
[Federal Register Volume 81, Number 232 (Friday, December 2, 2016)]
[Proposed Rules]
[Pages 87003-87016]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2016-27544]


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ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63

[EPA-HQ-OAR-2016-0069; FRL-9955-22-OAR]
RIN 2060-AT17


Revisions to Method 301: Field Validation of Pollutant 
Measurement Methods From Various Waste Media

AGENCY: Environmental Protection Agency (EPA).

ACTION: Proposed rule.

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SUMMARY: In this action, the Environmental Protection Agency (EPA) 
proposes editorial and technical revisions to the EPA's Method 301 
``Field Validation of Pollutant Measurement Methods from Various Waste 
Media'' in order to correct and update the method. In addition, the EPA 
is clarifying the applicability of Method 301 as well as its utility to 
other regulatory provisions. The proposed revisions include ruggedness 
testing for validation of test methods for application at multiple 
sources, determination of limit of detection for all method 
validations, incorporating procedures for determining the limit of 
detection, revising the sampling requirements for the comparison 
procedure, adding storage and sampling procedures for sorbent sampling 
systems, and clarifying acceptable statistical results for candidate 
test methods. We also propose to clarify the applicability of Method 
301 to our regulations and to add 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.
    Changes made to the Method 301 field validation protocol under this 
proposed action would apply only to methods submitted to the EPA for 
approval after the effective date of this action.

DATES: Comments. Comments must be received on or before January 31, 
2017.
    Public Hearing. If anyone contacts the EPA requesting a public 
hearing by December 12, 2016, the EPA will hold a public hearing on 
January 3, 2017 from 1:00 p.m. (Eastern Standard Time) to 5:00 p.m. 
(Eastern Standard Time) at the U.S. Environmental Protection Agency 
building located at 109 T.W. Alexander Drive, Research Triangle Park, 
NC 27711. Information regarding a hearing will be posted at http://www3.epa.gov/ttn/emc/methods/.

ADDRESSES: Submit your comments, identified by Docket ID No. EPA-HQ-
OAR-2016-0069, to the Federal eRulemaking Portal: http://www.regulations.gov. Follow the online instructions for submitting 
comments. Once submitted, comments cannot be edited or withdrawn. The 
EPA may publish any comment received to its public docket. Do not 
submit electronically any information you consider to be Confidential 
Business Information (CBI) or other information whose disclosure is 
restricted by statute.
    Multimedia submissions (audio, video, etc.) must be accompanied by 
a written comment. The written comment is considered the official 
comment and should include discussion of all points you wish to make. 
The EPA will generally not consider comments or comment contents 
located outside of the primary submission (i.e., on the Web, Cloud, or 
other file sharing system). For additional submission methods, the full 
EPA public comment policy, information about CBI or multimedia 
submissions, and general guidance on making effective comments, please 
visit http://www2.epa.gov/dockets/commenting-epa-dockets.

FOR FURTHER INFORMATION CONTACT: For information concerning this 
proposal, contact Ms. Kristen J. Benedict, Office of Air Quality 
Planning and Standards, Air Quality Assessment Division (E143-02), 
Environmental Protection Agency, Research Triangle Park, NC 27711; 
telephone number: (919) 541-1394; fax number: (919) 541-0516; email 
address: benedict.kristen@epa.gov.

SUPPLEMENTARY INFORMATION:

Table of Contents

I. General Information
    A. Does this action apply to me?
    B. What should I consider as I prepare my comments?
    C. Where can I get a copy of this document and other related 
information?
II. Background
III. Summary of Proposed Revisions
    A. Technical Revisions
    B. Clarifying and Editorial Changes
IV. Request for Comments
V. Statutory and Executive Order Reviews
    A. Executive Order 12866: Regulatory Planning and Review and 
Executive Order 13563: Improving Regulation and Regulatory Review
    B. Paperwork Reduction Act (PRA)
    C. Regulatory Flexibility Act (RFA)
    D. Unfunded Mandates Reform Act (UMRA)
    E. Executive Order 13132: Federalism
    F. Executive Order 13175: Consultation and Coordination With 
Indian Tribal Governments
    G. Executive Order 13045: Protection of Children From 
Environmental Health Risks and Safety Risks
    H. Executive Order 13211: Actions That Significantly Affect 
Energy Supply, Distribution, or Use

[[Page 87004]]

    I. National Technology Transfer and Advancement Act (NTTAA)
    J. Executive Order 12898: Federal Actions To Address 
Environmental Justice in Minority Populations and Low-Income 
Populations

I. General Information

A. Does this action apply to me?

    Method 301 affects/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 are an appropriate 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 any 
questions regarding the applicability of the proposed changes to Method 
301, contact the person listed in the preceding FOR FURTHER INFORMATION 
CONTACT section.

B. What should I consider as I prepare my comments?

    Submitting CBI: Clearly mark the part or all of the information 
that you claim to be CBI. For CBI information in a disk or CD-ROM that 
you mail to the EPA, mark the outside of the disk or CD-ROM as CBI and 
then identify electronically within the disk or CD-ROM the specific 
information that is claimed as CBI. In addition to one complete version 
of the comment that includes information claimed as CBI, a copy of the 
comment that does not contain the information claimed as CBI must be 
submitted for inclusion in the public docket. Information marked as CBI 
will not be disclosed except in accordance with procedures set forth in 
title 40 CFR part 2.
    Do not submit information that you consider to be CBI or otherwise 
protected through http://www.regulations.gov or email. Send or deliver 
information identified as CBI to: OAQPS Document Control Officer (Room 
C404-02), U.S. EPA, Research Triangle Park, NC 27711, Attention Docket 
ID No. EPA-HQ-OAR-2016-0069.
    If you have any questions about CBI or the procedures for claiming 
CBI, please consult the person identified in the FOR FURTHER 
INFORMATION CONTACT section.
    Docket: All documents in the docket are listed in the http://www.regulations.gov index. Although listed in the index, some 
information is not publicly available, e.g., CBI or other information 
whose disclosure is restricted by statute. Certain other material, such 
as copyrighted material, will be publicly available only in hard copy. 
Publicly available docket materials are available either electronically 
in http://www.regulations.gov or in hard copy at the EPA Docket Center, 
EPA/DC, EPA WJC West Building, Room 3334, 1301 Constitution Ave. NW., 
Washington, DC. This Docket Facility is open from 8:30 a.m. to 4:30 
p.m., Monday through Friday, excluding legal holidays. The telephone 
number for the Public Reading Room is (202) 566-1744, and the telephone 
number for the Air Docket is (202) 566-1742.

C. 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 proposed method revisions is available on the Technology Transfer 
Network (TTN) Web site at http://www3.epa.gov/ttn/emc/methods/. The TTN 
provides information and technology exchange in various areas of air 
pollution control.

II. Background

    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 in support of the Early Reductions Program of 
Part 63 when test methods were unavailable. On March 16, 1994, the EPA 
incorporated Method 301 into 40 CFR 63.7 (59 FR 12430) as a means to 
validate 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. To date, subsequent revisions of Method 301 have not 
distinguished requirements for source-specific applications of a 
candidate method versus application of a candidate test method at 
multiple sources. The EPA's 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, or for use as a means for 
showing compliance with a regulatory standard in 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 would be considered 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.
    Additionally, the EPA recognized that there were a number of ways 
Method 301 could be clarified while reviewing submitted data and 
answering questions from facilities, environmental labs, and technology 
vendors on the application and requirements of the method.

III. Summary of Proposed Revisions

    In this action, we propose clarifications to the applicability and 
utility of Method 301 to additional regulatory provisions, and propose 
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 the current version of Method 301, the procedures for conducting 
ruggedness testing in sections 3.1 and 14.0, and for determining the 
limit of detection (LOD) in sections 3.1 and 15.0, are optional 
procedures that are not required for validation of a candidate test 
method. In this action, we propose to amend 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 would continue to be optional for validation of 
methods intended for source-specific applications. We also propose to 
amend sections 3.1 and 15.0 to require determination of the LOD for 
validation of all methods (i.e., those intended for both source and 
multi-source application). Additionally, we propose clarifications to 
the LOD definition in section 15.1.

[[Page 87005]]

    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 source-specific validations will 
account for the sensitivity of the candidate test method to ensure it 
meets applicable regulatory requirements.
2. Limit of Detection Procedures
    The EPA proposes revisions to the requirements for determining the 
LOD specified in section 15.2 and Table 301-5 (Procedure I) to 
incorporate procedures of the EPA's proposed revisions to 40 CFR part 
136, appendix B (80 FR 8955). The proposed revisions address laboratory 
blank contamination and account for intra-laboratory variability, 
consistent with the proposed changes to 40 CFR part 136. We propose to 
require Procedure I of Table 301-5 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 this proposed rule, LOD would be equivalent to 
the calculated method detection limit (MDL) determined using the 
procedures specified in proposed 40 CFR part 136, appendix B. Through 
this proposed change, laboratories would be required to consider media 
blanks when performing LOD calculations. If the revisions to 40 CFR 
part 136, appendix B are finalized as proposed prior to a final action 
on this proposal, we will cross-reference appendix B. If appendix B is 
finalized before this action and the revisions do not incorporate the 
procedures as described above, the EPA intends to incorporate the 
specific procedures for determining the LOD in the final version of 
Method 301 consistent with this proposal. If appendix B is not 
finalized before these proposed revisions, the EPA also intends to 
incorporate the specific procedures directly into Method 301. Other 
than the proposed revisions to 40 CFR part 136, appendix B, as 
discussed above, changes addressed under that rulemaking are outside 
the scope of this proposed action.
3. Storage and Sampling Procedures
    Currently, the number of samples required by Method 301 when using 
a quadruplicate sampling system for conducting the analyte spiking 
procedure and for conducting the comparison procedure is not 
consistent. In this action, we propose revisions to section 11.1.3 and 
Table 301-1 to require six sets of quadruplicate samples (a total of 24 
samples for the analyte spiking or comparison procedures) rather than 
four sets. This proposed revision will ensure the bias and precision 
requirements are consistent in the method and decrease the amount of 
uncertainty in the calculations for bias and precision when comparing 
an alternative test method with a validated method. Bias and precision 
(standard deviation and variance) are all 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 goes up, the bias and precision 
estimates go down. Larger data sets provide better estimates of the 
standard deviation or variance and the distribution of the data. The 
proposed revision to collect a total of 24 samples when using the 
analyte spiking approach is also consistent with the number of samples 
required for the isotopic spiking approach. 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 for an unspiked sample and one for a spiked sample.
    In this action, we also propose revisions to section 9.0 to specify 
that either paired sampling or quadruplicate sampling systems may be 
used for isotopic spiking, while only quadruplicate sampling systems 
may be used to establish precision for analyte spiking or when 
comparing an alternative method to a validated method.
    For validations conducted by comparing the candidate test method to 
a validated test method, we propose to add: (1) Storage and sampling 
procedures for sorbent systems requiring thermal desorption to Table 
301-2; and (2) a new Table 301-4 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 propose an amendment to the 
reference list in section 18.0 to include the source of the F values.
4. Bias Criteria for Multi-Source Versus Source-Specific Validation
    In this action, we propose clarification to sections 8.0, 10.3, and 
11.1.3 to specify that candidate test methods intended for use at 
multiple sources must have a bias less than or equal to 10 percent. We 
propose that candidate test methods with a bias greater than 10 
percent, but less than 30 percent, apply only at the source at which 
the validation testing was conducted and that data collected in the 
future be adjusted for bias using a source-specific correction factor. 
A source-specific correction factor is not necessarily appropriate for 
use at multiple sources. This proposed change provides flexibility for 
source-specific Method 301 application while limiting the acceptance 
criteria for use of the method at multiple sources. We believe that the 
Method 301 results from a single source are not sufficient to allow us 
to establish a correction factor that can be applied at multiple 
sources.
5. Relative Standard Deviation Assessment
    In this action, we propose amendments to sections 9.0 and 12.2 to 
clarify 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 propose that the RSD of a candidate test method must be 
less than or equal to 20 percent. Accordingly, we propose to remove 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 are proposing an 
acceptance criteria of less than or equal to 20 percent for analyte and 
isotopic spiking sampling procedures.
6. Applicability of Method 301
    Currently, Method 301 states that it is applicable for determining 
alternative test methods for standards under 40 CFR part 63 (National 
Emission Standards for Hazardous Air Pollutants for Source Categories). 
Although 40 CFR 65.158(a)(2)(iii) specifically cross-references Method 
301, Method 301 has not previously been revised to reference Part 65. 
For parts 63 and 65, Method 301 must be used for establishing an 
alternative test method. In this action, we propose revisions 
clarifying that Method 301 is applicable to both parts 63 and 65 and 
that Method 301 is also

[[Page 87006]]

appropriate for validating alternative test methods for use under the 
following parts under title 40 of the Clean Air Act:

 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 as the 
testing provisions are very similar to those under parts 63 and 65. To 
accommodate the expanded applicability and suitability, we propose to 
revise the references in sections 2.0, 3.2, 5.0, 13.0, 14.0, and 16.1 
to refer to all five regulatory parts.
7. Equation Additions
    In this action, we propose to clarify 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 propose revisions to the denominator of Equation 22 to use 
the variable ``CS'' rather than ``VS.'' Additionally, we propose 
revisions to the text of Method 301, where needed, to list and define 
all variables used in the method equations. These proposed changes are 
intended to improve the readability of the method and ensure that 
required calculations and acceptance criteria for each of Method 301's 
three validation approaches are clear.

B. Clarifying and Editorial Changes

    In this action, we propose minor edits throughout the text of 
Method 301 to clarify the descriptions and requirements for assessing 
bias and precision, to ensure consistency when referring to citations 
within the method, to renumber equations and tables (where necessary), 
and to remove passive voice.
    We propose edits to clarify several definitions in section 3.2. In 
the definition of ``Paired sampling system,'' we propose a minor edit 
to note that the system is collocated. For the definition of 
``Quadruplet sampling system,'' we propose to replace the term 
``Quadruplet'' with ``Quadruplicate'' and to add descriptive text to 
the definition to provide examples of replicate samples. We are also 
proposing companion edits throughout the method text to reflect the 
change in terminology from ``quadruplet'' to ``quadruplicate.'' 
Additionally, we propose clarifying edits to the definition of 
``surrogate compound.''
    We also propose 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 proposes the following updates and 
corrections by:
     Updating the address for submitting waivers in section 
17.2.
     Adding the t-value for 11 degrees of freedom to Table 301-
2.
     Correcting the t-value for four degrees of freedom in 
Table 301-2.

IV. Request for Comments

    The EPA specifically requests public comments on the expanded 
applicability of Method 301 to 40 CFR part 59 and to note the 
suitability of Method 301 for validation of alternative test methods 
under 40 CFR parts 60 and 61. In addition, we specifically request 
comment on the following proposed technical amendments to Method 301:
    (A) Requiring ruggedness testing and determination of LOD for 
validation of test methods intended for multi-source and source-
specific applications.
    (B) Incorporating the procedures specified in the proposed 
revisions to 40 CFR part 136, appendix B, into the Method 301 
procedures for determining LOD.
    (C) Revising the sampling requirements for the method comparison 
procedure to require six sets of quadruplicate samples rather than four 
sets, and adding storage and sampling procedures for sorbent systems 
that require thermal desorption.
    (D) Clarifying that candidate test methods that are intended for 
use at multiple sources must have a bias less than or equal to 10 
percent and that test methods, where the bias is greater than 10 
percent but less than to 30 percent, are applicable only on a source-
specific basis with the use of a correction factor.
    (E) Clarifying that the RSD of a candidate test method validated 
using the analyte spiking or isotopic spiking procedure must be less 
than or equal to 20 percent for the method to be acceptable.
    (F) Adding equations to calculate the: (1) Correction factor (if 
required) when using isotopic spiking; (2) standard deviation when 
using the analyte spiking procedure; (3) estimated variance of 
validated test method when using the comparison procedure; and (4) 
standard deviation of differences and t-statistic when using the 
analyte spiking or comparison procedures.

V. Statutory and Executive Order Reviews

A. Executive Order 12866: Regulatory Planning and Review and Executive 
Order 13563: Improving Regulation and Regulatory Review

    This proposed action is not a significant regulatory action and 
was, therefore, not submitted to the Office of Management and Budget 
(OMB) for review.

B. Paperwork Reduction Act (PRA)

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

C. Regulatory Flexibility Act (RFA)

    I certify that this proposed 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. 
The proposed revisions to Method 301 do not impose any requirements on 
regulated entities beyond those specified in the current regulations, 
nor do they change any emission standard. We have therefore concluded 
that this proposed action will have no net regulatory burden for all 
directly regulated small entities.

D. Unfunded Mandates Reform Act (UMRA)

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

E. Executive Order 13132: Federalism

    This proposed 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

[[Page 87007]]

responsibilities among the various levels of government.

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

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

G. 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 proposed action is not 
subject to Executive Order 13045 because it does not concern an 
environmental health risk or safety risk.

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

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

I. National Technology Transfer and Advancement Act (NTTAA)

    This proposed 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).

J. 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 would make 
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.

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: November 8, 2016.
Gina McCarthy,
Administrator.

    For the reasons stated in the preamble, the EPA proposes to amend 
title 40, chapter I of the Code of the 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 Pollutant Measurement Methods From 
Various Waste Media

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

Sec.

Using Method 301

1.0 What is the purpose of Method 301?
2.0 When must I use Method 301?
3.0 What does Method 301 include?
4.0 How do I perform Method 301?

Reference Materials

5.0 What reference materials must I use?

Sampling Procedures

6.0 What sampling procedures must I use?
7.0 How do I ensure sample stability?

Bias and Precision

8.0 What are the requirements for bias?
9.0 What are the requirements for precision?
10.0 What calculations must I perform for isotopic spiking?
11.0 What calculations must I perform for comparison with a 
validated method if I am using quadruplicate replicate sampling 
systems?
12.0 What calculations must I perform for analyte spiking?
13.0 How do I conduct tests at similar sources?

Optional Requirements

14.0 How do I use and conduct ruggedness testing?
15.0 How do I determine the Limit of Detection 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?

Using Method 301

1.0 What is the purpose of Method 301?

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

2.0 What approval must I have to use Method 301?

    If you want to use a candidate test method to meet requirements 
in a subpart of 40 CFR part 59, 60, 61, 63, or 65, you must also 
request approval to use the candidate test method according to the 
procedures in Section 16 of this method and the appropriate section 
of the part (Sec.  59.104, Sec.  59.406, Sec.  60.8(b), Sec.  
61.13(h)(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

[[Page 87008]]

candidate test methods that are to be applied at a single source.
    3.2 Definitions.
    Affected source means an affected source as defined in the 
relevant part and subpart under title 40 (e.g., 40 CFR parts 59, 60, 
61, 63, and 65).
    Candidate test method means the sampling and analytical 
methodology selected for field validation using the procedures 
described in Method 301. The candidate test method may be an 
alternative test method under 40 CFR part 59, 60, 61, 63, or 65.
    Paired sampling system means a sampling system capable of 
obtaining two replicate samples that are collected as closely as 
possible in sampling time and sampling location (collocated).
    Quadruplicate sampling system means a sampling system capable of 
obtaining four replicate samples (e.g., two pairs of measured data, 
one pair from each method when comparing a candidate test method 
against a validated test method, or analyte spiking with two spiked 
and two unspiked samples) that are collected as close as possible in 
sampling time and sampling location.
    Surrogate compound means a compound that serves as a model for 
the target compound(s) being measured (i.e., similar chemical 
structure, properties, behavior). The surrogate compound can be 
distinguished by the candidate test method from the compounds being 
analyzed.

4.0 How do I perform Method 301?

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

Reference Materials

5.0 What reference materials must I use?

    You must use reference materials (a material or substance with 
one or more properties that are sufficiently homogenous to the 
analyte) that are traceable to a national standards body (e.g., 
National Institute of Standards and Technology (NIST)) at the level 
of the applicable emission limitation or standard that the subpart 
in 40 CFR part 59, 60, 61, 63, or 65 requires. If you want to expand 
the applicable range of the candidate test method, you must conduct 
additional test runs using analyte concentrations higher and lower 
than the applicable emission limitation or the anticipated level of 
the target analyte. You must obtain information about your analyte 
according to the procedures in Sections 5.1 through 5.4 of this 
method.
    5.1 Exhaust Gas Test Concentration. You must obtain a known 
concentration of each analyte from an independent source such as a 
specialty gas manufacturer, specialty chemical company, or chemical 
laboratory. You must also obtain the manufacturer's certification of 
traceability, uncertainty, and stability for the analyte 
concentration.
    5.2 Tests for Other Waste Media. You must obtain the pure liquid 
components of each analyte from an independent manufacturer. The 
manufacturer must certify the purity, traceability, uncertainty, and 
shelf life of the pure liquid components. You must dilute the pure 
liquid components in the same type medium or matrix as the waste 
from the affected source.
    5.3 Surrogate Analytes. If you demonstrate to the 
Administrator's satisfaction that a surrogate compound behaves as 
the analyte does, then you may use surrogate compounds for highly 
toxic or reactive compounds. A surrogate may be an isotope or 
compound that contains a unique element (e.g., chlorine) that is not 
present in the source or a derivation of the toxic or reactive 
compound if the derivative formation is part of the method's 
procedure. You may use laboratory experiments or literature data to 
show behavioral acceptability.
    5.4 Isotopically-Labeled Materials. Isotope mixtures may contain 
the isotope and the natural analyte. The concentration of the 
isotopically-labeled analyte must be more than five times the 
concentration of the naturally-occurring analyte.

Sampling Procedures

6.0 What sampling procedures must I use?

    You must determine bias and precision by comparison against a 
validated test method, using isotopic spiking, or using analyte 
spiking (or the equivalent). Isotopic spiking can only be used with 
candidate test methods capable of measuring multiple isotopes 
simultaneously such as test methods using mass spectrometry or 
radiological procedures. You must collect samples according to the 
requirements specified in Table 301-1 of this method. You must 
perform the sampling according to the procedures in Sections 6.1 
through 6.4 of this method.
    6.1 Isotopic Spiking. Spike all 12 samples with isotopically-
labelled analyte at an analyte mass or concentration level 
equivalent to the emission limitation or standard specified in the 
applicable regulation. If there is no applicable emission limitation 
or standard, spike the analyte at the expected level of the samples. 
Follow the applicable spiking procedures in Section 6.3 of this 
method.
    6.2 Analyte Spiking. In each quadruplicate set, spike half of 
the samples (two out of the four samples) with the analyte according 
to the applicable procedure in Section 6.3 of this method. You 
should spike at an analyte mass or concentration level equivalent to 
the emission limitation or standard specified in the applicable 
regulation. If there is no applicable emission limitation or 
standard, spike the analyte at the expected level of the samples. 
Follow the applicable spiking procedures in Section 6.3 of this 
method.
    6.3 Spiking Procedure.
    6.3.1 Gaseous Analyte With Sorbent or Impinger Sampling Train. 
Sample the analyte being spiked (in the laboratory or preferably in 
the field) at a mass or concentration that is approximately 
equivalent to the applicable emission limitation or standard (or the 
expected sample concentration or mass where there is no standard) 
for the time required by the candidate test method, and then sample 
the stack gas stream for an equal amount of time. The time for 
sampling both the analyte and stack gas stream should be equal; 
however, you must adjust the sampling time to avoid sorbent 
breakthrough. You may sample the stack gas and the gaseous analyte 
at the same time. You must introduce the analyte as close to the tip 
of the sampling probe as possible.
    6.3.2 Gaseous Analyte With Sample Container (Bag or Canister). 
Spike the sample containers after completion of each test run with 
an analyte mass or concentration to yield a concentration 
approximately equivalent to the applicable emission limitation or 
standard (or the expected sample concentration or mass where there 
is no standard). Thus, the final concentration of the analyte in the 
sample container would be approximately equal to the analyte 
concentration in the stack gas plus the equivalent of the applicable 
emission standard (corrected for spike volume). The volume amount of 
spiked gas must be less than 10 percent of the sample volume of the 
container.
    6.3.3 Liquid or Solid Analyte With Sorbent or Impinger Trains. 
Spike the sampling trains with an amount approximately equivalent to 
the mass or concentration in the applicable emission limitation or 
standard (or the expected sample concentration or mass where there 
is no standard) before sampling the stack gas. If possible, do the 
spiking in the field. If it is not possible to do the spiking in the 
field, you must spike the sampling trains in the laboratory.
    6.3.4 Liquid and Solid Analyte With Sample Container (Bag or 
Canister). Spike the containers at the completion of each test run 
with an analyte mass or concentration approximately equivalent to 
the applicable emission limitation or standard in the subpart (or 
the expected sample concentration or mass where there is no 
standard).
    6.4 Probe Placement and Arrangement for Stationary Source Stack 
or Duct Sampling. To sample a stationary source, you must place the 
paired or quadruplicate probes according to the procedures in this 
subsection. You must place the probe tips in the same horizontal 
plane.
    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. 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 pitot tubes (where required) 
are used.
    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

[[Page 87009]]

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 time period between 
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 
two weeks of the initial analysis to identify the effect of storage 
duration on analyte samples. The minimum time period between 
collection and storage should be as soon as possible, but no longer 
than 72 hours after collection of the sample.
    7.4 Sample Stability. After you have conducted sampling and 
analysis according to Section 7.2 or 7.3 of this method, compare the 
results at the minimum and maximum storage durations. Calculate the 
difference in the results using Equation 301-1 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.000

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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.001

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 
of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.002

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.

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

[[Page 87010]]

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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.003

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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.004

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 of this method. 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] TP02DE16.005

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 of 
this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.006

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 of 
this method, 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.

[[Page 87011]]

[GRAPHIC] [TIFF OMITTED] TP02DE16.007

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 of 
this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.008

Where:

RSD = Relative standard deviation of the candidate test method.
SD = Standard deviation of the candidate test method calculated in 
Equation 301-5 of this method.
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 I am using quadruplicate replicate sampling 
systems?

    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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.009

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 i\th\ quadruplicate sampling train.
V2i = Second measured value with the validated method in 
the i\th\ quadruplicate sampling train.
P1i = First measured value with the candidate test method 
in the i\th\ quadruplicate sampling train.
P2i = Second measured value with the candidate test 
method in the i\th\ quadruplicate sampling train.

    Calculate the numerical value of the bias using Equation 301-11 
of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.010

Where:

B = Numerical bias.
di = Difference between the candidate test method and the 
validated method for the i\th\ 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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.011

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 
of this method.

[[Page 87012]]

[GRAPHIC] [TIFF OMITTED] TP02DE16.012

Where:

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

    For the procedure comparing a candidate test method to a 
validated test method listed in Table 301-1 of this method, n equals 
six. Compare the calculated t-statistic with the critical value of 
the t-statistic, and determine if the bias is significant at the 95 
percent confidence level (see Table 301-3 of this method). When six 
runs are conducted, as specified in Table 301-1 of this method, the 
critical value of the t-statistic is 2.571 for five degrees of 
freedom. If the calculated t-value is less than or equal to the 
critical value, the bias is not statistically significant and the 
data are acceptable. If the calculated t-value is greater than the 
critical value, the bias is statistically significant, and you must 
evaluate the magnitude of the relative bias using Equation 301-14 of 
this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.013

Where:

BR = Relative bias.
B = Bias as calculated in Equation 301-11 of this method.
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 of 
this method (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 
of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.014

Where:

Sp\2\ = Estimated variance of the candidate test method.
di = The difference between the i\th\ 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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.015

Where:

Sv\2\ = Estimated variance of the validated test method.
di = The difference between the i\th\ 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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.016

Where:

F = Calculated F value.
Sp\2\ = The estimated variance of the candidate test method.
Sv\2\ = 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

[[Page 87013]]

sampling trains is followed. If the calculated F value is greater 
than the critical F value, the difference in precision is 
significant, and the data and the candidate test method are 
unacceptable.

12.0 What calculations must I perform for analyte spiking?

    You must analyze the data for analyte spike testing according to 
this section.
    12.1 Bias Analysis. Test the bias for statistical significance 
at the 95 percent confidence level by calculating the t-statistic.
    12.1.1 Bias. Determine the bias, which is defined as the mean of 
the differences between the spiked samples and the unspiked samples 
in each quadruplicate sampling train minus the spiked amount, using 
Equation 301-18 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.017

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 
of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.018

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 of this 
method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.019

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 
of this method, 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] TP02DE16.020

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 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.021


[[Page 87014]]


Where:

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

    If the relative bias is less than or equal to 10 percent, the 
bias of the candidate test method is acceptable. On a source-
specific basis, if the relative bias is greater than 10 percent but 
less than or equal to 30 percent, and if you correct all data 
collected with the candidate test method in the future for the 
magnitude of the bias using Equation 301-8, the bias of the 
candidate test method is acceptable for application to the tested 
source at which the validation testing was conducted. Proceed to 
evaluate precision of the candidate test method.
    12.2 Precision. Calculate the standard deviation using Equation 
301-23 of this method.
[GRAPHIC] [TIFF OMITTED] TP02DE16.022

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 of this method, where SD and Sm are the values from 
Equation 301-23 of this method. 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 proposed 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 http://www2.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)(ii), or Sec.  
65.158(a)(2)(iii)). You cannot use a candidate test method to meet 
any requirement under these parts until the Administrator has 
approved your request. The request must include a field validation 
report containing the information in Section 16.2 of this method. 
You must submit the request to the Group Leader, Measurement 
Technology Group, U.S. Environmental Protection Agency, E143-02, 
Research Triangle Park, NC 27711.
    16.2 Field Validation Report. The field validation report must 
contain the information in Sections 16.2.1 through 16.2.8 of this 
method.
    16.2.1 Regulatory Objectives for the Testing, Including a 
Description of the Reasons for the Test, Applicable Emission Limits, 
and a Description of the Source.
    16.2.2 Summary of the Results and Calculations Shown in Sections 
6.0 Through 16.0 of This Method, as Applicable.
    16.2.3 Reference Material Certification and Value(s).
    16.2.4 Discussion of Laboratory Evaluations.
    16.2.5 Discussion of Field Sampling.
    16.2.6 Discussion of Sample Preparation and Analysis.
    16.2.7 Storage Times of Samples (and Extracts, if Applicable).
    16.2.8 Reasons for Eliminating Any Results.

17.0 How do I request a waiver?

    17.1 Conditions for Waivers. If you meet one of the criteria in 
Section 17.1.1 or 17.1.2 of this method, the Administrator may waive 
the requirement to use the procedures in this method to validate an 
alternative or other candidate test method. In addition, if the EPA 
currently recognizes an appropriate test method or considers the 
candidate test method to be satisfactory for a particular source, 
the Administrator may waive the use of this protocol or may specify 
a less rigorous validation procedure.
    17.1.1 Similar Sources. If the alternative or other candidate 
test method that you want to use was validated for source-specific 
application at another source and you can demonstrate to the 
Administrator's satisfaction that your affected source is similar to 
that validated source, then the Administrator may waive the 
requirement for you to validate the alternative or other candidate 
test method. One procedure you may use to demonstrate the 
applicability of the method to your affected source is to conduct a 
ruggedness test as described in Section 14.0 of this method.
    17.1.2 Documented Methods. If the bias and precision 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 and

[[Page 87015]]

precision apply to your application, then the Administrator may 
waive the requirement to use this method or to use part of this 
method.
    17.2 Submitting Applications for Waivers. You must sign and 
submit each request for a waiver from the requirements in this 
method in writing. The request must be submitted to the 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 18.17 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/.

                    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).
------------------------------------------------------------------------


[[Page 87016]]


  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
------------------------------------------------------------------------
                   Degrees of freedom                           t95
------------------------------------------------------------------------
1.......................................................          12.706
2.......................................................           4.303
3.......................................................           3.182
4.......................................................           2.777
5.......................................................           2.571
6.......................................................           2.447
7.......................................................           2.365
8.......................................................           2.306
9.......................................................           2.262
10......................................................           2.228
11......................................................           2.201
------------------------------------------------------------------------


   Table 301-4--Upper Critical Values of the F Distribution for the 95
                        Percent Confidence Limit
------------------------------------------------------------------------
 Numerator (k1) and  denominator (k2) degrees of
                     freedom                      F{F>F.05(k1,k2){time}
------------------------------------------------------------------------
1,1.............................................                 161.4
2,2.............................................                  19.0
3,3.............................................                   9.3
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
------------------------------------------------------------------------


                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 greater
 LOD or an analyte in a sample matrix    than twice the calculated LOD,
 was collected prior to an analytical    use Procedure II as follows
 measurement, use Procedure I as
 follows..
Procedure I                             Procedure II
Determine the LOD by calculating a      Prepare two additional standards
 method detection limit (MDL) as         (LOD2 and LOD3) at
 described in proposed 40 CFR part       concentration levels lower than
 136, appendix B.                        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. 2016-27544 Filed 12-1-16; 8:45 am]
BILLING CODE 6560-50-P


