Source: http://www.docstoc.com/docs/581831/National-Emission-Standards-for-Hazardous-Air-Pollutants
Timestamp: 2013-12-19 22:26:32
Document Index: 729377617

Matched Legal Cases: ['art 2', 'art 63', 'art 63', 'art 9', 'art 63', 'art 63', 'art 63', 'art 62', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63', 'art 63']

[OAR-2004-0080, FRL-7851-9]
RIN 2060-AF00
National Emission Standards for Hazardous Air Pollutants: Appendix A - Test
Methods; Method 301 for the
SUMMARY: This action proposes to amend procedures for validating alternative
emissions test methods, to rewrite the EPA’s Method 301 in plain language, reorganize
the method for clarity, correct technical errors, and revise the technical procedures. The
revisions to the technical procedures include replacing quantitation limits with detection
limits, revising the bias acceptance criteria and eliminating the correction factors,
revising the precision acceptance criteria, and allowing analyte spiking as an option even
when there is an existing test method.
DATES: Comments. Comments must be received on or before [INSERT DATE 60
DAYS AFTER PUBLICATION IN THE FEDERAL REGISTER].
Public Hearing. If anyone contacts the EPA requesting a public hearing by [INSERT
DATE 20 DAYS AFTER PUBLICATION IN THE FEDERAL REGISTER], a public
hearing will be held on [INSERT DATE 30 DAYS AFTER PUBLICATION IN THE
ADDRESSES: Comments. Submit your comments, identified by Docket ID No. OAR-
2004-0080, by one of the following methods.
•      Federal eRulemaking Portal: http:///www.regulations.gov. Follow the on-line
•      Agency Website: http://www.epa.gov/edocket. EDOCKET, EPA’s electronic
public docket and comment system, is EPA’s preferred method for receiving
comments. Follow the on-line instructions for submitting comments.
•      Mail: Air and Radiation Docket and Information Center (Mail Code 6102T),
Attention Docket Number OAR-2004-0080, Room B108, U.S. EPA, 1301
Constitution Avenue, NW., Washington, DC 20460. The EPA requests that a
separate copy also be sent to the contact person listed below (see FOR FURTHER
INFORMATION CONTACT). Send submissions containing such proprietary or
confidential business information (CBI) directly to the following address, and not
to the public docket, to ensure that proprietary or CBI is not inadvertently placed
in the public docket: Attention: Mr. Roberto Morales, U.S. Environmental
Protection Agency, OAQPS Document Control Officer, 109 TW Alexander
Drive, Room C404-02, RTP, NC, 27711.
•      Hand Delivery: Air and Radiation Docket and Information Center (Mail Code
6102T), Attention Docket Number OAR-2004-0080, Room B102, U.S. EPA,
1301 Constitution Avenue, NW, Washington, DC 20460. Such deliveries are
only accepted during the Docket’s normal hours of operation, and special
arrangements should be made for deliveries of boxed information. The EPA
requests a separate copy also be sent to the contact person listed below (see FOR
Instructions. Direct your comments to Docket ID No. OAR-2004-0080. The EPA’s
policy is that all comments received will be included in the public docket without change
and may be made available online at http://www.epa.gov/edocket, including any
personal information provided, unless the comment includes information claimed to be
Confidential Business Information (CBI) or other information whose disclosure is
restricted by statute. Do not submit information that you consider to be CBI or otherwise
protected through EDOCKET, regulations.gov websites, or e-mail. The EPA EDOCKET
and the Federal regulations.gov websites are “anonymous access” systems, which means
the EPA will not know your identity or contact information unless you provide it in the
body of your comment. If you send an e-mail comment directly to the EPA without
going through EDOCKET OR regulations.gov, your e-mail address will be automatically
captured and included as part of the comment that is placed in the public docket and
made available on the internet. If you submit an electronic comment, the EPA
recommends that you include your name and other contact information in the body of
your comment and with any disk or CD-ROM you submit. If the EPA cannot read your
comment due to technical difficulties and cannot contact you for clarification, the EPA
may not be able to consider your comment. Electronic files should avoid the use of
special characters, any form of encryption, and be free of any defects or viruses. For
additional information about EPA’s public docket visit EDOCKET on-line or see the
Federal Register of May 31, 2002 (67 FR 38102).
Docket. All documents in the docket are listed in the EDOCKET index at
http://www.epa.gov/edocket. Although listed in the index, some information is not
publicly available, i.e., 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 hardcopy form. Publicly available docket materials are
available either electronically in EDOCKET or in hard copy at the EPA Docket Center
(Air Docket), EPA West, Room B-108, 1301 Constitution Avenue, NW., Washington,
DC 20004. The Docket Center 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.
Public Hearing. People interested in presenting oral testimony or inquiring as to whether
a hearing is to be held should contact Ms. Corlis McCormick, Source Measurement
Technology Group, Emission Measurement Center (D243-02), U.S. Environmental
Protection Agency, Research Triangle Park, NC, 27711, telephone number:
(919) 541-5545, at least 2 days in advance of the public hearing. People interested in
attending the public hearing must also call Ms. McCormick to verify the time, date, and
location of the hearing. The public hearing will provide interested parties the opportunity
to present data, views, or arguments concerning the proposed changes to Method 301. If
a public hearing is held, it will be held at 10:00 a.m. in the EPA&#39;s Auditorium in Research
Triangle Park, North Carolina, or at an alternate site nearby.
proposed standards, contact Mr. Gary McAlister, Source Measurement Technology
Group, Emission Measurement Center (D243-02), U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina 27711, telephone number: (919) 541-
1062, electronic mail address: mcalister.gary@epa.gov.
The information in this preamble is organized as follows.
C. Availability of the Proposed Rule
III. What changes Are We Proposing?
A. Use Plain Language
B. Reorganize Method 301
C. Correct Technical Errors
D. Make Technical Revisions
A. Executive Order 12866 - Regulatory Planning and Review
E. Executive Order 13132 - Federalism
F. Executive Order 13175 - Consultation and Coordination with Indian Tribal
G. Executive Order 13045 -Protection of Children from Environmental Health Risks and
H. Executive Order 13211, Actions Concerning Regulations That Significantly Affect
Method 301 affects/applies to you if you want to propose a test method to meet an
EPA requirement in absence of a validated method.
1. Submitting CBI. Do not submit this information to the EPA through
EDOCKET, regulations.gov, or e-mail. 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 so marked will not be disclosed except in
2. Tips for Preparing Your Comments. When submitting comments, remember
i. Identify the rulemaking by docket number and other identifying information
(e.g., subject heading, Federal Register proposal publication date and reference page
number(s)).
ii. Follow directions - The EPA may ask you to respond to specific questions or
organize comments by referencing a Code of Federal Regulations (CFR) part or section
iii. Explain why you agree or disagree; suggest alternatives and provide
iv. Describe any assumptions and provide any technical information and/or data
v. If you estimate potential costs or burdens, explain how you arrived at your
vi. Provide specific examples to illustrate your concerns, and suggest
vii. Explain your views as clearly as possible, avoiding the use of profanity or
viii. Make sure to submit your comments by the specified comment period
Commenters wishing to submit proprietary information for consideration must
clearly distinguish such information from other comments and clearly label it as CBI.
Send submissions containing such proprietary information directly to the following
address, and not to the public docket, to ensure that proprietary information is not
inadvertently placed in the docket: Attention: Mr. Roberto Morales, U.S. Environmental
Protection Agency, OAQPS Document Control Officer, 109 TW Alexander Drive, Room
C404-02, RTP, NC, 27711. The EPA will disclose information identified as CBI only to
the extent allowed by the procedures set forth in 40 CFR Part 2. If no claim of
confidentiality accompanies a submission when it is received by the EPA, the
information may be made available to the public without further notice to the commenter.
In addition to being available in the docket, an electronic copy of the proposed
changes to Method 301 is also available on the Internet through the Technology Transfer
Network (TTN). Following signature, a copy of Method 301 will be posted on the TTN’s
policy and guidance page for newly proposed or promulgated rules
http://www.epa.gov/ttn/oarpg. The TTN provides information and technology exchange
in various areas of air pollution control. If more information regarding the TTN is
Today’s action proposes to amend EPA’s Method 301; Field Validation of
Pollutant Measurement Methods from Various Waste Media. Method 301 can be found
in Appendix A of 40 CFR, Part 63 (Test Methods). Method 301 was promulgated with
40 CFR, Part 63, Subpart D (Regulations Governing Compliance Extensions for Early
Reductions of Hazardous Air Pollutants)(58 FR 27338, June 13, 1991) pursuant to
Section 112 of the Clean Air Act (as amended in 1990). You would use Method 301
whenever you propose to use a test method to meet an EPA requirement in absence of a
validated method. The method specifies procedures for determining and documenting
the precision and bias of measured concentrations from various media (e.g., sludge,
exhaust gas, wastewater) at the level of an applicable standard for a source. Bias (or
systemic error) is established by comparing your proposed method against a reference
value. A correction factor is employed to eliminate/minimize bias. This correction factor
is established from data obtained during your validation test. Methods that have bias
correction factors outside a specified range are considered unacceptable. Method
precision (or random error) at the level of the standard must be demonstrated to be as
precise as the validated method for acceptance.
Today’s action proposes to amend those provisions by correcting technical errors,
and simplifying and clarifying procedures. Section II of this preamble discusses the
proposed Method 301 rule, and Section III presents the administrative requirements for
In compliance with President Clinton’s June 1, 1998, Executive Memorandum on
Plain Language in government writing, Method 301 has been rewritten in plain language.
The use of plain language clarifies the requirements of Method 301, thus, reducing the
burden (time) associated with understanding the Method. When Method 301 refers to
“you,” it means the owner or operator of the affected source.
We have reorganized the information in Method 301 to make it easier to follow
the requirements and to understand the relationships among the various requirements.
The reorganization did not create new requirements, but it does incorporate various
corrections to technical errors and technical revisions. These corrections and revisions,
as well as the rationale for the changes, are discussed in Sections III C and D of this
Section 17.0 of today’s rule (What detection limits must I use?) shall apply
instead of Section 9.0 (Practical Quantitation Limits) of the promulgated Method 301
rule. We have retained all other sections from the promulgated Method 301, but you will
find them in new places. Where necessary for clarity, we have put the information from
one section of Promulgated Method 301 into several new sections. Some information has
been put into tables at the end of the Method. Section 2.0 presents new information. It
has been added to explain when you must use Method 301 and to identify the
requirement for receiving written approval from the Administrator before using the
alternative test method. Table 1 of this preamble specifies where the sections in the
promulgated Method 301 are found in the proposed Method 301 rule.
The equations of the promulgated Method 301 have also been amended. Some of
the promulgated equations have been modified; some have been replaced by other
equations, and some have simply been renumbered or reordered. The technical reasons
for the changes to the equations are discussed in Section III. D of this preamble. Table 2
indicates whether each equation in the proposed amended rule has changed from the
promulgated rule. Equations 301-5 and 301-10 (correction factors when using isotopic
spiking and paired sampling systems with a validated test method comparison) of
promulgated Method 301 rule have been removed for the reasons discussed in Section III
D of this preamble.
Table 1. Comparison of Sections in Proposed Method 301. to Those in
Promulgated Method 301.
Proposed New Section                                Promulgated Method Section
Using Method 301
1.0     What is the purpose of Method 301?          1.1     Applicability
2.0     When must I use Method 301?                 None
3.0     What does Method 301 include?               1.1.2
4.0     How do I perform Method 301?                1.2     Principle
Reference Materials and Performance Audits
5.0     What reference materials must I use?        3.0     Reference Materials
6.0     How do I conduct the performance audit?     4.0     EPA Performance Audit Materials
7.0     What sampling procedures must I use?        5.0     Procedure for Determination of Bias
and Precision in the Field
8.0     How do I ensure sample stability?           8       Procedure for Sample Stability in Bias
and Precision Evaluations
9.0     What are the requirements for bias?         1.2.1   Bias
10.0    What are the requirements for precision?    1.2.2   Precision
11.0    What calculations must I perform for        6.1     Isotopic Sampling
isotopic sampling?
12.0    What calculations must I perform for        6.2.1   Comparison with a validated method:
comparison with a validated method if I             Paired Sampling Systems
am using paired sampling systems?
13.0    What calculations must I perform for        6.2.2   Comparison with a validated method:
comparison with a validated method if I             Quadruplet Replicate Sampling
am using quadruplet replicate sampling              Systems
14.0    What calculations must I perform for        6.3     Analyte Spiking
analyte spiking?
15.0    How do I conduct followup tests?            11      Followup Testing
16.0    How do I use and conduct ruggedness         7       Ruggedness Testing
17.0    What detection limits must I use?           9       Practical Limit of Quantitation
18.0    How do I apply for approval to use an       10       Field Validation Report Requirements
19.0    How do I request a waiver?                  1.1.1    Procedure for Obtaining a Waiver
20.0    What definitions apply to this method?      2        Definitions
21.0    Where can I find additional information?    13       Bibliography
Table 2. Equations in Proposed Method 301
The following equation in proposed Method 301. . .      is...                 The following
Method 301...
301-1     Difference in Sample Results                  new
301-7     Relative Magnitude of Bias                    new
301-9     Relative Magnitude of Bias for Comparing      new
Against Validated Methods Using Paired
Equations When Using Isotopic Spiking
301-4     Numerical Value of Bias                       a revision of         301-1
301-5     Standard Deviation                            the same as           301-2
301-6     t Test                                        a replacement for     301-3 and 301-4
301-8     Relative Standard Deviation                   a revision of         301-6
Equations When Comparing Against Validated Method Using Paired Sampling Systems
301-2     Standard Deviation                            for paired sampling   301-2
301-3     t Test                                        the same as           301-9
301-10    Variance                                      a replacement for     301-7
301-11    Pooled Variance                               new
301-12    Alternative Test Method Variance              a replacement for     301-9a
301-13    F test                                        the same as           301-8
Equations When Comparing Against Validated Method Using Quadruplet Replicate Sampling
301-14    Bias                                          the same as           301-12
301-15    Alternative Test Method Variance              the same as           301-11
Equations When Using Analyte Spiking
301-16    Bias                                          the same as           301-14
301-17    t Test                                        a replacement for     301-4
301-18    Standard Deviation for Spiked Samples         a revision of         301-13
301-19    Standard Deviation for Unspiked Samples       a replacement for     301-13 and 301-6
The following equation in proposed Method 301. . .   is...               The following
301-20    F test                                     new
301-21    Pooled Standard Deviation                  a replacement for   301-15
Some of the equations in promulgated Method 301 are incorrect. We are
proposing to correct these equations with today’s action. For a discussion of new
equations due to technical revisions, see Section III D of this preamble. We revised
several equations to clarify their intent. Under the new numbering system, the revised
equations are 301-4 (numerical value of bias), 301-6 (t Test), 301-8 (relative standard
deviation), 301-18 (standard deviation for spiked samples), and 301-19 (standard
deviation for unspiked samples). These changes were editorial/defining changes and not
technical changes. For example, we added or changed subscripts or redefined a variable.
We added Equations 301-1, 301-7, and 301-9. Equation 301-1 is used to
calculate the difference in minimum and maximum storage times under the new sample
stability procedures. Equation 301-7 is used to calculate relative magnitude of bias for
isotopic spiking. This new equation was needed when we dropped the use of correction
factors. Likewise, Equation 301-9 was needed for calculating relative magnitude of bias
when comparing against a validated method using paired sampling systems.
We also added Equation 301-11 and changed Equations 301-12, 301-17, 301-18,
and 301-19 to correct technical errors in promulgated Method 301. Equations 301-11
(Pooled Variance) and 301-12 (Alternative Test Method Variance) are being proposed to
correct a technical error in the promulgated method. Addition and subtraction can only
be performed on the variance. It cannot be performed on the standard deviation. The
proposed Equation 301-11 is a new equation that calculates the pooled variance of both
methods when comparing against validated methods using paired sampling systems. The
proposed Equation 301-12 replaces the standard deviation with the variance.
Equations 301-17 (calculation of the test “t-statistic”) and 301-21 (calculation of
the pooled standard deviation) were changed because the divisor was wrong. Equation
301-20 (F test) was added so that the tester could determine if the spiked and unspiked
samples had the same precision, thereby allowing them to be pooled to calculate the
overall precision.
The proposed Equation 301-2 (Standard Deviation) replaces the promulgated
Equation 301-2 when comparing against validated methods using paired sampling
systems. The text in promulgated 6.2.1.4 directs the analyst to determine the mean of the
paired sample differences by substituting dm (mean of the paired sample differences) and
di (standard deviation of the differences) for Si and Sm in the proposed Equation 301-2.
We created the proposed Equation 301-2 to incorporate these changes.
We are proposing five major technical changes to Method 301. These technical
(1) Replacing the Practical Limit of Quantitation (PLQ) with a procedure to
determine the Limit of Detection,
(2) Revising the bias acceptance criteria and eliminating correction factors,
(3) Revising precision acceptance criteria when using analyte spiking,
(4) Allowing analyte spiking even when there is an existing test method, and
(5) Establishing new procedures for ensuring sample stability.
1. Practical Limit of Quantitation. We are proposing to replace the determination
of the PLQ with a procedure to determine the Limit of detection (LOD). The purpose of
establishing a measurement limit is to ensure that a test method is appropriate for its
intended use. The LOD is a better parameter for this purpose.
The PLQ is defined as the level or concentration at which the precision of a test
method reaches an acceptable value. There are several problems with this concept. The
first is the idea that there is an absolute value for acceptable precision. To a certain
extent, a tester can compensate for imprecision by collecting additional data so there is
no absolute level at which the imprecision of a test method becomes so great that the
method is no longer useful. This concept works best when the precision of the test
method is independent of the concentration of the analyte being measured. As the
concentration of the analyte increases, the imprecision of the method as a percentage of
the measured quantity decreases. In this case, the relative imprecision will actually
decrease as the quantity measured increases.
However, for most environmental measurements, it appears that the precision is a
function of the concentration of the analyte being measured. Thus, the relative
imprecision will not decrease as the quantity measured increases. In this case, the PLQ
The LOD is the minimum level or concentration of an analyte that produces a
signal or response that is distinguishable from the signal or response produced when no
analyte is present. This is a measurable quantity that can be determined regardless of the
method’s precision or whether that precision varies with the level of the analyte. For all
of these reasons, we believe that the LOD is a more useful parameter to characterize a
test method’s performance.
2. Bias Acceptance Criteria. We are also proposing to change the acceptance
criteria for the bias in a proposed alternative method from + 30% to + 10% and
concurrently to eliminate the requirement for correcting all data collected with the
method. We believe that twelve pairs of results from a single source are not sufficient to
allow us to establish a correction factor that can or should be applied to all future uses of
the method. In addition, keeping track of correction factors to ensure that they are
applied to future uses of the method is a huge administrative burden both for the users of
the method and the regulatory agencies who oversee its use. If we do not use correction
factors, method biases of up to 30 percent are undesirably large. Therefore, we are
proposing to reduce the acceptable bias to + 10% and eliminate the requirement to correct
the data. With this change, the bias of alternative methods will be acceptable; the criteria
for using the alternative test method at similar sources will be clear, and the
administrative burden will be reduced.
3. Precision Acceptance Criteria. We are proposing to change the acceptance
criteria for method precision when using analyte spiking from + 50% to + 20%. In
addition, we are proposing to eliminate the requirement for different numbers of replicate
samples depending on the method’s relative precision. All future testing using an
alternative test method at similar sources will require only three replicate samples. The
requirement in the existing procedure was an attempt to compensate for the poorer
precision of some candidate alternative test methods by increasing the amount of data
that the user was required to collect. While more data does compensate for the
imprecision of any future data collected with the method, allowing candidate alternative
test methods with poor precision creates other problems. One problem is that poor
precision makes it more difficult to detect potential bias in a test method. For this reason,
we are proposing to tighten the acceptance criteria for the precision of candidate
4. Analyte Spiking. We are also proposing to allow the tester to use analyte
spiking to evaluate an alternative test method even when there is an existing compliance
test method. If the NESHAP specifies a test method, promulgated Method 301 requires
the tester to evaluate an alternative method by direct comparison. We believe that this is
too restrictive in some cases. For example, a change in process technology may cause a
previously unbiased test method to develop an interference that biases its results. If the
tester is required to compare the alternative test method to the existing test method, the
alternative method could never demonstrate acceptable performance if it were unbiased.
We believe that it is sufficient for an alternative method to demonstrate acceptable
performance by using the analyte spiking procedure and that this is a reasonable
alternative to direct comparison.
5. Sample Stability. Finally, we are proposing procedures for sample stability.
Method 301 previously lacked specific procedures for ensuring that samples collected
under proposed alternative methods were analyzed within an appropriate time. New
Section 8.4 includes a requirement to calculate the difference in the sampling results at
the minimum and maximum storage times, determine the standard deviation of the
differences, and test the difference in the results for statistical significance by calculating
the t-statistic and determining if the mean of the differences between the initial results
and the results after storage is significant at the 95 percent confidence level. We have
also added Table 1 to compare the calculated t-statistic with the critical value of the t-
statistic. These procedures are necessary to ensure sample stability and should have been
included in promulgated Method 301.
Under Executive Order 12866 (58 FR 51735, October 4, 1993), the EPA must
determine whether the regulatory action is &quot;significant&quot; and, therefore, subject to review
by the Office of Management and Budget (OMB) and the requirements of the Executive
Order. The Executive Order defines &quot;significant regulatory action&quot; as one that is likely
(1) Have an annual effect on the economy of $100 million or more or adversely
(2) Create a serious inconsistency or otherwise interfere with an action taken or
(3) Materially alter the budgetary impact of entitlements, grants, user fees, or
loan programs, or the rights and obligation of recipients thereof; or
(4) Raise novel legal or policy issues arising out of legal mandates, the
President&#39;s priorities, or the principles set forth in the Executive Order.
It has been determined that this proposed regulatory action is not a &quot;significant
regulatory action&quot; under the terms of Executive Order 12866 and is, therefore, not subject
to OMB review.
This action does not impose or change the information collection burden under
the provisions of the Paperwork Reduction Act 44 U.S.C. 3501, et seq. Burden means
the total time, effort, or financial resources expended by persons to generate, maintain,
retain, or disclose or provide information to or for a Federal agency. This includes the
time needed to review instructions; develop, acquire, install, and utilize technology and
systems for the purposes of collecting, validating, and verifying information, processing
and maintaining information, and disclosing and providing information; adjust the
existing ways to comply with any previously applicable instructions and requirements;
train personnel to be able to respond to a collection of information; search data sources;
complete and review the collection of information; and transmit or otherwise disclose the
An agency may not conduct or sponsor, and a person is not required to respond to
a collection of information unless it displays a currently valid OMB control number. The
OMB control numbers for EPA’s regulations are listed in 40 CFR Part 9 and 48 CFR
The RFA generally requires an agency to prepare a regulatory flexibility analysis
of any rule subject to notice and comment rulemaking requirements under the
Administrative Procedure Act or any other statute unless the agency certifies that the rule
Small entities include small businesses, small organizations, and small governmental
For the purposes of assessing the impacts of today&#39;s proposed rule on small
entities, small entity is defined as: (1) A small business that meets the definitions for
small business based on the Small Business Association (SBA) size standards which, for
this proposed action, are operations that have fewer than 1,000 employees; (2) A small
governmental jurisdiction that is a government of a city, county, town, school district or
special district with a population of less than 50,000; and (3) A small organization that is
any not-for-profit enterprise which is independently owned and operated and is not
After considering the economic impacts of today’s proposed rule on small
entities, I certify that this proposed action will not have a significant economic impact on
a substantial number of small entities. In determining whether a rule has significant
economic impact on a substantial number of small entities, the impact of concern is any
significant adverse economic impact on small entities since the primary purpose of the
regulatory flexibility analysis is to identify and address regulatory alternatives “which
minimize any significant economic impact of the proposed rule on small entities,” (5
U.S.C. 603 and 604). Thus, 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, or otherwise has a positive economic effect on all of the small entities subject to
the rule. This proposed rule will not impose any requirements on small entities. This
rule establishes procedures for using alternative methods. As such, small entities and
other sources are not required to comply with this proposed rule, but may elect to use
Method 301. The proposed rule offers additional flexibility to all sources, including
small entities that may be subject to requirements under the CAA. Additionally, this
proposed amended rule clarifies and simplifies the procedures for using alternative
methods. We continue to be interested in the potential impacts of the proposed rule on
small entities and welcome comments on issues related to such impacts.
Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), Public Law
1044, establishes requirements for Federal agencies to assess the effects of their
regulatory actions on State, local, and tribal governments and the private sector. Under
Section 202 of the UMRA, the EPA generally must prepare a written statement, including
cost-benefit analysis, for proposed and final rules with &quot;Federal mandates&quot; that may
result in expenditures to State, local, and tribal governments, in the aggregate, or to the
private sector, of $100 million or more in any one year. Before promulgating an EPA
rule for which a written statement is needed, Section 205 of the UMRA generally
requires the EPA to identify and consider a reasonable number of regulatory alternatives
and adopt the least costly, most cost-effective, or least burdensome alternative if the
Administrator publishes with the final rule an explanation why that alternative was not
adopted. Before EPA establishes any regulatory requirements that may significantly or
uniquely affect small governments, including tribal governments, it must have developed
under Section 203 of the UMRA a small government agency plan. The plan must
provide for notifying potentially affected small governments, enabling official of affected
small governments to have meaningful and timely input in the development of EPA
regulatory proposals with significant Federal intergovernmental mandates, and
informing, educating, and advising small governments on compliance with the regulatory
We have determined that today’s proposed amended rule does not contain Federal
mandates for State, local, or tribal governments or the private sector. Therefore, this
proposed amended rule is not subject to the requirements of Sections 202 and 205 of the
Executive Order 13132, entitled &quot;Federalism&quot; (64 FR 43255, August 10, 1999),
requires the EPA to develop an accountable process to ensure “meaningful and timely
input by State and local officials in the development of regulatory policies that have
federalism implications.&quot; &quot;Policies that have federalism implications&quot; is defined in the
Executive Order to include regulations that have &quot;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.&quot;
Under Executive Order 13132, the EPA may not issue a regulation that has
federalism implications, that imposes substantial direct compliance costs, and that is not
required by statute, unless the Federal government provides the funds necessary to pay
the direct compliance costs incurred by State and local governments, or the EPA consults
with State and local officials early in the process of developing the proposed regulation.
The EPA also may not issue a regulation that has federalism implications and that
preempts State law unless the Agency consults with State and local officials early in the
process of developing the proposed regulation.
Today’s proposed amended rule will not have federalism implications. They will
not have substantial direct effects on the States, on the relationship between the national
government and the States, or on the distribution of power and responsibilities among the
various levels of government, as specified in Executive Order 13132. Today’s proposed
amended rule clarifies and simplifies the procedures for using alternative methods. Thus,
the requirements of Section 6 of the Executive Order do not apply.
Executive Order 13175, entitled “Consultation and Coordination with Indian
Tribal Governments” (65 FR 67249, November 9, 2000), requires EPA to develop an
accountable process to ensure “meaningful and timely input by tribal officials in the
development of regulatory policies that have tribal implications.” The proposed amended
rule does not have tribal implications, as specified in Executive Order 13175. The
proposed action serves to clarify and simplify procedures for using alternative methods.
Therefore, Executive Order 13175 does not apply to the proposed amended rule.
G. Executive Order 13045 - Protection of Children from Environmental Health Risks
Executive Order 13045, “Protection of Children from Environmental Health
Risks and Safety Risks” (62 FR 19885, April 23, 1997), applies to any rule that the EPA
determines is: (1) &quot;economically significant&quot; as defined under E.O. 12866; and (2)
concerns an environmental health or safety risk that the EPA has reason to believe may
have a disproportionate effect on children. If the regulatory action meets both criteria,
the EPA must evaluate the environmental health or safety effects of the planned rule on
children and explain why the planned regulation is preferable to other potentially
effective and reasonable alternatives considered by the EPA.
The EPA interprets Executive Order 13045 as applying only to those regulatory
actions that are based on health or safety risks, such that the analysis required under
Section 5-501 of the Executive Order has the potential to influence the regulation. The
proposed amended rule is not subject to Executive Order 13045 because it is not
economically significant as defined in Executive Order 12866, and because this proposed
amended rule is not based on health or safety risks. Thus, Executive Order 13045 does
not apply to this proposed amended rule.
This rule is not subject to Executive Order 13211, “Actions Concerning
Regulations That Significantly Affect Energy Supply, Distribution, or Use”
(66FR28355(May22, 2001)) because it is not a significant regulatory action under
Section 112(d) of the National Technology Transfer and Advancement Act of
1995 (NTTAA), Public Law No. 104-113, Section 12(d)915 U.S.C. 272 note), directs all
Federal agencies to use voluntary consensus standards instead of government unique
Method 301 - Page 24 of 62
standards in their regulatory activities unless to do so would be inconsistent with
specifications, test methods, sampling procedures, and business practices, etc.) that are
developed or adopted by one or more voluntary consensus standards bodies. Examples
of organizations, generally regarded as voluntary consensus standards bodies, include the
American Society for Testing and Materials (ASTM), the National Fire Protection
Association (NFPA), and the Society of Automotive Engineers (SAE). The NTTAA
requires Federal agencies like EPA to provide Congress through OMB with explanations
when an agency decides not to use available and applicable voluntary consensus
standards. This proposed amended rule clarifies and simplifies, already promulgated,
procedures for use of alternative standards. The intent of the Method 301 is to allow
owners and operators of sources regulated by Part 63 standards the flexibility and option
to use alternative standards. Today’s proposed amended rule is intended to simplify and
clarify the procedures for using alternative standards. Therefore, the EPA is not
considering the use of any voluntary consensus standards with today’s proposed action.
Environmental protection, Alternative test method, Air pollution control, Field
validation, Hazardous air pollutants, Method 301.
For the reasons stated in the preamble, Title 40, Chapter I, Part 63, of the Code of
the Federal Regulations is proposed to be amended as follows:
2. Part 63 is amended by revising Appendix A to read as follows:
Appendix A to Part 62 - Test Methods
Method 301--Field Validation of Pollutant Measurement Methods From Various Waste
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?
5.0 What reference materials must I use?
6.0 How do I conduct the performance audit?
7.0 What sampling procedures must I use?
8.0    How do I ensure sample stability?
9.0 What are the requirements for bias?
10.0 What are the requirements for precision?
11.0 What calculations must I perform for isotopic spiking?
12.0 What calculations must I perform for comparison with a validated method if I am
using paired sampling systems?
13.0 What calculations must I perform for comparison with a validated method if I am
using quadruplet replicate sampling systems?
14.0 What calculations must I perform for analyte spiking?
15.0 How do I conduct tests at similar sources?
16.0 How do I use and conduct ruggedness testing?
17.0 What detection limits must I use?
18.0 How do I apply for approval to use an alternative test method?
19.0 How do I request a waiver?
20.0 What definitions apply to this method?
21.0 Where can I find additional information?
This method describes the minimum procedures that you, the owner or operator of
an affected source subject to requirements under 40 CFR Part 63, must use to validate an
alternative test method to a test method required in 40 CFR Part 63.
If you want to request to use an alternative test method to meet requirements in a
subpart of 40 CFR Part 63, you must use Method 301 to validate the alternative test
method. You must request approval to use the alternative test method according to the
procedures in Section 18 and &#167;63.7(f). You must receive the Administrator’s written
approval to use the alternative test method before you use the alternative test method to
meet requirements under 40 CFR Part 63. In some cases, the Administrator may decide
to waive the requirement to use Method 301. Section 19 describes the requirements for
obtaining a waiver.
This method includes minimum procedures to determine and document
systematic error (bias) and random error (precision) of measured concentrations from
exhaust gases, wastewater, sludge, and other media. It contains procedures for ensuring
sample stability if such procedures are not included in the test method. This method also
includes optional procedures for ruggedness and detection limits.
First, you introduce a known concentration of an analyte or compare the
alternative test method against a validated test method to determine the alternative test
method&#39;s bias. Then, you collect multiple, collocated simultaneous samples to determine
the alternative test method&#39;s precision. Sections 5.0 through 17.0 describe these
You must use reference materials (that is, analytes) at the level of the applicable
emission limitation or standard that the subpart in 40 CFR Part 63 requires. If you want
to expand the applicable range of the method, you must conduct additional runs with
higher and lower analyte concentrations. The additional runs must be conducted
according to the ruggedness procedures in 16.0. You must use the analytes according to
the procedures in 5.1 through 5.4.
5.1 Exhaust Gas Tests. You must get a known concentration of each analyte
from an independent source such as a speciality gas manufacturer, specialty chemical
company, or chemical laboratory. You must also get the manufacturer’s stability data for
the analyte concentration and recommendations for recertification.
5.2 Tests for Other Waste Media. You must get the pure liquid components of
each analyte from an independent manufacturer. The manufacturer must certify the
purity and shelf life of the pure liquid components. You must dilute the pure liquid
components in the same type medium as the waste from the affected source. You must
verify the accuracy of the concentration of each diluted analyte by comparing its
response to the pure liquid components.
5.3 Surrogate Analytes. If you demonstrate to the Administrator’s satisfaction
that a surrogate compound behaves as the analyte does, then you may use surrogate
compounds for highly toxic or reactive compounds. A surrogate may be an isotope or
one that contains a unique element (for example, chlorine) that is not present in the
source or a derivation of the toxic or reactive compound, if the derivative formation is
part of the method’s procedure. You may use laboratory experiments or literature data to
show behavioral acceptability.
5.4 Isotopically Labeled Materials. Isotope mixtures may contain the isotope and
the natural analyte. The isotope labeled analyte concentration must be more than five
times the natural concentration of the analyte.
6.1 Getting Performance Audit Material. If EPA has performance audit material
for the analytes that you are testing, you must use it to assess method bias. You can get a
list of performance audit materials at http://www.epa.gov/ttn/emc/email.html#audit or by
contacting EMC at (919) 541-5545. You must request the performance audit material at
least 30 days before the validation test.
6.2 Sampling and Analyzing Performance Audit Material. You must sample and
analyze the performance audit material three times according to the instructions provided
with the audit sample. You must submit the three results with the field validation report.
Although there are no acceptance criteria for these performance audit results, you and the
Administrator may use them to assess the relative error of sample recovery, sample
preparation, and analytical procedures and then consider the relative error in evaluating
the measured emissions.
You may determine bias and precision by comparing against a validated test
method, using isotopic sampling, or using analyte spiking. Isotopic sampling can only be
used for procedures requiring mass spectrometry. You must collect samples according to
the requirements in Table 1. You must perform the sampling according to the procedures
in Sections 7.1 through 7.5.
7.1 Comparison Against a Validated Test Method. If you are comparing the
results from the validated test method, it is recommended that you conduct a performance
audit according to the procedures in Section 6.
7.2 Isotopic Spiking. Spike all 12 samples with the analyte at the concentration
in the applicable emission limitation or standard in the subpart of 40 CFR Part 63. If
there is no applicable emission limitation or standard, spike at the expected level of the
samples. Follow the appropriate spiking procedures in 7.4.1 through 7.4.2 for the
applicable waste medium.
7.3 Analyte Spiking. In each quadruplet set, spike half of the samples (two out of
the four) with the analyte according to the applicable procedure in Section 7.4.
7.4 Spiking Procedure.
7.4.1 Gaseous Analyte with Sorbent or Impinger Sampling Trains. Sample the
analyte (in the laboratory or in the field) at a concentration that is close to the
concentration in the applicable emission limitation or standard in the subpart of 40 CFR
Part 63 (or the expected sample concentration where there is no standard) for the time
required by the method, and then sample the gas stream for an equal amount of time. The
time for sampling both the analyte and gas stream should be equal; however, the time
should be adjusted to avoid sorbent breakthrough. The stack gas and the gaseous analyte
may be sampled at the same time. The analyte must be introduced as close to the tip of
the sampling train as possible.
7.4.2 Gaseous Analyte with Sample Container (Bag or Canister). Spike the
sample containers after completion of each test run with an amount equal to the
Part 63 (or the expected sample concentration where there is no standard). The final
concentration of the analyte shall approximate the level of the emission concentration in
the stack. The volume amount of analyte shall be less than 10 percent of the sample
7.4.3 Liquid and Solid Analyte with Sorbent or Impinger Trains. Spike the trains
with an amount equal to the concentration in the applicable emission limitation or
standard in the subpart of 40 CFR Part 63 (or the expected sample concentration where
there is no standard) before sampling the stack gas. If possible, do the spiking in the
field. If it is not possible to do the spiking in the field, you can do it in the laboratory.
7.4.4 Liquid and Solid Analyte with Sample Container (Bag or Canister). Spike
the containers at the completion of each test run with an amount equal to the
Part 63 (or the expected sample concentration where there is no standard).
7.5 Probe Placement and Arrangement for Stationary Source Stack or Duct
Sampling. To sample a stationary source as defined in 40 CFR 63.2, you must place the
probe according to the procedures in 7.5. You must place the probes in the same
7.5.1 For Paired Sample Probes, the sample probe tip should be 2.5 cm from the
outside edge of the other sample probe, with a pitot tube on the outside of each probe.
The Administrator may approve a validation request where other paired arrangements for
the pitot tube are used.
7.5.2 For Quadruplet Sampling Probes, the tips should be in a 6.0 cm x 6.0 cm
square area measured from the center line of the opening of the probe tip with a single
pitot tube in the center or two pitot tubes with their location on either side of the probe tip
configuration. You must propose an alternative arrangement whenever the cross-
sectional area of the probe tip configuration is approximately 5 percent or more of the
stack or duct cross-sectional area.
8.0 How do I ensure sample stability?
8.1 Developing Storage and Analysis Procedures. If the alternative test method
includes well-established procedures supported by experimental data for sample storage
and the time within which the collected samples must be analyzed, you must store the
samples according to the procedures in the alternative test method. You are not required
to conduct the procedures in Section 8.2 or 8.3. If the alternative test method does not
include such procedures, you must propose procedures for storing and analyzing samples
to ensure sample stability. At a minimum, your proposed procedures must meet the
requirements in Section 8.2 or 8.3. The minimum storage time should be as soon as
possible, but no longer than 24 hours after collection of the sample. The maximum
storage time should be four weeks or less.
8.2 Storage and Sampling Procedures for Stack Test Emissions. You must store
and analyze samples of stack test emissions according to Table 3. If you are using
analyte spiking procedures, you must include equal numbers of spiked and unspiked
8.3 Storage and Sampling Procedures for Testing Other Waste Media. You must
analyze half of the replicate samples at the proposed minimum storage time and the other
half at the proposed maximum storage time to identify the effect of storage times on
analyte samples. The minimum storage time should be as soon as possible, but no longer
than 24 hours after collection of the sample. The maximum storage time should be two
8.4 Sample Stability. After you have conducted sampling and analysis
according to 8.2 or 8.3, compare the results at the minimum and maximum storage times.
Calculate the difference in the results using Equation 301-1.
di = Rmin i − Rmax i                            Eq. 301-1
Where            di = difference between the results of the ith sample.
Rmini = results from the ith sample at the minimum storage time
Rmaxi = results from the ith sample at the maximum storage time.
8.4.1 Standard Deviation. Determine the standard deviation, SDd, of the
differences, di&#39;s, of the paired samples using Equation 301-2.
Eq.    301-2
Vm =    validated method
Pm =    proposed alternative test method
di =    The difference between the i-th pair of samples, Vm - Pm
dm = The mean of the paired sample differences.
n = total number of paired samples
8.4.2 t Test. Test the difference in the results for statistical significance by
calculating the t-statistic and determining if the mean of the differences between the
initial results and the results after storage is significant at the 95 percent confidence level.
Calculate the value of the t-statistic using Equation 301-3.
Eq. 301-3
Where:          n is the total number of paired samples.
Compare the calculated t-statistic with the critical value of the t-statistic from
Table 2. If the calculated t-value is less than the critical value, the difference is not
statistically significant, thus, the sampling and analysis procedure ensures stability, and
you may submit a request for validation of the proposed alternative test method. If the
calculated t-value is greater than the critical value, the difference is statistically
significant and you must repeat the procedures in 8.2 or 8.3 with new samples using
shorter proposed maximum storage times.
You must establish bias by comparing the results of the sampling using the
alternative test method against a reference value. The bias must be no more than +/-10%
for the alternative test method to be acceptable.
At a minimum, you must use paired sampling systems to establish precision. If
you are using analyte spiking, including isotopic samples, the precision expressed as the
relative standard deviation (RSD), of the alternative test method at the level of the
applicable emission limitation or standard in the subpart of 40 CFR Part 63 must be less
than or equal to 20 percent. If you are comparing to a validated test method, the
alternative test method must be at least as precise as the validated method at the level of
the applicable emission limitation or standard in the subpart of 40 CFR Part 63 as
determined by an F test.
You must analyze the bias, precision, relative standard deviation, and data
acceptance for isotopic spiking tests according to the provisions in Sections 11.1 through
11.1. Numerical Bias. Calculate the numerical value of the bias using the results
from the analysis of the isotopically spiked field samples and the calculated value of the
isotopically labeled spike according to Equation 301-4.
Eq. 301-4
B=     Bias at the spike level.
11.2. Standard Deviation. Calculate the standard deviation of the Si values
according to Equation 301-5.
Eq. 301-5
Si =    Measured value of the isotopically labeled analyte in the i-th field sample,
n =     Number of isotopically spiked samples, 12.
11.3 t Test. Test the bias for statistical significance by calculating the t-statistic
using Equation 301-6. Use the standard deviation determined in Section 11.2 and the
numerical bias determined in section 11.1.
Eq. 301-6
Compare the calculated t-value with the critical value of the two-sided t-distribution at
the 95 percent confidence level and n-1 degrees of freedom. When spiking is conducted
according to the procedures specified in Sections 7.2 and 7.4 as required, this critical
value is 2.201 for the eleven degrees of freedom. If the calculated t-value is less than the
critical value, the bias is not statistically significant and the data are acceptable. If the
calculated t-value is greater than the critical value, the bias is statistically significant and
you must evaluate the relative magnitude of the bias using Equation 301-7.
BR =                x    100%                         Eq. 301-7
BR = Relative bias.
If the relative bias is less than or equal to 10 percent, then the data are acceptable. You
may proceed to evaluate the precision. If not the candidate method will not meet the
requirements of Method 301.
11.4 Relative Standard Deviation. Calculate the RSD according to Equation 301-
Eq. 301-8
where Sm is the measured mean of the isotopically labeled spiked samples. The data and
alternative test method are unacceptable if the RSD is greater than 20 percent.
You must analyze the data for comparison with a validated method according to
Section 12. Conduct these procedures to determine if an alternative test method produces
results equivalent to a validated method. If the data from the alternative test method fail
either the bias or precision test, the data and the alternative test method are unacceptable.
12.1 Bias Analysis.
12.1.1 Standard Deviation. Determine the standard deviation, SDd, of the
12.1.2 t Test. Test the bias for statistical significance by calculating the t-statistic
and determine if the mean of the differences between the alternative test method and the
validated method is significant at the 95 percent confidence level. Calculate the value of
the t-statistic using Equation 301-3. For the spiking procedure for paired sampling
systems, according to Section 7.1 and Table 1, n equals nine.
Compare the calculated t-statistic with the critical value of the t-statistic. When
nine runs are conducted, as specified in Section 7.1 and Table 1, the critical value of the
t-statistic is 1.397 for eight degrees of freedom. If the calculated t-value is less than the
you must evaluate the relative magnitude of the bias using Equation 301-9. If the relative
bias is less than or equal to 10 percent, then the data are acceptable. Proceed to evaluate
BR =            x 100%                                                    Eq. 301-9
B = Bias = mean of the di’s
VS = mean measured by the validated method
12.2. Precision. Compare the variance of the alternative test method to that of
the validated method. If a significant difference is determined using the F test, the
alternative test method and the results are rejected. If the F test does not show a
significant difference, then the alternative test method has acceptable precision. This
procedure requires that you know the standard deviation of the validated method, SDv.
Use the value furnished with the method. If the standard deviation of the validated
method is not available, the paired replicate sampling procedure may not be used.
12.2.1 Variance. Calculate the variance of the validated method, Sv2, using
Equation 301-10.
Eq. 301-10
SDv = Standard deviation provided with the validated method.
12.2.2 Pooled Variance. Calculate the pooled variance of both methods, S2pooled,
according to Equation 301-11.
Eq. 301-11
di = The difference between the i-th pair of validated and alternative
method samples.
n = The number of pairs of samples.
12.2.3 Alternative Test Method Variance. Calculate the variance of the alternative test
method, S2p, from the S2pooled using Equation 301-12.
Eq. 301-12
(If S2v &gt; S2pooled, let S2p = S2pooled/2).
12.2.4 The F test. Determine if the variance of the alternative test method is
significantly different from that of the validated method by performing the F test.
Calculate the experimental F-value using Equation 301-13.
Eq. 301-13
Compare the experimental F value with the critical range of F at a 95 percent confidence
level. When the procedure specified in Section 7.1 and Table 1 for paired trains is
followed as required, the critical range is 0.291 to 3.44. If the calculated F is outside the
critical range, the difference in precision is significant and the data and alternative test
method are unacceptable.
If you are using quadruplet replicate sampling systems to compare an alternative
test method to a validated method, then you must analyze the data according to the
provisions in 13.0. If the data from the alternative test method fail either the bias or
precision test, the data and the alternative test method are unacceptable. If the
Administrator determines that the affected source has highly variable emission rates, the
Administrator may require additional precision checks.
13.1 Bias Analysis. Test the bias for statistical significance at the 95 percent
confidence level by calculating the t-statistic.
13.1.1 Bias. Determine the bias, which is defined as the mean of the differences
between the alternative test method and the validated method (dm). Calculate di
according to Equation 301-14.
Eq. 301-14
Where:                    V1i = First measured value with the validated method in the i-th
V2i =   Second measured value with the validated method in the i-
P1i =   First measured value with the alternative test method in the
i-th sample.
P2i =   Second measured value with the alternative test method in
the i-th sample.
13.1.2 Standard Deviation of the Differences. Calculate the standard deviation of
the differences, SDd, using Equation 301-2.
13.1.3 T Test. Calculate the t-statistic using Equation 301-3, where n is the total
number of test sample differences (di). For the quadruplet sampling system procedure in
Section 7.1 and Table 1, n equals four. Compare the calculated t-statistic with the critical
value from of the t-statistic and determine if the bias is significant at the 95 percent
confidence level. When four runs are conducted, as specified in Section 7.2 and Table 1,
the critical value of the t-statistic is 1.638 for three degrees of freedom. If the calculated
t-value is less than the critical value, the bias is not statistically significant and the data
are acceptable. If the calculated t-value is greater than the critical value, the bias is
statistically significant and you must evaluate the relative magnitude of the bias using
Equation 301-9. If the relative bias is less than or equal to 10 percent, then the data are
acceptable. Proceed to evaluate precision of the alternative test method.
13.2 Precision. Compare the variance of the alternative test method to that of the
validated method. If a significant difference is determined using the F test, the
procedure requires the standard deviation of the validated method, SDv, to be known.
Use the value furnished with the method. If there are no published values, calculate the
variance of the validated method using Equation 301-15.
13.2.1 Alternative Test Method Variance. Calculate the variance of the
alternative test method, Sp2, according to Equation 301-15.
Eq. 301-15
di = The difference between the i-th pair of samples collected with the
13.2.2 The F test. Determine if the variance of the alternative test method is
greater than that of the validated method by calculating the F-value using Equation 301-
13. Compare the experimental F value with the critical range of F. The critical range is
0.264 to 3.79 for the 95 percent confidence level when the procedure specified in Section
7.1 and Table 1 for quadruplet trains is followed. If the calculated F is outside the critical
range, the difference in precision is significant, and the data and the alternative test
You must analyze the data for analyte spike testing according to Section 14.
14.1 Bias Analysis.
14.1.1 Bias. Calculate the numerical value of the bias using the results from the
analysis of the spiked field samples, the unspiked field samples, and the calculated value
of the spike using Equation 301-16.
Eq. 301-16
B =    Bias at the spike level.
Sm =   Mean of the spiked samples.
14.1.2 T Test. Test the bias for statistical significance by calculating the
t-statistic using Equation 301-17 and comparing it with the critical value of the two-sided
t-distribution at the 95 percent confidence level and n-2 degrees of freedom. This critical
value is 2.228 for the ten degrees of freedom.
Eq. 301-17
S2u = (SDu)2, SDu is calculated in Equation 301-19.
S2s = (SDs)2, SDs is calculated in Equation 301-18.
If the calculated t-value is less than the critical value, the bias is not statistically
significant and the data are acceptable. If the calculated t-value is greater than the critical
value, the bias is statistically significant and you must evaluate the relative magnitude of
the bias using Equation 301-7. If the relative bias is less than or equal to 10 percent, then
the data are acceptable. You may proceed to evaluate precision.
14.2 Precision. Calculate the standard deviation and the RSD of the alternative
14.2.1 Spiked Samples. Calculate the difference, di, between the pairs of the
spiked alternative test method measurements for each replicate sample set. Determine
the standard deviation (SDs) of the spiked values using Equation 301-18.
Eq. 301-18
Where:              dis = Difference between the i-th pair of spiked              samples.
n = Number of paired samples.
14.2.2 Unspiked Samples. Calculate the standard deviation of the unspiked
values using Equation 301-19.
Eq. 301-19
Where:              diu = Difference between the i-th pair of unspiked samples.
14.2.3 Pooled Standard Deviation. Calculate the pooled standard deviation of the
spiked and unspiked samples if the standard deviations are not significantly different.
Test for this difference using Equation 301-20.
Eq. 301-20
Where Su2 and Ss2 are defined in Equation 301-17.
For the case where n = 6 and a 95 percent confidence level, the standard deviations may
be pooled if the calculated F lies between 0.139 and 7.146. Calculate the pooled standard
deviation (SDpooled) using Equation 301-21.
Eq. 301-21
If the variances are significantly different and cannot be pooled, use the standard
deviation of the spiked samples for the bias analysis in Section 14.1.2.
14.2.4 Relative Standard Deviation. Calculate the RSD of the alternative test
method using Equation 301-8 and the pooled standard deviation determined from
Section 14.2.3. If the pooled standard deviation or the standard deviation from the
unspiked samples is used, Sm is the mean of the unspiked samples. If the standard
deviation of the spiked samples is used, Sm is the mean of the spiked samples. The data
and alternative test method are unacceptable if the RSD is greater than 20 percent.
If the Administrator has approved the use of an alternative test method to a test
method required in 40 CFR Part 63 for an affected source, and the Administrator has
approved the use of the alternative test method at your similar source according to the
procedures in 19.1.1, you must meet the requirements in this section. You must have at
least three replicate samples for each test that you conduct at the similar source. You
must average the results of the samples to determine the pollutant concentration.
If you want to use a validated test method at a concentration that is different from
the concentration in the applicable emission limitation in the subpart of 40 CFR Part 63
or for a source category that is different from the source category that the test method
specifies, then you must conduct ruggedness testing according to the procedures in
Citation 10 of Section 18.0 and submit a request for a waiver according to 19.1.1.
Ruggedness testing is a laboratory study to determine the sensitivity of a method
to parameters such as sample collection rate, interferant concentration, collecting medium
temperature, and sample recovery temperature. You conduct ruggedness testing by
changing several variables simultaneously instead of changing one variable at a time.
For example, you can determine the effect of seven variables in eight experiments instead
of one. (W.J. Youden, Statistical Manual of the Association of Official Analytical
Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp.
17.0 How do I determine the Limit of Detection for the alternative method?
17.1 Limit of Detection. The Limit of Detection (LOD) is the lowest level above
which you may obtain quantitative results with an acceptable degree of confidence. For
this protocol, the LOD is defined as 3 times the standard deviation, So, at the blank level.
This LOD corresponds to an uncertainty of &#177;30% at the 99 percent confidence level.
17.2 Purpose. The LOD will be used to establish the lower limit of the test
method. If the estimated LOD is no more than twice the calculated LOD, use Procedure I
in Table 4 to determine So. If the LOD is greater than twice the calculated LOD, use
Procedure II in Table 4 to determine So.
18.0 How do I apply for approval of an alternative test method?
18.1 Submitting Requests. You must request to use an alternative test method
according to the procedures in &#167;63.7(f). You may not use an alternative test method to
meet any requirement under 40 CFR Part 63 until the Administrator has approved your
request. The request must include a field validation reporting containing the information
in 18.2. The request must be submitted to the Director, Emissions Monitoring and
Analysis Division, U.S. Environmental Protection Agency, C304-02, Research Triangle
Park, NC 27711.
18.2 Field Validation Report. The field validation report must contain the
information in 18.2.1 through 18.2.9.
18.2.1 Regulatory objectives for the testing, including a description of the
reasons for the test, applicable emission limits, and a description of the source.
18.2.2 Summary of the results and calculations shown in Sections 7.0 through 17,
18.2.3 Analyte certification and value(s).
18.2.4 Laboratory demonstration of the quality of the spiking system.
18.2.5 Discussion of laboratory evaluations.
18.2.6 Discussion of field sampling.
18.2.7 Discussion of sample preparations and analysis.
18.2.8 Storage times of samples (and extracts, if applicable).
18.2.9 Reasons for eliminating any results.
19.1 Conditions for Waivers. If you meet one of the criteria in 19.1.1 through
19.1.3, the Administrator may waive the requirement to use the procedures in this method
to validate an alternative test method. In addition, if the EPA currently recognizes an
appropriate test method or considers the analyst’s test method to be satisfactory for a
particular source, the Administrator may waive the use of this protocol or may specify a
less rigorous validation procedure.
19.1.1 Similar Sources. If the alternative test method that you want to use has
been validated at another source and you can demonstrate to the Administrator’s
satisfaction that your affected source is similar to that source, then the Administrator may
waive the requirement for you to validate the alternative test method. One procedure you
may use to demonstrate the applicability of the method to your affected source is by
conducting a ruggedness test as described in 16.0.
19.1.2 Documented Methods. If the bias and precision of the alternative test
method that you are proposing have been demonstrated through laboratory tests or
protocols different from this method, and you can demonstrate to the Administrator’s
satisfaction that the bias and precision apply to your application, then the Administrator
may waive the requirement to use this method or to use part of this method.
19.1.3 Conditional Test Methods. If the alternative test method has been
demonstrated to be valid at several sources, you may ask the Administrator to designate
the alternative test method as a conditional test method. If the Administrator has
designated a test method as a conditional test method and you are using the conditional
method within its stated applicability, you do not have to validate it according to the
procedures in this method. You can find a list of conditional test methods at
http://www.epa.gov/ttn/emc/ctm.html.
19.2 Submitting Applications for Waivers. You must sign and submit each
request for a waiver from the requirements in this method in writing. The request must
be submitted to the Director, Emissions Monitoring and Analysis Division, U.S.
Environmental Protection Agency, C304-02, Research Triangle Park, NC 27711.
19.3 Information Application for Waiver. The request for a waiver must contain
a thorough description of the test method, the intended application, and results of any
validation or other supporting documents. The request for a waiver must contain, at a
minimum, the information in 19.3.1 through 19.3.4. The Administrator may request
additional information if necessary to determine whether this method can be waived for a
19.3.1 A Clearly Written Test Method. The method should be written preferably
in the format of 40 CFR 60, Appendix A Test Methods. It must include an applicability
statement, concentration range, precision, bias (accuracy), and minimum and maximum
storage time in which samples must be analyzed.
19.3.2 Summaries (see Section 18.3) of previous validation tests or other
supporting documents. If a different procedure from that described in this method was
used, you must submit documents substantiating the bias and precision values to the
Administrator’s satisfaction.
19.3.3 Ruggedness Testing Results. You must submit results of ruggedness
testing conducted according to Section 16, sample stability conducted according to
Section 8, and detection limits conducted according to Section 17, as applicable. For
example, you would not need to submit ruggedness testing results if you will be using the
method at the same concentration level as the concentration level at which it was
19.3.4 Applicability Statement and Arguments for Waiver Approval. Discussion
of the applicability statement and arguments for approval of the waiver. This discussion
should address as applicable the following: applicable regulation, emission standards,
effluent characteristics, and process operations.
Affected source means affected source as defined in 40 CFR 63.2 and in the
relevant subpart under 40 CFR Part 63.
Alternative test method means the sampling and analytical methodology selected
for field validation using the method described in this appendix.
Paired sampling system means a sampling system capable of obtaining two
replicate samples that were collected as closely as possible in sampling time and
Quadruplet sampling system means a sampling system capable of obtaining four
Surrogate compound means a compound that serves as a model for the types of
compounds being analyzed (i.e., similar chemical structure, properties, behavior). The
model can be distinguished by the method from the compounds being analyzed.
You can find additional information in the references in paragraphs 21.1 through
21.1 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.
21.2 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.
21.3 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,
21.4 Maxwell, E.A. 1974. Estimating variances from one or two measurements on
each sample. Amer. Statistician 28:96-97.
21.5 Midgett, M.R. 1977. How EPA Validates NSPS Methodology. Environ. Sci. &amp;
Technol. 11(7):655-659.
21.6 Mitchell, W.J., and M.R. Midgett. 1976. Means to evaluate performance of
stationary source test methods. Environ. Sci. &amp; Technol. 10:85-88.
21.7 Plackett, R.L., and J.P. Burman. 1946. The design of optimum multifactorial
experiments. Biometrika, 33:305.
21.8 Taylor, J.K. 1987. Quality Assurance of Chemical Measurements. Lewis
Publishers, Inc., pp. 79-81.
21.9 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.
21.10 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.
21.11 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.
21.12 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.
Table 1 of Appendix A. Sampling Procedures
If you are...                              You must collect...
comparing against a validated method       nine sets of replicate samples using a paired sampling
system (a total of 18 samples) or four sets of replicate
samples using a quadruplet sampling system (a total of 16
samples). In each sample set, you must use the validated
test method to collect and analyze half of the samples.
using isotopic spiking (can only be used   a total of 12 replicate samples. You may collect the
for procedures requiring mass              samples either by obtaining six sets of paired samples or
spectrometry)                              three sets of quadruplet samples.
using analyte spiking                      a total of 24 samples using the quadruplet sampling system
(a total of 6 sets of replicate samples).
Table 2. of Appendix A. Critical Values of t for the two tailed 95 percent
Degrees of freedom                                  t95
1                                        3=078
2                                        1=886
3                                        1=638
4                                        1=533
5                                        1=476
6                                        1=44
7                                        1=415
8                                        1=397
9                                        1=383
10                                       1=372
Table 3 of Appendix A. Storage and Sampling Procedures for Stack Test
If you are...               With...                      Then you must...
using isotopic or analyte   sample container (bag or     analyze six of the samples at the proposed
spiking procedures          canister) and impinger       minimum storage time and then analyze
sampling systems             the same six samples at the proposed
maximum storage time.
sorbent and impinger         extract or digest six of the samples at the
sampling systems that        proposed minimum storage time and
require extraction or        extract or digest six other samples at the
digestion                    proposed maximum storage time. Analyze
an aliquot of the first six extracts
(digestates) at both the proposed minimum
and proposed maximum storage times.
This will allow analysis of extract storage
sorbent sampling systems     analyze six samples at the proposed
that require thermal         minimum storage time. Analyze another
desorption                   set of six samples at the proposed
comparing an alternative    sampling method that does    analyze half of the samples (8 or 9) at the
test method against a       not include sorbent and      proposed minimum storage time and half
validated test method       impinger sampling systems    of the samples (8 or 9) at the proposed
that require extraction or   maximum storage time.
Table 4. to Appendix A. Procedures for Estimating So
If the estimated LOD is no more than twice              If the LOD is greater than twice the
the calculated LOD, use Procedure I as                  calculated LOD, use Procedure II as
follows.                                                follows.
Estimate the LOD and prepare a test standard at         Prepare two additional standards at concentration
this level. The test standard could consist of a        levels lower than the standard used in Procedure I.
dilution of the analyte described in Section 5.0.
Using the normal sampling and analytical                Sample and analyze each of these standards at
procedures for the method, sample and analyze           least seven times.
this standard at least seven times in the laboratory.
Calculate the standard deviation, So, of the            Calculate the standard deviation for each
measured values.                                        concentration level.
Calculate the LOD as 3 times So.                        Plot the standard deviations of the three test
standards as a function of the standard
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 LOD as 3 times So.
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