-P
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