[Federal Register Volume 83, Number 54 (Tuesday, March 20, 2018)]
[Rules and Regulations]
[Pages 12118-12133]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[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: (919) 541-0893; fax number: (919) 541-0516; 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

[[Page 12119]]

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

[[Page 12120]]

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

[[Page 12121]]

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

[[Page 12122]]

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.

[[Page 12123]]

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

[[Page 12124]]

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

[[Page 12125]]

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.

[[Page 12126]]

[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.

[[Page 12127]]

[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.



[[Page 12128]]


    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.

[[Page 12129]]

    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-

[[Page 12130]]

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

[[Page 12131]]

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.

[[Page 12132]]



                    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.


[[Page 12133]]


        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