[Federal Register Volume 69, Number 245 (Wednesday, December 22, 2004)]
[Proposed Rules]
[Pages 76642-76655]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 04-27985]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 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 Field Validation of
Pollutant Measurement Methods From Various Waste Media
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed rule.
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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 February 22,
2005.
Public Hearing. If anyone contacts the EPA requesting a public
hearing by January 11, 2005, a public hearing will be held on January
21, 2005.
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 instructions for submitting comments.
Agency Web site: 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 FURTHER INFORMATION CONTACT).
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 Web
sites, or e-mail. The EPA EDOCKET and the Federal regulations.gov Web
sites 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
[[Page 76643]]
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 a.m. in the EPA's Auditorium in
Research Triangle Park, North Carolina, or at an alternate site nearby.
FOR FURTHER INFORMATION CONTACT: For information concerning the
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:
[email protected].
SUPPLEMENTARY INFORMATION:
Preamble Outline
The information in this preamble is organized as follows.
I. General Information
A. Does This Action Apply to Me?
B. What Should I Consider as I Prepare My Comments for the EPA?
C. Availability of the Proposed Rule
II. Introduction
III. What Changes Are We Proposing?
A. Use Plain Language
B. Reorganize Method 301
C. Correct Technical Errors
D. Make Technical Revisions
IV. What Are the Administrative Requirements?
A. Executive Order 12866--Regulatory Planning and Review
B. Paperwork Reduction Act
C. Regulatory Flexibility Act (RFA)
D. Unfunded Mandates Reform Act
E. Executive Order 13132--Federalism
F. Executive Order 13175--Consultation and Coordination With
Indian Tribal Governments
G. Executive Order 13045--Protection of Children From
Environmental Health Risks and Safety Risks
H. Executive Order 13211, Actions Concerning Regulations That
Significantly Affect Energy Supply, Distribution, or Use
I. National Technology Transfer and Advancement Act of 1995
I. General Information
A. Does This Action Apply to Me?
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.
B. What Should I Consider as I Prepare My Comments for the EPA?
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 accordance with
procedures set forth in 40 CFR part 2.
2. Tips for Preparing Your Comments. When submitting comments,
remember to:
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 number.
iii. Explain why you agree or disagree; suggest alternatives and
provide substitute language for your requested changes.
iv. Describe any assumptions and provide any technical information
and/or data that you used.
v. If you estimate potential costs or burdens, explain how you
arrived at your estimate in sufficient detail to allow for it to be
reproduced.
vi. Provide specific examples to illustrate your concerns, and
suggest alternatives.
vii. Explain your views as clearly as possible, avoiding the use of
profanity or personal threats.
viii. Make sure to submit your comments by the specified comment
period deadline.
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.
C. Availability of the Proposed Rule
In addition to being available in the docket, an electronic copy of
the proposed changes to Method 301 is also
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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 needed, call the TTN HELP line at
(919) 541-5384.
II. Introduction
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 this action.
III. What Changes Are We Proposing?
A. Use Plain Language
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.
B. Reorganize Method 301
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 preamble.
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
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Proposed new section Promulgated method section
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Using Method 301
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1.0 What is the purpose of Method 1.1 Applicability.
301?.
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.
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Reference Materials and Performance Audits
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5.0 What reference materials must I 3.0 Reference Materials.
use?.
6.0 How do I conduct the 4.0 EPA Performance Audit
performance audit?. Materials.
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Sampling Procedures
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7.0 What sampling procedures must 5.0 Procedure for Determination of
I use?. Bias and Precision in the Field.
8.0 How do I ensure sample 8 Procedure for Sample Stability in
stability?. Bias and Precision Evaluations.
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Bias and Precision
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9.0 What are the requirements for 1.2.1 Bias.
bias?.
10.0 What are the requirements for 1.2.2 Precision.
precision?.
11.0 What calculations must I 6.1 Isotopic Sampling.
perform for isotopic sampling?
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12.0 What calculations must I 6.2.1 Comparison with a validated
perform for comparison with a method: Paired Sampling Systems.
validated method if I am using
paired sampling systems?
13.0 What calculations must I 6.2.2 Comparison with a validated
perform for comparison with a method: Quadruplet Replicate
validated method if I am using Sampling Systems.
quadruplet replicate sampling
systems?
14.0 What calculations must I 6.3 Analyte Spiking.
perform for analyte spiking?
15.0 How do I conduct followup 11 Followup Testing.
tests?.
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Optional Requirements
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16.0 How do I use and conduct 7 Ruggedness Testing.
ruggedness testing?
17.0 What detection limits must I 9 Practical Limit of Quantitation.
use?
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Other Requirements and Information
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18.0 How do I apply for approval to 10 Field Validation Report
use an alternative method? Requirements.
19.0 How do I request a waiver?.... 1.1.1 and 12 Procedure for
Obtaining a Waiver.
20.0 What definitions apply to this 12 Definitions.
method?.
21.0 Where can I find additional 13 Bibliography.
information?.
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TABLE 2.--EQUATIONS IN PROPOSED METHOD 301
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The following
The following equation in equation in
proposed method 301 . . . is . . . promulgated
method 301 . . .
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301-1 Difference in Sample New...............
Results.
301-7 Relative Magnitude of Bias. New...............
301-9 Relative Magnitude of Bias New...............
for Comparing Against Validated
Methods Using Paired Sampling
Systems.
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Equations When Using Isotopic Spiking
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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.
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Equations When Comparing Against Validated Method Using Paired Sampling
Systems
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301-2 Standard Deviation......... For paired 301-2.
sampling systems,
a replacement for.
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 A replacement for. 301-9a.
Variance.
301-13 F test.................... The same as....... 301-8.
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Equations When Comparing Against Validated Method Using Quadruplet
Replicate Sampling Systems
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301-14 Bias...................... The same as....... 301-12.
301-15 Alternative Test Method The same as....... 301-11.
Variance.
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Equations When Using Analyte Spiking
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301-16 Bias...................... The same as....... 301-14.
301-17 t Test.................... A replacement for. 301-4.
301-18 Standard Deviation for A revision of..... 301-13
Spiked Samples.
301-19 Standard Deviation for A replacement for. 301-13 and 301-6.
Unspiked Samples.
301-20 F test.................... New...............
301-21 Pooled Standard Deviation. A replacement for. 301-15.
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C. Correct Technical Errors
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.
[[Page 76646]]
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.
D. Make Technical Revisions
We are proposing five major technical changes to Method 301. These
technical changes include the following:
(1) Replacing the Practical Limit of Quantitation (PLQ) with a
procedure to determine the Limit of Detection,
(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 has no meaning.
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 alternative test methods.
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.
[[Page 76647]]
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.
IV. What Are the Administrative Requirements?
A. Executive Order 12866--Regulatory Planning and Review
Under Executive Order 12866 (58 FR 51735, October 4, 1993), the EPA
must determine whether the regulatory action is ``significant'' and,
therefore, subject to review by the Office of Management and Budget
(OMB) and the requirements of the Executive Order. The Executive Order
defines ``significant regulatory action'' as one that is likely to
result in a rule that may:
(1) Have an annual effect on the economy of $100 million or more or
adversely affect in a material way the economy, a sector of the
economy, productivity, competition, jobs, the environment, public
health or safety, or State, local, or tribal governments or
communities;
(2) Create a serious inconsistency or otherwise interfere with an
action taken or planned by another agency;
(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's priorities, or the principles set forth in
the Executive Order.
It has been determined that this proposed regulatory action is not
a ``significant regulatory action'' under the terms of Executive Order
12866 and is, therefore, not subject to OMB review.
B. Paperwork Reduction Act
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
collection of information.
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 chapter 15.
C. Regulatory Flexibility Act (RFA)
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 will not have a
significant economic impact on a substantial number of small entities.
Small entities include small businesses, small organizations, and small
governmental jurisdictions.
For the purposes of assessing the impacts of today'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
dominant in its field.
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.
D. Unfunded Mandates Reform Act
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 ``Federal mandates'' 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
[[Page 76648]]
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
requirements.
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 UMRA.
E. Executive Order 13132--Federalism
Executive Order 13132, entitled ``Federalism'' (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.''
``Policies that have federalism implications'' is defined in the
Executive Order to include regulations that 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.''
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.
F. Executive Order 13175--Consultation and Coordination With Indian
Tribal Governments
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 and Safety 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) ``Economically
significant'' 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.
H. Executive Order 13211, Actions Concerning Regulations That
Significantly Affect Energy Supply, Distribution, or Use
This rule is not subject to Executive Order 13211, ``Actions
Concerning Regulations That Significantly Affect Energy Supply,
Distribution, or Use'' (66 FR 28355(May 22, 2001)) because it is not a
significant regulatory action under Executive Order 12866.
I. National Technology Transfer and Advancement Act of 1995
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 standards in their regulatory
activities unless to do so would be inconsistent with applicable law or
otherwise impractical.
Voluntary consensus standards are technical standards (e.g.,
materials 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.
List of Subjects in 40 CFR Part 63
Environmental protection, Alternative test method, Air pollution
control, Field validation, Hazardous air pollutants.
Dated: December 16, 2004.
Michael O. Leavitt,
Administrator.
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:
PART 63--[AMENDED]
1. The authority citation for part 63 continues to read as follows:
Authority: 42 U.S.C. 7401, et seq.
2. Appendix A is amended by revising Method 301 to read as follows:
[[Page 76649]]
Appendix A to Part 63--Test Methods
Method 301--Field Validation of Pollutant Measurement Methods From
Various Waste Media
Sec.
Using Method 301
1.0 What Is the Purpose of Method 301?
2.0 When Must I Use Method 301?
3.0 What Does Method 301 Include?
4.0 How Do I Perform Method 301?
Reference Materials and Performance Audits
5.0 What Reference Materials Must I Use?
6.0 How do I conduct the performance audit?
Sampling Procedures
7.0 What Sampling Procedures Must I Use?
8.0 How Do I Ensure Sample Stability?
Bias and Precision
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?
Optional Requirements
16.0 How Do I Use and Conduct Ruggedness Testing?
17.0 What Detection Limits Must I Use?
Other Requirements and Information
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?
Using Method 301
1.0 What Is the Purpose of Method 301?
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.
2.0 When Must I Use Method 301?
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 Sec. 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.
3.0 What Does Method 301 Include?
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.
4.0 How Do I Perform Method 301?
First, you introduce a known concentration of an analyte or
compare the alternative test method against a validated test method
to determine the alternative test method's bias. Then, you collect
multiple, collocated simultaneous samples to determine the
alternative test method's precision. Sections 5.0 through 17.0
describe these procedures in detail.
Reference Materials and Performance Audits
5.0 What Reference Materials Must I Use?
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.
6.0 How Do I Conduct the Performance Audit?
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.
Sampling Procedures
7.0 What Sampling Procedures Must I Use?
You may determine bias and precision by comparing against a
validated test method, using isotopic sampling, or using analyte
spiking. 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
[[Page 76650]]
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 concentration in the applicable emission
limitation or standard in the subpart of 40 CFR part 63 (or the
expected sample concentration where there is no standard). The final
concentration of the analyte 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 volume.
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 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).
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 horizontal plane.
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 samples.
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 weeks or less.
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.000
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's, of the paired
samples using Equation 301-2.
[GRAPHIC] [TIFF OMITTED] TP22DE04.001
Where:
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.002
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.
Bias and Precision
9.0 What Are the Requirements for Bias?
You must establish bias by comparing the results of the sampling
using the alternative test method against a reference value. The
bias must be no more than +/-10% for the alternative test method to
be acceptable.
10.0 What Are the Requirements for Precision?
At a minimum, you must use paired sampling systems to establish
precision. If you are using analyte spiking, including isotopic
samples, the precision expressed as the relative standard deviation
(RSD), of the alternative test method at the level of the applicable
emission limitation or standard in the subpart of 40 CFR part 63
must be less than or equal to 20 percent. 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.
11.0 What Calculations Must I Perform for Isotopic Spiking?
You must analyze the bias, precision, relative standard
deviation, and data acceptance for isotopic spiking tests according
to the provisions in sections 11.1 through 11.3.
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.003
Where:
B = Bias at the spike level.
Sm = Mean of the measured values of the isotopically
spiked samples.
CS = Calculated value of the isotopically labeled spike.
11.2 Standard Deviation. Calculate the standard deviation of the
Si values according to Equation 301-5.
[GRAPHIC] [TIFF OMITTED] TP22DE04.004
Where:
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.
[[Page 76651]]
[GRAPHIC] [TIFF OMITTED] TP22DE04.005
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.006
Where:
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 301-8
[GRAPHIC] [TIFF OMITTED] TP22DE04.007
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.
12.0 What Calculations Must I Perform for Comparison With a
Validated Method If I Am Using Paired Sampling Systems?
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 differences, di's, of the paired
samples using Equation 301-2.
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 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.008
Where:
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.009
Where:
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.010
Where:
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.011
(If S2v > 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.012
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.
13.0 What Calculations Must I Perform for Comparison With a
Validated Method If I Am Using Quadruplet Replicate Sampling
Systems?
If you are using quadruplet replicate sampling systems to
compare an alternative test method to a validated method, then you
must analyze the data according to the provisions in 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.013
Where:
V1i = First measured value with the validated method in
the i-th sample.
V2i = Second measured value with the validated method in
the i-th sample.
P1i = First measured value with the alternative test
method in the i-th sample.
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 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 alternative test method and the
results are rejected. If the
[[Page 76652]]
F test does not show a significant difference, then the alternative
test method has acceptable precision. This 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.014
Where:
di = The difference between the i-th pair of samples
collected with the alternative test method.
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 method are unacceptable.
14.0 What calculations must I perform for analyte spiking?
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.020
Where:
B = Bias at the spike level.
Sm = Mean of the spiked samples.
Mm = Mean of the unspiked samples.
CS = Calculated value of the spiked level.
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.015
Where:
Su2 = (SDu) 2,
SDu is calculated in Equation 301-19.
Ss2 = (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 test method.
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.016
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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.017
Where:
diu = Difference between the i-th pair of unspiked
samples.
n = Number of paired 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.018
Where Su\2\ and Ss\2\ 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.
[GRAPHIC] [TIFF OMITTED] TP22DE04.019
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.
15.0 How do I conduct tests at similar sources?
If the Administrator has approved the use of an alternative test
method to a test method required in 40 CFR part 63 for an affected
source, and the Administrator has approved the use of the
alternative test method at your similar source according to the
procedures in 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.
Optional Requirements
16.0 How do I use and conduct ruggedness testing?
If you want to use a validated test method at a concentration
that is different from the concentration in the applicable emission
limitation in the subpart of 40 CFR part 63 or for a source category
that is different from the source category that the test method
specifies, then you must conduct ruggedness testing according to the
procedures in Citation 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. 33-36).
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 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.
Other Requirements and Information
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 Sec. 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.
[[Page 76653]]
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, as applicable.
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.
19.0 How do I request a waiver?
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 particular application.
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 validated.
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.
20.0 What definitions apply to this method?
Affected source means affected source as defined in 40 CFR 63.2
and in the relevant subpart under 40 CFR part 63.
Alternative test method means the sampling and analytical
methodology selected for field validation using the method described
in this appendix.
Paired sampling system means a sampling system capable of
obtaining two replicate samples that were collected as closely as
possible in sampling time and sampling location.
Quadruplet sampling system means a sampling system capable of
obtaining four replicate samples that were collected as closely as
possible in sampling time and sampling location.
Surrogate compound means a compound that serves as a model for
the types of compounds being analyzed (i.e., similar chemical
structure, properties, behavior). The model can be distinguished by
the method from the compounds being analyzed.
21.0 Where can I find additional information?
You can find additional information in the references in
paragraphs 21.1 through 21.12.
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, DC.
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. & 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. &
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.
[[Page 76654]]
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 A total of 12 replicate
used for procedures requiring mass samples. You may collect the
spectrometry). either samples by obtaining
six sets of paired samples or
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 Confidence Limit
------------------------------------------------------------------------
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
Emissions
------------------------------------------------------------------------
Then you must . .
If you are . . . With . . . .
------------------------------------------------------------------------
Using isotopic or analyze Sample container Analyze six of the
spiking procedures. (bag or canister) samples at the
and impinger proposed minimum
sampling systems. storage time and
then analyze the
same six samples
at the proposed
maximum storage
time.
Sorbent and Extract or digest
impinger sampling six of the
systems that samples at the
require proposed minimum
extraction or storage time and
digestion. extract or digest
six other samples
at the 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
impacts.
Sorbent sampling Analyze six
systems that samples at the
require thermal proposed minimum
desorption. storage time.
Analyze another
set of six
samples at the
proposed maximum
storage time.
Comparing an alternative test Sampling method Analyze half of
method against a validated test that does not the samples (8 or
method. include sorbent 9) at the
and impinger proposed minimum
sampling systems storage time and
that require half of the
extraction or samples (8 or 9)
digestion. at the proposed
maximum storage
time.
Sorbent and Extract or digest
impinger sampling six of the
systems that samples at the
require proposed minimum
extraction or storage time and
digestion. extract or digest
six other samples
at the 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
impacts.
------------------------------------------------------------------------
Table 4 to Appendix A.--Procedures for Estimating So
------------------------------------------------------------------------
If the estimated LOD is no more than If the LOD is greater than
twice the calculated LOD, use Procedure twice the calculated LOD, use
I as follows Procedure II as follows.
------------------------------------------------------------------------
Estimate the LOD and prepare a test Prepare two additional
standard at this level. The test standards at concentration
standard could consist of a dilution levels lower than the standard
of the analyze described in Section used in Procedure I.
5.0..
Using the normal sampling and Sample and analyze each of
analytical procedures for the method, these standards at least seven
sample and analyze this standard at times.
least seven times in the laboratory.
Calculate the standard deviation, So, Calculate the standard
of the measured values. deviation for each
concentration level.
Calculate the LOD as 3 times So........ Plot the standard deviations of
the three test standards as a
function of the standard
concentrations.
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.
------------------------------------------------------------------------
[[Page 76655]]
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[FR Doc. 04-27985 Filed 12-21-04; 8:45 am]
BILLING CODE 6560-50-P