[Federal Register Volume 83, Number 54 (Tuesday, March 20, 2018)]
[Rules and Regulations]
[Pages 12118-12133]
[FR Doc No: 2018-05400]

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ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63

[EPA-HQ-OAR-2016-0069; FRL-9975-62-OAR]
RIN 2060-AT17

Revisions to 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: The Environmental Protection Agency (EPA) is publishing
editorial and technical revisions to the EPA's Method 301 ``Field
Validation of Pollutant Measurement Methods from Various Waste Media''
to correct and update the method. In addition, the EPA is clarifying
the regulatory applicability of Method 301 as well as its suitability
for use with other regulations. The revisions include ruggedness
testing for validation of test methods intended for application at
multiple sources, determination of the limit of detection for all
method validations, incorporating procedures for determining the limit
of detection, revising the sampling requirements for the method
comparison procedure, adding storage and sampling procedures for
sorbent sampling systems, and clarifying acceptable statistical results
for candidate test methods. We are also clarifying the applicability of
Method 301 to our regulations and adding equations to clarify
calculation of the correction factor, standard deviation, estimated
variance of a validated test method, standard deviation of differences,
and t-statistic for all validation approaches. We have also made minor
changes in response to public comments. Changes made to the Method 301
field validation protocol under this action apply only to methods
submitted to the EPA for approval after the effective date of this
final rule.

DATES: The final rule is effective on March 20, 2018.

ADDRESSES: We have established a docket for this rulemaking under
Docket ID Number EPA-HQ-OAR-2016-0069. All documents in the docket are
listed on the https://www.regulations.gov website. 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 electronically through https://www.regulations.gov.

FOR FURTHER INFORMATION CONTACT: Ms. Robin Segall, Office of Air
Quality Planning and Standards, Air Quality Assessment Division (E143-
02), Environmental Protection Agency, Research Triangle Park, NC 27711;
telephone number:<PHONE_NUMBER>; fax number:<PHONE_NUMBER>; email
address: [email protected].

SUPPLEMENTARY INFORMATION: The information in this preamble is
organized as follows:

Table of Contents

I. General Information
    A. Does this action apply to me?
    B. Where can I get a copy of this document and other related
information?
    C. Judicial Review and Administrative Reconsideration
II. Background
III. Summary of Final Amendments
    A. Technical Revisions
    B. Clarifying and Editorial Changes
IV. Response to Comment
V. Statutory and Executive Order Reviews
    A. Executive Order 12866: Regulatory Planning and Review and
Executive Order 13563: Improving Regulation and Regulatory Review
    B. Executive Order 13771: Reducing Regulations and Controlling
Regulatory Costs
    C. Paperwork Reduction Act (PRA)
    D. Regulatory Flexibility Act (RFA)
    E. Unfunded Mandates Reform Act (UMRA)
    F. Executive Order 13132: Federalism
    G. Executive Order 13175: Consultation and Coordination With
Indian Tribal Governments
    H. Executive Order 13045: Protection of Children From
Environmental Health Risks and Safety Risks
    I. Executive Order 13211: Actions That Significantly Affect
Energy Supply, Distribution, or Use
    J. National Technology Transfer and Advancement Act (NTTAA) and
1 CFR Part 51
    K. Executive Order 12898: Federal Actions To Address
Environmental Justice in Minority Populations and Low-Income
Populations
    L. Congressional Review Act (CRA)

I. General Information

A. Does this action apply to me?

    Method 301 applies to you, under 40 CFR 63.7(f) or 40 CFR
65.158(a)(2)(iii), when you want to use an alternative to a required
test method to meet an applicable requirement or when there is no
required or validated test method. In addition, the validation
procedures of Method 301 may be used as a tool for demonstration of the
suitability of alternative test methods under 40 CFR 59.104 and 59.406,
40 CFR 60.8(b), and 40 CFR 61.13(h)(1)(ii). If you have questions
regarding the applicability of the changes to Method 301, contact the
person listed in the preceding FOR FURTHER INFORMATION CONTACT section.

B. Where can I get a copy of this document and other related
information?

    In addition to being available in the docket, an electronic copy of
the method revisions is available on the Air Emission Measurement
Center (EMC) website at https://www.epa.gov/emc/. The EMC provides
information regarding stationary source air emissions test methods and
procedures.

C. Judicial Review and Administrative Reconsideration

    Under Clean Air Act (CAA) section 307(b)(1), judicial review of
this final action is available only by filing a petition for review in
the United States Court of Appeals for the District of Columbia Circuit
by May 21, 2018. Under CAA section 307(b)(2), the requirements
established by these final rules may not be challenged separately in
any civil or criminal proceedings brought by the EPA to enforce the
requirements.
    Section 307(d)(7)(B) of the CAA provides that ``[o]nly an objection
to a rule or procedure which was raised with reasonable specificity
during the period for public comment (including any public hearing) may
be raised during judicial review.'' This section also provides a
mechanism for the EPA to reconsider the rule ``[i]f the person raising
an objection can demonstrate to the Administrator that it was
impracticable to raise such objection within [the period for public
comment] or if the grounds for such objection arose after the period
for public comment (but within the time specified for judicial review)
and if such objection is of central relevance to the outcome of the
rule.'' Any person seeking to make such a demonstration should submit a

Petition for Reconsideration to the Office of the Administrator, U.S.
EPA, Room 3000, WJC Building, 1200 Pennsylvania Ave. NW, Washington, DC
20460, with a copy to both the person listed in the preceding FOR
FURTHER INFORMATION CONTACT section, and the Associate General Counsel
for the Air and Radiation Law Office, Office of General Counsel (Mail
Code 2344A), U.S. EPA, 1200 Pennsylvania Ave. NW, Washington, DC 20460.

II. Background

    The EPA proposed revisions to Method 301 on December 2, 2016 (81 FR
87003). The EPA received one comment letter on the proposed revisions
to EPA Method 301, which is addressed in Section IV of this preamble.
    The EPA originally published Method 301 (appendix A to 40 CFR part
63, Test Methods) on December 29, 1992 (57 FR 61970), as a field
validation protocol method to be used to validate new test methods for
hazardous air pollutants (HAP) in support of the Early Reductions
Program of part 63 when existing test methods were inapplicable. On
March 16, 1994, the EPA incorporated Method 301 into 40 CFR 63.7 (59 FR
12430) to provide procedures for validating a candidate test method as
an alternative to a test method specified in a standard or for use
where no test method is provided in a standard.
    Method 301 specifies procedures for determining and documenting the
bias and precision of a test method that is a candidate for use as an
alternative to a test method specified in an applicable regulation.
Method 301 has also been required for validating test methods to be
used in demonstrating compliance with a regulatory standard in the
absence of a validated test method. Method 301 is required for these
purposes under 40 CFR 63.7(f) and 40 CFR 65.158(a)(2)(iii), and is an
appropriate tool for demonstration and validation of alternative
methods under 40 CFR 59.104 and 59.406, 40 CFR 60.8(b), and 40 CFR
61.13(h)(1)(ii). The procedures specified in Method 301 are applicable
to various media types (e.g., sludge, exhaust gas, wastewater).
    Bias (or systemic error) is established by comparing measurements
made using a candidate test method against reference values, either
reference materials or a validated test method. Where needed, a
correction factor for source-specific application of the method is
employed to eliminate/minimize bias. This correction factor is
established from data obtained during the validation test. Methods that
have bias correction factors outside a specified range are considered
unacceptable. Method precision (or random error) must be demonstrated
to be as precise as the validated method for acceptance or less than or
equal to 20 percent when the candidate method is being evaluated using
reference materials.
    Neither the Method as originally established on December 29, 1992,
nor the subsequent revision on May 18, 2011 (76 FR 28664), have
distinguished requirements for single-source applications of a
candidate method from those that apply at multiple sources. The
revisions promulgated in this action recognize that requirements
related to bias and ruggedness testing should differ between single-
source and multiple-source application of an alternative method.
Additionally, through our reviews of submitted Method 301 data packages
and response to questions from industry, technology vendors, and
testing organizations seeking to implement the method, we recognized
that there was confusion with the specific testing requirements and the
statistical calculations associated with each of the three ``Sampling
Procedures.'' To improve the readability and application of Method 301,
we proposed and are finalizing minor edits throughout the method text
to clarify the descriptions and requirements for assessing bias and
precision for each ``Sampling Procedure'' and have added equations to
ensure that required calculations and acceptance criteria for each of
the three sampling approaches are clear.

III. Summary of Final Amendments

    In this section, we discuss the final amendments to Method 301, the
changes since proposal, and the rationale for the changes. We are
finalizing clarifications to the regulatory applicability of Method 301
and its suitability for use with other regulations, as well as
finalizing technical revisions and editorial changes intended to
clarify and update the requirements and procedures specified in Method
301.

A. Technical Revisions

1. Applicability of Ruggedness Testing and Limit of Detection
Determination
    In this action, we are amending sections 3.1 and 14.0 to require
ruggedness testing when using Method 301 to validate a candidate test
method intended for application to multiple sources. Ruggedness testing
is optional for validation of methods intended for single-source
applications. We are also amending sections 3.1 and 15.0 to require
determination of the limit of detection (LOD) for validation of all
methods (i.e., those intended for both single-source and multi-source
application). Additionally, we are clarifying the LOD definition in
section 15.1.
    Ruggedness testing of a test method is a laboratory study to
determine the sensitivity of the method by measuring its capacity to
remain unaffected by small, but deliberate variations in method
parameters such as sample collection rate and sample recovery
temperature to provide an indication of its reliability during normal
usage. Requiring ruggedness testing and determination of the LOD for
validation of a candidate test method that is intended for use at
multiple sources will further inform the EPA's determination of whether
the candidate test method is valid across a range of source emission
matrices, varying method parameters, and conditions. Additionally,
conducting an LOD determination for both single- and multi-source
validations will account for the sensitivity of the candidate test
method to ensure it meets applicable regulatory requirements.
2. Limit of Detection Procedures
    In this action, the EPA is finalizing revisions to the requirements
for determining the LOD specified in section 15.2 and Table 301-5
(Procedure I) of Method 301 to reference the procedures for determining
the method detection limit (MDL) in 40 CFR part 136, appendix B, as
revised on August 28, 2017 (82 FR 40836), which addresses laboratory
blank contamination and accounts for intra-laboratory variability.
Procedure I of Table 301-5 of Method 301 is used for determining an LOD
when an analyte in a sample matrix is collected prior to an analytical
measurement or the estimated LOD is no more than twice the calculated
LOD. For the purposes of Method 301, LOD will now be equivalent to the
calculated MDL determined using the procedures specified in 40 CFR part
136, appendix B.
    When EPA proposed revisions to Method 301 (81 FR 87003; December 2,
2016), we noted in the preamble that the Method 301 revisions were
referencing proposed revisions to the MDL calculation procedures of 40
CFR part 136, appendix B. At that time, we stated, ``If the revisions
to 40 CFR part 136, appendix B are finalized as proposed prior to a
final action on this [Method 301] proposal, we will cross-reference
appendix B. If appendix B is finalized before this action and the

revisions do not incorporate the procedures as described above, the EPA
intends to incorporate the specific procedures for determining the LOD
in the final version of Method 301 consistent with this proposal.'' The
appendix B provisions of 40 CFR part 136 were recently finalized with
the Clean Water Act Methods Update Rule on August 28, 2017 (82 FR
40836). As a result of comments on the proposed Methods Update rule,
there were minor clarifications, but ``[n]o significant revisions were
made to the proposed MDL procedure'' of appendix B as stated in Section
III.I of the preamble to that rule. Because the Methods Update rule
containing the MDL procedure was finalized with no significant changes,
and we have determined that the final requirements of appendix B are
appropriate for the CAA programs at issue, we are cross-referencing the
finalized MDL determination calculation procedure of 40 CFR part 136,
appendix B, in section 15.2 and Table 301-5 of Method 301.
3. Storage and Sampling Procedures
    In this action, we are finalizing the proposed revisions to
sections 9.0 and 11.1.3 and Table 301-1 of Method 301 to require, at a
minimum, six sets of quadruplicate samples (a total of 24 samples) for
comparison of a candidate method against a validated method rather than
four sets of quadruplicate samples or nine sets of paired samples, as
currently required. These revisions ensure that the bias and precision
requirements are consistent between the various sampling approaches in
the method and decreases the amount of uncertainty in the calculations
for bias and precision when comparing an alternative or candidate test
method with a validated method. Bias and precision (standard deviation
and variance) are inversely related to the number of sampling trains
(sample results) used to estimate the difference between the
alternative test method and the validated method. As the number of
trains increases, the uncertainty in the bias and precision estimates
decreases. Larger data sets provide better estimates of the standard
deviation or variance and the distribution of the data. The revision to
collect a total of 24 samples when using the comparison against a
validated method approach is also consistent with the number of samples
required for both the analyte spiking and the isotopic spiking
approaches. The 12 samples collected when conducting the isotopic
spiking approach are equivalent to the 24 samples collected using the
analyte spiking approach because the isotopic labelling of the spike
allows each of the 12 samples to yield two results (one result for an
unspiked sample, and one result for a spiked sample).
    For validations conducted by comparing the candidate test method to
a validated test method, we are also finalizing the following
additions: (1) Storage and sampling procedures for sorbent systems
requiring thermal desorption to Table 301-2 of Method 301, and (2) a
new Table 301-4 of Method 301 to provide a look-up table of F values
for the one-sided confidence level used in assessing the precision of
the candidate test method. We also are amending the reference list in
section 18.0 to include the source of the F values in Table 301-4.
4. Bias Criteria for Multi-Source Versus Single-Source Validation
    In this action, we are finalizing revisions that clarify sections
8.0, 10.3, and 11.1.3 of Method 301 to specify that candidate test
methods intended for use at multiple sources must have a bias less than
or equal to 10 percent. Candidate test methods with a bias greater than
10 percent, but less than 30 percent, are applicable only at the source
at which the validation testing was conducted, and data collected in
the future must be adjusted for bias using a source-specific correction
factor. A single-source correction factor is not appropriate for use at
multiple sources. This change provides flexibility for source-specific
Method 301 application while limiting the acceptance criteria for use
of the method at multiple sources.
5. Relative Standard Deviation Assessment
    In sections 9.0 and 12.2 of Method 301, we are finalizing language
regarding the interpretation of the relative standard deviation (RSD)
when determining the precision of a candidate test method using the
analyte spiking or isotopic spiking procedures. For a test method to be
acceptable, we proposed that the RSD of a candidate test method must be
less than or equal to 20 percent. Accordingly, we are removing the
sampling provisions for cases where the RSD is greater than 20 percent,
but less than 50 percent. Poor precision makes it difficult to detect
potential bias in a test method. For this reason, we proposed and are
now finalizing an acceptance criterion of less than or equal to 20
percent for analyte and isotopic spiking sampling procedures.
6. Applicability of Method 301
    Although 40 CFR 65.158(a)(2)(iii) specifically cross-references
Method 301, Method 301 formerly did not reference part 65. For parts 63
and 65, Method 301 must be used for establishing an alternative test
method. Thus, in this action, we are finalizing language that clarifies
that Method 301 is applicable to both parts 63 and 65 and that Method
301 may be used for validating alternative test methods under the
following parts of Title 40 of the CAA:
     Part 59 (National Volatile Organic Compound Emission
Standards for Consumer and Commercial Products).
     Part 60 (Standards of Performance for New Stationary
Sources).
     Part 61 (National Emission Standards for Hazardous Air
Pollutants).
    We believe that the Method 301 procedures for determining bias and
precision provide a suitable technical approach for assessing candidate
or alternative test methods for use under these regulatory parts
because the testing provisions are very similar to those under parts 63
and 65. To accommodate the expanded applicability and suitability, we
are revising the references in sections 2.0, 3.2, 5.0, 13.0, 14.0, and
16.1 of Method 301 to refer to all five regulatory parts.
7. Equation Additions
    In this action, we are clarifying the procedures in Method 301 by
adding the following equations:
     Equation 301-8 in section 10.3 for calculating the
correction factor.
     Equation 301-11 in section 11.1.1 and Equation 301-19 in
section 12.1.1 for calculating the numerical bias.
     Equation 301-12 in section 11.1.2 and Equation 301-20 in
section 12.1.2 for determining the standard deviation of differences.
     Equation 301-13 in section 11.1.3 and Equation 301-21 in
section 12.1.3 for calculating the t-statistic.
     Equation 301-15 in section 11.2.1 to estimate the variance
of the validated test method.
     Equation 301-23 in section 12.2 for calculating the
standard deviation.
    We also are revising the denominator of Equation 301-22 to use the
variable ``CS'' rather than ``VS.'' Additionally, we are revising the
text of Method 301, where needed, to list and define all variables used
in the method equations. These changes are intended to improve the
readability of the method and ensure that required calculations and
acceptance criteria for each of the three validation approaches in
Method 301 are clear.

B. Clarifying and Editorial Changes

    In this action, we are applying minor edits throughout the text of
Method 301 to clarify the descriptions and

requirements for assessing bias and precision, to ensure consistency
when referring to citations within the method, to renumber equations
and tables (where necessary), and to remove passive voice.
    In addition, we are clarifying several definitions in section 3.2.
In the definition of ``Paired sampling system,'' we are modifying the
definition to provide that a paired sampling system is collocated with
respect to sampling time and location. For the definition of
``Quadruplet sampling system,'' we are replacing the term
``Quadruplet'' with ``Quadruplicate'' and adding descriptive text to
the definition to provide examples of replicate samples. We are also
making companion edits throughout the method text to reflect the change
in terminology from ``quadruplet'' to ``quadruplicate.'' Additionally,
we are revising the definition of ``surrogate compound'' to clarify
that a surrogate compound must be distinguishable from other compounds
being measured by the candidate method.
    We are also replacing the term ``alternative test method'' with
``candidate test method'' in section 3.2 and throughout Method 301 to
maintain consistency when referring to a test method that is subject to
the validation procedures specified in Method 301.
    Additionally, the EPA is making the following updates and
corrections:
     Updating the address for submitting waivers in section
17.2.
     Correcting the t-value for four degrees of freedom in
Table 301-3 ``Critical Values of t'' as well as expanding the table to
include t-values up to 20 degrees of freedom. We originally proposed
expanding the table to only 11 degrees of freedom, but recognized that
users may occasionally want to use significantly more than the minimum
number of test runs and samples.
     Including a Table 301-4 ``Upper Critical Values of the F
Distribution'' and an associated reference in section 18.0 to provide
method users with convenient access to the F values needed to perform
the required statistical calculations in Method 301. For the same
reason that we originally included the Table 301-3 ``Critical Values of
t'' in the 2011 revisions to Method 301, we recognized in finalizing
the proposed revisions that we should additionally include a table for
the F distribution.

IV. Response to Comment

    We received one public comment letter submitted on behalf of the
Utility Air Regulatory Group presenting two comments.
    Comment: The commenter notes that section 6.4.1 of Method 301
requires that the probe tips for each of the paired sampling probes be
2.5 centimeters away from each other with a pitot tube on the outside
of each probe and claims that the collocation criteria of Method 301
are infeasible for many currently accepted test methods including
Method 30B. The commenter states that if the outside diameter of the
validated test method probe is 3 inches (as is common for Method 30B
probes), it is impossible for a second probe of equal diameter to meet
the probe tip location requirement even if the two probes are
immediately adjacent. In addition, the commenter claims that if the
sample port being used to perform the validation testing has an inside
diameter of 4 inches, a common port size, then two paired sampling
probes with an outside diameter of 3 inches cannot physically fit into
the sample port making collocation impossible. The commenter notes that
sections 6.4.1 and 17.1 provide for some latitude for waivers of the
probe placement requirements, but believes the waiver language is
inadequate and recommends that EPA provide alternative probe placements
that are practically achievable.
    Response: We recommend that organizations conducting validation
testing seek to use 6-inch ports, which are fairly common. Should 6-
inch ports not be available at a source where validation testing must
be conducted, then they should be installed if practicable. However, we
recognize that there still may be instances where the sampling probes
requirements are not feasible in a specific situation. Current Method
301 addresses this situation by providing in section 6.4.1 for
Administrator approval of a validation request with other paired
arrangements for the pitot tube. While we do not agree with the
commenter that EPA should provide alternative probe tip and pitot tube
placement options within Method 301, we do appreciate that the
Administrator approval language provided in the method could confirm
additional flexibility with regard to both pitot tube and probe tip
placement and we have revised the language of section 6.4.1 and
relocated it to section 6.4 to clarify that it is applicable to all
aspects of sampling probe/pitot placement.
    Comment: The commenter points out that section 8.0 of Method 301
specifies the bias of a candidate method as compared to a reference
method be no more than 10 percent. The commenter contends this
criterion is inadequate and unachievable at low concentrations, which
are now more frequently occurring, and recommends that the Method 301
bias criterion be modified to include an alternative performance
criterion based on an absolute difference rather than a percent of the
measurement to address field validation measurements made at low
levels.
    Response: The EPA disagrees with the commenter that the Method 301
bias criterion should be modified to include an alternative performance
criterion based on an absolute difference rather than a percent of the
measurement. It is important to understand that the 10 percent bias
criterion applies only to candidate methods that will be applied to
multiple sources. A candidate method to be applied to a single source
is allowed a bias up to 30 percent when coupled with a source-specific
bias correction factor if the bias exceeds 10 percent. Though we
recognize that emission levels are decreasing, when a candidate method
is being validated for broad applicability to multiple sources, there
is the opportunity to optimize field validation by conducting testing
at sources with relatively higher emissions. As Method 301 is designed
for validation of methods for many pollutants emitted from a large
range of source categories under many different rules, EPA believes it
would, at best, be extremely difficult to specify generic alternative
criteria for validation at low levels. Such issues are part of the
rationale for the flexibility under section 17.0 of Method 301; with
this language EPA maintains the ability to waive some or all the
procedures of Method 301 if it can be demonstrated to the
Administrator's satisfaction that the bias and precision of a candidate
method are suitable for the stated application. To clarify that these
provisions apply to all required facets of Method 301, we have revised
section 17.2 to include the LOD determination along with bias and
precision.

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 and was,
therefore, not submitted to the Office of Management and Budget (OMB)
for review.

B. Executive Order 13771: Reducing Regulations and Controlling
Regulatory Costs

    This action is not an Executive Order 13771 regulatory action
because this

action is not significant under Executive Order 12866.

C. Paperwork Reduction Act (PRA)

    This action does not impose an information collection burden under
the PRA. The revisions in this action to Method 301 do not add
information collection requirements, but make corrections and updates
to existing testing methodology.

D. Regulatory Flexibility Act (RFA)

    I certify that this action will not have a significant economic
impact on a substantial number of small entities under the RFA. This
action will not impose any requirements on small entities. In making
this determination, the impact of concern is any significant adverse
economic impact on small entities. An agency may certify that a rule
will not have a significant economic impact on a substantial number of
small entities if the rule relieves regulatory burden, has no net
burden or otherwise has a positive economic effect on the small
entities subject to the rule. The revisions to Method 301 do not impose
any requirements on regulated entities beyond those specified in the
current regulations and they do not change any emission standard. We
have therefore concluded that this action will have no net regulatory
burden for all directly regulated small entities.

E. Unfunded Mandates Reform Act (UMRA)

    This action does not contain any unfunded mandate of $100 million
or more as described in UMRA, 2 U.S.C. 1531-1538. The action imposes no
enforceable duty on any state, local, or tribal governments or the
private sector.

F. 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.

G. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments

    This action does not have tribal implications, as specified in
Executive Order 13175. This action corrects and updates the existing
procedures specified in Method 301. Thus, Executive Order 13175 does
not apply to this action.

H. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks

    The EPA interprets Executive Order 13045 as applying only to those
regulatory actions that concern environmental health or safety risks
that the EPA has reason to believe may disproportionately affect
children, per the definition of ``covered regulatory action'' in
section 2-202 of the Executive Order. This action is not subject to
Executive Order 13045 because it does not concern an environmental
health risk or safety risk.

I. Executive Order 13211: Actions That Significantly Affect Energy
Supply, Distribution, or Use

    This action is not subject to Executive Order 13211, because it is
not a significant regulatory action under Executive Order 12866.

J. National Technology Transfer and Advancement Act (NTTAA) and 1 CFR
part 51

    This action involves technical standards. The agency previously
identified ASTM D4855-97 (Standard Practice for Comparing Test Methods)
as being potentially applicable in previous revisions of Method 301,
but determined that the use of ASTM D4855-97 was impractical (section V
in 76 FR 28664, May 18, 2011).

K. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations

    The EPA believes that this action is not subject to Executive Order
12898 (59 FR 7629, February 16, 1994) because it does not establish an
environmental health or safety standard. This action makes corrections
and updates to an existing protocol for assessing the precision and
accuracy of alternative test methods to ensure they are comparable to
the methods otherwise required; thus, it does not modify or affect the
impacts to human health or the environment of any standards for which
it may be used.

L. Congressional Review Act (CRA)

    This action is subject to the CRA, and the EPA will submit a rule
report to each House of the Congress and to the Comptroller General of
the United States. This action is not a ``major rule'' as defined by 5
U.S.C. 804(2).

List of Subjects in 40 CFR Part 63

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

    Dated: March 8, 2018.
E. Scott Pruitt,
Administrator.

    For the reasons stated in the preamble, the EPA amends title 40,
chapter I of the Code of Federal Regulations 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 to part 63 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 What approval must I have to 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?

Determination of 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?
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 for the candidate
test method?

Other Requirements and Information

16.0 How do I apply for approval to use a candidate test method?
17.0 How do I request a waiver?
18.0 Where can I find additional information?
19.0 Tables.

Using Method 301

1.0  What is the purpose of Method 301?

    Method 301 provides a set of procedures for the owner or operator
of an affected source to validate a candidate test method as an
alternative to a required test method based on established precision
and bias criteria.

These validation procedures are applicable under 40 CFR part 63 or 65
when a test method is proposed as an alternative test method to meet an
applicable requirement or in the absence of a validated method.
Additionally, the validation procedures of Method 301 are appropriate
for demonstration of the suitability of alternative test methods under
40 CFR parts 59, 60, and 61. If, under 40 CFR part 63 or 60, you choose
to propose a validation method other than Method 301, you must submit
and obtain the Administrator's approval for the candidate validation
method.

2.0  What approval must I have to use Method 301?

    If you want to use a candidate test method to meet requirements in
a subpart of 40 CFR part 59, 60, 61, 63, or 65, you must also request
approval to use the candidate test method according to the procedures
in Section 16 of this method and the appropriate section of the part
(Sec.  59.104, Sec.  59.406, Sec.  60.8(b), Sec.  61.13(h)(1)(ii),
Sec.  63.7(f), or Sec.  65.158(a)(2)(iii)). You must receive the
Administrator's written approval to use the candidate test method
before you use the candidate test method to meet the applicable federal
requirements. In some cases, the Administrator may decide to waive the
requirement to use Method 301 for a candidate test method to be used to
meet a requirement under 40 CFR part 59, 60, 61, 63, or 65 in absence
of a validated test method. Section 17 of this method describes the
requirements for obtaining a waiver.

3.0  What does Method 301 include?

    3.1 Procedures. Method 301 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. Bias is established by comparing the results of sampling
and analysis against a reference value. Bias may be adjusted on a
source-specific basis using a correction factor and data obtained
during the validation test. Precision may be determined using a paired
sampling system or quadruplicate sampling system for isotopic spiking.
A quadruplicate sampling system is required when establishing precision
for analyte spiking or when comparing a candidate test method to a
validated method. If such procedures have not been established and
verified for the candidate test method, Method 301 contains procedures
for ensuring sample stability by developing sample storage procedures
and limitations and then testing them. Method 301 also includes
procedures for ruggedness testing and determining detection limits. The
procedures for ruggedness testing and determining detection limits are
required for candidate test methods that are to be applied to multiple
sources and optional for candidate test methods that are to be applied
at a single source.
    3.2 Definitions.
    Affected source means an affected source as defined in the relevant
part and subpart under Title 40 (e.g., 40 CFR parts 59, 60, 61, 63, and
65).
    Candidate test method means the sampling and analytical methodology
selected for field validation using the procedures described in Method
301. The candidate test method may be an alternative test method under
40 CFR part 59, 60, 61, 63, or 65.
    Paired sampling system means a sampling system capable of obtaining
two replicate samples that are collected as closely as possible in
sampling time and sampling location (collocated).
    Quadruplicate sampling system means a sampling system capable of
obtaining four replicate samples (e.g., two pairs of measured data, one
pair from each method when comparing a candidate test method against a
validated test method, or analyte spiking with two spiked and two
unspiked samples) that are collected as close as possible in sampling
time and sampling location.
    Surrogate compound means a compound that serves as a model for the
target compound(s) being measured (i.e., similar chemical structure,
properties, behavior). The surrogate compound can be distinguished by
the candidate test method from the compounds being analyzed.

4.0  How do I perform Method 301?

    First, you use a known concentration of an analyte or compare the
candidate test method against a validated test method to determine the
bias of the candidate test method. Then, you collect multiple,
collocated simultaneous samples to determine the precision of the
candidate test method. Additional procedures, including validation
testing over a broad range of concentrations over an extended time
period are used to expand the applicability of a candidate test method
to multiple sources. Sections 5.0 through 17.0 of this method describe
the procedures in detail.

Reference Materials

5.0  What reference materials must I use?

    You must use reference materials (a material or substance with one
or more properties that 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 59, 60, 61, 63, or 65 requires. If you want to expand the
applicable range of the candidate test method, you must conduct
additional test runs using analyte concentrations higher and lower than
the applicable emission limitation or the anticipated level of the
target analyte. You must obtain information about your analyte
according to the procedures in Sections 5.1 through 5.4 of this method.
    5.1 Exhaust Gas Test Concentration. You must obtain a known
concentration of each analyte from an independent source such as a
specialty gas manufacturer, specialty chemical company, or chemical
laboratory. You must also obtain the manufacturer's certification of
traceability, uncertainty, and stability for the analyte concentration.
    5.2 Tests for Other Waste Media. You must obtain the pure liquid
components of each analyte from an independent manufacturer. The
manufacturer must certify the purity, traceability, uncertainty, and
shelf life of the pure liquid components. You must dilute the pure
liquid components in the same type medium or matrix 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 compound that contains a
unique element (e.g., 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 concentration of the
isotopically-labeled analyte must be more than five times the
concentration of the naturally-occurring analyte.

Sampling Procedures

6.0  What sampling procedures must I use?

    You must determine bias and precision by comparison against a
validated test method using isotopic spiking or using analyte spiking
(or the equivalent). Isotopic spiking can only be

used with candidate test methods capable of measuring multiple isotopes
simultaneously such as test methods using mass spectrometry or
radiological procedures. You must collect samples according to the
requirements specified in Table 301-1 of this method. You must perform
the sampling according to the procedures in Sections 6.1 through 6.4 of
this method.
    6.1 Isotopic Spiking. Spike all 12 samples with isotopically-
labelled analyte at an analyte mass or concentration level equivalent
to the emission limitation or standard specified in the applicable
regulation. If there is no applicable emission limitation or standard,
spike the analyte at the expected level of the samples. Follow the
applicable spiking procedures in Section 6.3 of this method.
    6.2 Analyte Spiking. In each quadruplicate set, spike half of the
samples (two out of the four samples) with the analyte according to the
applicable procedure in Section 6.3 of this method. You should spike at
an analyte mass or concentration level equivalent to the emission
limitation or standard specified in the applicable regulation. If there
is no applicable emission limitation or standard, spike the analyte at
the expected level of the samples. Follow the applicable spiking
procedures in Section 6.3 of this method.
    6.3 Spiking Procedure.
    6.3.1 Gaseous Analyte with Sorbent or Impinger Sampling Train.
Sample the analyte being spiked (in the laboratory or preferably in the
field) at a mass or concentration that is approximately equivalent to
the applicable emission limitation or standard (or the expected sample
concentration or mass where there is no standard) for the time required
by the candidate test method, and then sample the stack gas stream for
an equal amount of time. The time for sampling both the analyte and
stack gas stream should be equal; however, you must adjust the sampling
time to avoid sorbent breakthrough. You may sample the stack gas and
the gaseous analyte at the same time. You must introduce the analyte as
close to the tip of the sampling probe 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
analyte mass or concentration to yield a concentration approximately
equivalent to the applicable emission limitation or standard (or the
expected sample concentration or mass where there is no standard).
Thus, the final concentration of the analyte in the sample container
would be approximately equal to the analyte concentration in the stack
gas plus the equivalent of the applicable emission standard (corrected
for spike volume). The volume amount of spiked gas must be less than 10
percent of the sample volume of the container.
    6.3.3 Liquid or Solid Analyte with Sorbent or Impinger Trains.
Spike the sampling trains with an amount approximately equivalent to
the mass or concentration in the applicable emission limitation or
standard (or the expected sample concentration or mass 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
must spike the sampling trains 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 analyte mass or concentration approximately equivalent to the
applicable emission limitation or standard in the subpart (or the
expected sample concentration or mass where there is no standard).
    6.4 Probe Placement and Arrangement for Stationary Source Stack or
Duct Sampling. To sample a stationary source, you must place the paired
or quadruplicate probes according to the procedures in this subsection.
You must place the probe tips in the same horizontal plane. Section
17.1 of Method 301 describes conditions for waivers. For example, the
Administrator may approve a validation request where other paired
arrangements for the probe tips or pitot tubes (where required) are
used.
    6.4.1 Paired Sampling Probes. For paired sampling probes, the first
probe tip should be 2.5 centimeters (cm) from the outside edge of the
second probe tip, with a pitot tube on the outside of each probe.
    6.4.2 Quadruplicate Sampling Probes. For quadruplicate 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 of the probe tips or two
pitot tubes, where required, with their location on either side of the
probe tip configuration. Section 17.1 of Method 301 describes
conditions for waivers. For example, 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 Sample Storage and Threshold Procedures. If the
candidate 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 candidate test method and you are
not required to conduct the procedures specified in Section 7.2 or 7.3
of this method. If the candidate test method does not include such
procedures, your candidate method must include 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 of
this method. The minimum duration between sample collection and storage
must be as soon as possible, but no longer than 72 hours after
collection of the sample. The maximum storage duration must not be
longer than 2 weeks.
    7.2 Storage and Sampling Procedures for Stack Test Emissions. You
must store and analyze samples of stack test emissions according to
Table 301-2 of this method. You may reanalyze the same sample at both
the minimum and maximum storage durations for: (1) Samples collected in
containers such as bags or canisters that are not subject to dilution
or other preparation steps, or (2) impinger samples not subjected to
preparation steps that would affect stability of the sample such as
extraction or digestion. For candidate test method samples that do not
meet either of these criteria, you must analyze one of a pair of
replicate samples at the minimum storage duration and the other
replicate at the proposed storage duration but no later than 2 weeks of
the initial analysis to identify the effect of storage duration on
analyte samples. If you are using the isotopic spiking procedure, then
you must analyze each sample for the spiked analyte and the native
analyte.
    7.3 Storage and Sampling Procedures for Testing Other Waste Media
(e.g., Soil/Sediment, Solid Waste, Water/Liquid). You must analyze one
of each pair of replicate samples (half the total samples) at the
minimum storage duration and the other replicate (other half of
samples) at the maximum storage duration or within 2 weeks of the
initial analysis to identify the effect of storage duration on analyte
samples. The minimum time period between collection and storage should
be as soon as possible, but no longer than 72 hours after collection of
the sample.
    7.4 Sample Stability. After you have conducted sampling and
analysis

according to Section 7.2 or 7.3 of this method, compare the results at
the minimum and maximum storage durations. Calculate the difference in
the results using Equation 301-1.
[GRAPHIC] [TIFF OMITTED] TR20MR18.000

Where:

di = Difference between the results of the ith
replicate pair of samples.
Rmini = Results from the ith replicate sample
pair at the minimum storage duration.
Rmaxi = Results from the ith replicate sample
pair at the maximum storage duration.

    For single samples that can be reanalyzed for sample stability
assessment (e.g., bag or canister samples and impinger samples that do
not require digestion or extraction), the values for Rmini
and Rmaxi will be obtained from the same sample rather than
replicate samples.
    7.4.1 Standard Deviation. Determine the standard deviation of the
paired samples using Equation 301-2.
[GRAPHIC] [TIFF OMITTED] TR20MR18.001

Where:

SDd = Standard deviation of the differences of the paired
samples.
di = Difference between the results of the ith
replicate pair of samples.
dm = 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 results at the minimum storage duration
and the results after the maximum storage duration 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] TR20MR18.002

Where:

t = t-statistic.
dm = The mean of the paired sample differences.
SDd = Standard deviation of the differences of the paired
samples.
n = Total number of paired samples.

    Compare the calculated t-statistic with the critical value of the
t-statistic from Table 301-3 of this method. If the calculated t-value
is less than the critical value, the difference is not statistically
significant. Therefore, the sampling, analysis, and sample storage
procedures ensure stability, and you may submit a request for
validation of the candidate 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
of this method with new samples using a shorter proposed maximum
storage duration or improved handling and storage procedures.

Determination of Bias and Precision

8.0  What are the requirements for bias?

    You must determine bias by comparing the results of sampling and
analysis using the candidate test method against a reference value. The
bias must be no more than 10 percent for the candidate test
method to be considered for application to multiple sources. A
candidate test method with a bias greater than 10 percent
and less than or equal to 30 percent can only be applied on
a source-specific basis at the facility at which the validation testing
was conducted. In this case, you must use a correction factor for all
data collected in the future using the candidate test method. If the
bias is more than 30 percent, the candidate test method is
unacceptable.

9.0  What are the requirements for precision?

    You may use a paired sampling system or a quadruplicate sampling
system to establish precision for isotopic spiking. You must use a
quadruplicate sampling system to establish precision for analyte
spiking or when comparing a candidate test method to a validated
method. If you are using analyte spiking or isotopic spiking, the
precision, expressed as the relative standard deviation (RSD) of the
candidate test method, must be less than or equal to 20 percent. If you
are comparing the candidate test method to a validated test method, the
candidate test method must be at least as precise as the validated
method as determined by an F test (see Section 11.2.2 of this method).

10.0  What calculations must I perform for isotopic spiking?

    You must analyze the bias, RSD, precision, and data acceptance for
isotopic spiking tests according to the provisions in Sections 10.1
through 10.4 of this method.
    10.1 Numerical Bias. Calculate the numerical value of the bias
using the results from the analysis of the isotopic spike in the field
samples and the calculated value of the spike according to Equation
301-4.

[GRAPHIC] [TIFF OMITTED] TR20MR18.003

Where:

B = Bias at the spike level.
Sm = Mean of the measured values of the isotopically-
labeled analyte in the samples.
CS = Calculated value of the isotopically-labeled spike level.

    10.2 Standard Deviation. Calculate the standard deviation of the
Si values according to Equation 301-5.
[GRAPHIC] [TIFF OMITTED] TR20MR18.004

Where:

SD = Standard deviation of the candidate test method.
Si = Measured value of the isotopically-labeled analyte
in the i\th\ field sample.
Sm = Mean of the measured values of the isotopically-
labeled analyte in the samples.
n = Number of isotopically-spiked samples.

    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 of this method and the numerical
bias determined in Section 10.1 of this method.
[GRAPHIC] [TIFF OMITTED] TR20MR18.005

Where:

t = Calculated t-statistic.
B = Bias at the spike level.
SD = Standard deviation of the candidate test method.
n = Number of isotopically spike samples.

    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 (see Table 301-3 of this method). When you conduct isotopic
spiking according to the procedures specified in Sections 6.1 and 6.3
of this method as required, this critical value is 2.201 for 11 degrees
of freedom. If the calculated t-value is less than or equal to 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] TR20MR18.006

Where:

BR = Relative bias.
B = Bias at the spike level.
CS = Calculated value of the spike level.

    If the relative bias is less than or equal to 10 percent, the bias
of the candidate test method is acceptable for use at multiple sources.
If the relative bias is greater than 10 percent but less than or equal
to 30 percent, and if you correct all data collected with the candidate
test method in the future for bias using the source-specific correction
factor determined in Equation 301-8, the candidate test method is
acceptable only for application to the source at which the validation
testing was conducted and may not be applied to any other sites. If
either of the preceding two cases applies, you may continue to evaluate
the candidate test method by calculating its precision. If not, the
candidate test method does not meet the requirements of Method 301.
[GRAPHIC] [TIFF OMITTED] TR20MR18.007

Where:

CF = Source-specific bias correction factor.
B = Bias at the spike level.
CS = Calculated value of the spike level.

    If the CF is outside the range of 0.70 to 1.30, the data and method
are considered unacceptable.
    10.4 Precision. Calculate the RSD according to Equation 301-9.

[GRAPHIC] [TIFF OMITTED] TR20MR18.008

Where:

RSD = Relative standard deviation of the candidate test method.
SD = Standard deviation of the candidate test method calculated in
Equation 301-5.
Sm = Mean of the measured values of the spike samples.

    The data and candidate 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 you are comparing a candidate test method to a validated method,
then you must analyze the data according to the provisions in this
section. If the data from the candidate test method fail either the
bias or precision test, the data and the candidate 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 candidate test method and the validated
method (dm). Calculate di according to Equation
301-10.
[GRAPHIC] [TIFF OMITTED] TR20MR18.009

Where:

di = Difference in measured value between the candidate
test method and the validated method for each quadruplicate sampling
train.
V1i = First measured value with the validated method in
the ith quadruplicate sampling train.
V2i = Second measured value with the validated method in
the ith quadruplicate sampling train.
P1i = First measured value with the candidate test method
in the ith quadruplicate sampling train.
P2i = Second measured value with the candidate test
method in the ith quadruplicate sampling train.

    Calculate the numerical value of the bias using Equation 301-11.
    [GRAPHIC] [TIFF OMITTED] TR20MR18.010

Where:

B = Numerical bias.
di = Difference between the candidate test method and the
validated method for the ith quadruplicate sampling train.
n = Number of quadruplicate sampling trains.

    11.1.2 Standard Deviation of the Differences. Calculate the
standard deviation of the differences, SDd, using Equation
301-12.
[GRAPHIC] [TIFF OMITTED] TR20MR18.011

Where:

SDd = Standard deviation of the differences between the
candidate test method and the validated method.
di = Difference in measured value between the candidate
test method and the validated method for each quadruplicate sampling
train.
dm = Mean of the differences, di, between the
candidate test method and the validated method.
n = Number of quadruplicate sampling trains.

    11.1.3 T Test. Calculate the t-statistic using Equation 301-13.
    [GRAPHIC] [TIFF OMITTED] TR20MR18.012

Where:

t = Calculated t-statistic.
dm = The mean of the differences, di, between
the candidate test method and the validated method.
SDd = Standard deviation of the differences between the
candidate test method and the validated method.
n = Number of quadruplicate sampling trains.

    For the procedure comparing a candidate test method to a validated
test method listed in Table 301-1 of this method, 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 (see Table 301-3 of this method). When six runs are conducted, as
specified in Table 301-1 of this method, the critical value of the t-
statistic is 2.571 for five degrees of freedom. If the calculated t-
value is less than or equal to 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 magnitude of the
relative bias using Equation 301-14.
[GRAPHIC] [TIFF OMITTED] TR20MR18.013

Where:

BR = Relative bias.
B = Bias as calculated in Equation 301-11.
VS = Mean of measured values from the validated method.

    If the relative bias is less than or equal to 10 percent, the bias
of the candidate test method is acceptable. On a source-specific basis,
if the relative bias is greater than 10 percent but less than or equal
to 30 percent, and if you correct all data collected in the future with
the candidate test method for the bias using the correction factor, CF,
determined in Equation 301-8 (using VS for CS), the bias of the
candidate test method is acceptable for application to the source at
which the validation testing was conducted. If either of the preceding
two cases applies, you may continue to evaluate the candidate test
method by calculating its precision. If not, the candidate test method
does not meet the requirements of Method 301.
    11.2 Precision. Compare the estimated variance (or standard
deviation) of the candidate test method to that of the validated test
method according to Sections 11.2.1 and 11.2.2 of this method. If a
significant difference is determined using the F test, the candidate
test method and the results are rejected. If the F test does not show a
significant difference, then the candidate test method has acceptable
precision.
    11.2.1 Candidate Test Method Variance. Calculate the estimated
variance of the candidate test method according to Equation 301-15.
[GRAPHIC] [TIFF OMITTED] TR20MR18.014

Where:

p = Estimated variance of the candidate test method.
di = The difference between the ith pair of
samples collected with the candidate test method in a single
quadruplicate train.
n = Total number of paired samples (quadruplicate trains).

    Calculate the estimated variance of the validated test method
according to Equation 301-16.
[GRAPHIC] [TIFF OMITTED] TR20MR18.015

Where:

v = Estimated variance of the validated test method.
di = The difference between the ith pair of
samples collected with the validated test method in a single
quadruplicate train.
n = Total number of paired samples (quadruplicate trains).

    11.2.2 The F test. Determine if the estimated variance of the
candidate test method is greater than that of the validated method by
calculating the F-value using Equation 301-17.
[GRAPHIC] [TIFF OMITTED] TR20MR18.016

Where:

F = Calculated F value.
p = The estimated variance of the candidate test method.
v = The estimated variance of the validated method.

    Compare the calculated F value with the one-sided confidence level
for F from Table 301-4 of this method. The upper one-sided confidence
level of 95 percent for F(6,6) is 4.28 when the procedure
specified in Table 301-1 of this method for quadruplicate sampling
trains is followed. If the calculated F value is greater than the
critical F value, 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, which is defined as the mean of
the differences between the spiked samples and the unspiked samples in
each quadruplicate sampling train minus the spiked amount, using
Equation 301-18.
[GRAPHIC] [TIFF OMITTED] TR20MR18.017

Where:

di = Difference between the spiked samples and unspiked
samples in each quadruplicate sampling train minus the spiked
amount.
S1i = Measured value of the first spiked sample in the
ith quadruplicate sampling train.
S2i = Measured value of the second spiked sample in the
ith quadruplicate sampling train.
M1i = Measured value of the first unspiked sample in the
ith quadruplicate sampling train.
M2i = Measured value of the second unspiked sample in the
ith quadruplicate sampling train.
CS = Calculated value of the spike level.

    Calculate the numerical value of the bias using Equation 301-19.

    [GRAPHIC] [TIFF OMITTED] TR20MR18.018

Where:

B = Numerical value of the bias.
di = Difference between the spiked samples and unspiked
samples in each quadruplicate sampling train minus the spiked
amount.
n = Number of quadruplicate sampling trains.

    12.1.2 Standard Deviation of the Differences. Calculate the
standard deviation of the differences using Equation 301-20.
[GRAPHIC] [TIFF OMITTED] TR20MR18.019

Where:

SDd = Standard deviation of the differences of paired
samples.
di = Difference between the spiked samples and unspiked
samples in each quadruplicate sampling train minus the spiked
amount.
dm = The mean of the differences, di, between
the spiked samples and unspiked samples.
n = Total number of quadruplicate sampling trains.

    12.1.3 T Test. Calculate the t-statistic using Equation 301-21,
where n is the total number of test sample differences (di).
For the quadruplicate sampling system procedure in Table 301-1 of this
method, n equals six.
[GRAPHIC] [TIFF OMITTED] TR20MR18.020

Where:

t = Calculated t-statistic.
dm = Mean of the difference, di, between the spiked
samples and unspiked samples.
SDd = Standard deviation of the differences of paired
samples.
n = Number of quadruplicate sampling trains.

    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 quadruplicate runs are conducted, as
specified in Table 301-1 of this method, the 2-sided confidence level
critical value is 2.571 for the five degrees of freedom. If the
calculated t-value is less than the critical value, the bias is not
statistically significant and the data are acceptable. If the
calculated t-value is greater than the critical value, the bias is
statistically significant and you must evaluate the magnitude of the
relative bias using Equation 301-22.
[GRAPHIC] [TIFF OMITTED] TR20MR18.021

Where:

BR = Relative bias.
B = Bias at the spike level from Equation 301-19.
CS = Calculated value at the spike level.

    If the relative bias is less than or equal to 10 percent, the bias
of the candidate test method is acceptable. On a source-

specific basis, if the relative bias is greater than 10 percent but
less than or equal to 30 percent, and if you correct all data collected
with the candidate test method in the future for the magnitude of the
bias using Equation 301-8, the bias of the candidate test method is
acceptable for application to the tested source at which the validation
testing was conducted. Proceed to evaluate precision of the candidate
test method.
    12.2 Precision. Calculate the standard deviation using Equation
301-23.
[GRAPHIC] [TIFF OMITTED] TR20MR18.022

Where:

SD = Standard deviation of the candidate test method.
Si = Measured value of the analyte in the ith
spiked sample.
Sm = Mean of the measured values of the analyte in all
the spiked samples.
n = Number of spiked samples.

    Calculate the RSD of the candidate test method using Equation 301-
9, where SD and Sm are the values from Equation 301-23. The
data and candidate test method are unacceptable if the RSD is greater
than 20 percent.

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 59, 60, 61, 63, or 65
for an affected source, and you would like to apply the alternative
test method to a similar source, then you must petition the
Administrator as described in Section 17.1.1 of this method.

Optional Requirements

14.0  How do I use and conduct ruggedness testing?

    Ruggedness testing is an optional requirement for validation of a
candidate test method that is intended for the source where the
validation testing was conducted. Ruggedness testing is required for
validation of a candidate test method intended to be used at multiple
sources. If you want to use a validated test method at a concentration
that is different from the concentration in the applicable emission
limitation under 40 CFR part 59, 60, 61, 63, or 65, 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 Reference 18.16 of Section 18.0 of this method and
submit a request for a waiver for conducting Method 301 at that
different source category according to Section 17.1.1 of this method.
    Ruggedness testing is a study that can be conducted in the
laboratory or the field to determine the sensitivity of a method to
parameters such as analyte concentration, sample collection rate,
interferent concentration, collection medium temperature, and sample
recovery temperature. You conduct ruggedness testing by changing
several variables simultaneously instead of changing one variable at a
time. For example, you can determine the effect of seven variables in
only eight experiments. (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 candidate test
method?

    Determination of the Limit of Detection (LOD) as specified in
Sections 15.1 and 15.2 of this method is required for source-specific
method validation and validation of a candidate test method intended to
be used for multiple sources.
    15.1 Limit of Detection. The LOD is the minimum concentration of a
substance that can be measured and reported with 99 percent confidence
that the analyte concentration is greater than zero. For this protocol,
the LOD is defined as three times the standard deviation,
So, at the blank level.
    15.2 Purpose. The LOD establishes the lower detection limit of the
candidate test method. You must calculate the LOD using the applicable
procedures found in Table 301-5 of this method. For candidate test
methods that collect the analyte in a sample matrix prior to an
analytical measurement, you must determine the LOD using Procedure I in
Table 301-5 of this method by calculating a method detection limit
(MDL) as described in 40 CFR part 136, appendix B. For the purposes of
this section, the LOD is equivalent to the calculated MDL. 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 https://www.epa.gov/radiation/marlap-manual-and-supporting-documents.

Other Requirements and Information

16.0  How do I apply for approval to use a candidate test method?

    16.1 Submitting Requests. You must request to use a candidate test
method according to the procedures in Sec.  63.7(f) or similar sections
of 40 CFR parts 59, 60, 61, and 65 (Sec.  59.104, Sec.  59.406, Sec.
60.8(b), Sec.  61.13(h)(1)(ii), or Sec.  65.158(a)(2)(iii)). You cannot
use a candidate test method to meet any requirement under these parts
until the Administrator has approved your request. The request must
include a field validation report containing the information in Section
16.2 of this method. You must submit the request to the Group Leader,
Measurement Technology Group, U.S. Environmental Protection Agency,
E143-02, 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 of this
method.
    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 16.0 of this method, as applicable.
    16.2.3 Reference material certification and value(s).
    16.2.4 Discussion of laboratory evaluations.
    16.2.5 Discussion of field sampling.
    16.2.6 Discussion of sample preparation 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
Section 17.1.1 or 17.1.2 of this method, the Administrator may waive
the requirement to use the procedures in this method to validate an
alternative or

other candidate test method. In addition, if the EPA currently
recognizes an appropriate test method or considers the candidate 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 or other candidate test
method that you want to use was validated for source-specific
application at another source and you can demonstrate to the
Administrator's satisfaction that your affected source is similar to
that validated source, then the Administrator may waive the requirement
for you to validate the alternative or other candidate test method. One
procedure you may use to demonstrate the applicability of the method to
your affected source is to conduct a ruggedness test as described in
Section 14.0 of this method.
    17.1.2 Documented Methods. If the bias, precision, LOD, or
ruggedness of the alternative or other candidate 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, precision, LOD, or
ruggedness 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 Group Leader, Measurement
Technology Group, U.S. Environmental Protection Agency, E143-02,
Research Triangle Park, NC 27711.
    17.3 Information Application for Waiver. The request for a waiver
must contain a thorough description of the candidate 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 of this method. 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 candidate test method
should be written preferably in the format of 40 CFR part 60, appendix
A, Test Methods. Additionally, the candidate test must include an
applicability statement, concentration range, precision, bias
(accuracy), and minimum and maximum storage durations in which samples
must be analyzed.
    17.3.2 Summaries of Previous Validation Tests or Other Supporting
Documents. If you use a different procedure from that described in this
method, 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 of this method,
sample stability conducted according to Section 7.0 of this method, and
detection limits conducted according to Section 15.0 of this method, as
applicable. For example, you would not need to submit ruggedness
testing results if you will be using the method at the same affected
source and 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, 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 18.18 of this method.

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 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.
In: Statistical Manual of the Association of Official Analytical
Chemists, Association of Official Analytical Chemists, Washington,
DC, 1975, pp. 33-36.
18.17 NIST/SEMATECH (current version), ``e-Handbook of Statistical
Methods,'' available from NIST, http://www.itl.nist.gov/div898/handbook/.
18.18 Statistical Table, http://www.math.usask.ca/~szafron/Stats244/
f_table_0_05.pdf.

19.0  Tables.

                    Table 301-1--Sampling Procedures
------------------------------------------------------------------------
            If you are . . .                  You must collect . . .
------------------------------------------------------------------------
Comparing the candidate test method      A total of 24 samples using a
 against a validated method.              quadruplicate sampling system
                                          (a total of six sets of
                                          replicate samples). In each
                                          quadruplicate sample set, you
                                          must use the validated test
                                          method to collect and analyze
                                          half of the samples.
Using isotopic spiking (can only be      A total of 12 samples, all of
 used with methods capable of             which are spiked with
 measurement of multiple isotopes         isotopically-labeled analyte.
 simultaneously).                         You may collect the samples
                                          either by obtaining six sets
                                          of paired samples or three
                                          sets of quadruplicate samples.
Using analyte spiking..................  A total of 24 samples using the
                                          quadruplicate sampling system
                                          (a total of six sets of
                                          replicate samples--two spiked
                                          and two unspiked).
------------------------------------------------------------------------

  Table 301-2--Storage and Sampling Procedures for Stack Test Emissions
------------------------------------------------------------------------
        If you are . . .            With . . .       Then you must . . .
------------------------------------------------------------------------
Using isotopic or analyte       Sample container   Analyze six of the
 spiking procedures.             (bag or            samples within 7
                                 canister) or       days and then
                                 impinger           analyze the same six
                                 sampling systems   samples at the
                                 that are not       proposed maximum
                                 subject to         storage duration or
                                 dilution or        2 weeks after the
                                 other              initial analysis.
                                 preparation
                                 steps.
                                Sorbent and        Extract or digest six
                                 impinger           of the samples
                                 sampling systems   within 7 days and
                                 that require       extract or digest
                                 extraction or      six other samples at
                                 digestion.         the proposed maximum
                                                    storage duration or
                                                    2 weeks after the
                                                    first extraction or
                                                    digestion. Analyze
                                                    an aliquot of the
                                                    first six extracts
                                                    (digestates) within
                                                    7 days and proposed
                                                    maximum storage
                                                    duration or 2 weeks
                                                    after the initial
                                                    analysis. This will
                                                    allow analysis of
                                                    extract storage
                                                    impacts.
                                Sorbent sampling   Analyze six samples
                                 systems that       within 7 days.
                                 require thermal    Analyze another set
                                 desorption.        of six samples at
                                                    the proposed maximum
                                                    storage time or
                                                    within 2 weeks of
                                                    the initial
                                                    analysis.
Comparing a candidate test      Sample container   Analyze at least six
 method against a validated      (bag or            of the candidate
 test method.                    canister) or       test method samples
                                 impinger           within 7 days and
                                 sampling systems   then analyze the
                                 that are not       same six samples at
                                 subject to         the proposed maximum
                                 dilution or        storage duration or
                                 other              within 2 weeks of
                                 preparation        the initial
                                 steps.             analysis.
                                Sorbent and        Extract or digest six
                                 impinger           of the candidate
                                 sampling systems   test method samples
                                 that require       within 7 days and
                                 extraction or      extract or digest
                                 digestion.         six other samples at
                                                    the proposed maximum
                                                    storage duration or
                                                    within 2 weeks of
                                                    the first extraction
                                                    or digestion.
                                                    Analyze an aliquot
                                                    of the first six
                                                    extracts
                                                    (digestates) within
                                                    7 days and an
                                                    aliquot at the
                                                    proposed maximum
                                                    storage durations or
                                                    within 2 weeks of
                                                    the initial
                                                    analysis. This will
                                                    allow analysis of
                                                    extract storage
                                                    impacts.
                                Sorbent systems    Analyze six samples
                                 that require       within 7 days.
                                 thermal            Analyze another set
                                 desorption.        of six samples at
                                                    the proposed maximum
                                                    storage duration or
                                                    within 2 weeks of
                                                    the initial
                                                    analysis.
------------------------------------------------------------------------

     Table 301-3--Critical Values of t for the Two-Tailed 95 Percent
                          Confidence Limit \1\
------------------------------------------------------------------------
                  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
11...................................................              2.201
12...................................................              2.179
13...................................................              2.160
14...................................................              2.145
15...................................................              2.131
16...................................................              2.120
17...................................................              2.110
18...................................................              2.101
19...................................................              2.093
20...................................................              2.086
------------------------------------------------------------------------
\1\ Adapted from Reference 18.17 in section 18.0.

        Table 301-4--Upper Critical Values of the F Distribution for the 95 Percent Confidence Limit \1\
----------------------------------------------------------------------------------------------------------------
           Numerator (k1) and denominator (k2) degrees of freedom                   F{F>F.05(k1,k2){time}
----------------------------------------------------------------------------------------------------------------
1,1.........................................................................                      161.40
2,2.........................................................................                       19.00
3,3.........................................................................                        9.28
4,4.........................................................................                        6.39
5,5.........................................................................                        5.05
6,6.........................................................................                        4.28
7,7.........................................................................                        3.79
8,8.........................................................................                        3.44
9,9.........................................................................                        3.18
10,10.......................................................................                        2.98
11,11.......................................................................                        2.82
12,12.......................................................................                        2.69
13,13.......................................................................                        2.58
14,14.......................................................................                        2.48
15,15.......................................................................                        2.40
16,16.......................................................................                        2.33
17,17.......................................................................                        2.27
18,18.......................................................................                        2.22
19,19.......................................................................                        2.17
20,20.......................................................................                        2.12
----------------------------------------------------------------------------------------------------------------
\1\ Adapted from References 18.17 and 18.18 in section 18.0.

                Table 301-5--Procedures for Estimating So
------------------------------------------------------------------------

------------------------------------------------------------------------
If the estimated LOD (LOD1, expected     If the estimated LOD (LOD1,
 approximate LOD concentration level)     expected approximate LOD
 is no more than twice the calculated     concentration level) is
 LOD or an analyte in a sample matrix     greater than twice the
 was collected prior to an analytical     calculated LOD, use Procedure
 measurement, use Procedure I as          II as follows.
 follows.
Procedure I:                             Procedure II:
    Determine the LOD by calculating a      Prepare two additional
     method detection limit (MDL) as         standards (LOD2 and LOD3)
     described in 40 CFR part 136,           at concentration levels
     appendix B.                             lower than the standard
                                             used in Procedure I (LOD1).
                                            Sample and analyze each of
                                             these standards (LOD2 and
                                             LOD3) at least seven times.
                                            Calculate the standard
                                             deviation (S2 and S3) for
                                             each concentration level.
                                            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.
------------------------------------------------------------------------

* * * * *

[FR Doc. 2018-05400 Filed 3-19-18; 8:45 am]
 BILLING CODE 6560-50-P