[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

[[Page 76644]]

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
------------------------------------------------------------------------
        Proposed new section              Promulgated method section
------------------------------------------------------------------------
                            Using Method 301
------------------------------------------------------------------------
 
 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.
------------------------------------
 
                Reference Materials and Performance Audits
------------------------------------------------------------------------
 
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.
------------------------------------
                           Sampling Procedures
------------------------------------------------------------------------
 
 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.
------------------------------------
                           Bias and Precision
------------------------------------------------------------------------
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?

[[Page 76645]]

 
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?.
------------------------------------
                          Optional Requirements
------------------------------------------------------------------------
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?
------------------------------------
                   Other Requirements and Information
------------------------------------------------------------------------
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?.
------------------------------------------------------------------------


               TABLE 2.--EQUATIONS IN PROPOSED METHOD 301
------------------------------------------------------------------------
                                                         The following
    The following equation in                             equation in
    proposed method 301 . . .           is . . .          promulgated
                                                        method 301 . . .
------------------------------------------------------------------------
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.
----------------------------------
                  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          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.
----------------------------------
   Equations When Comparing Against Validated Method Using Quadruplet
                       Replicate Sampling Systems
------------------------------------------------------------------------
301-14 Bias......................  The same as.......  301-12.
301-15 Alternative Test Method     The same as.......  301-11.
 Variance.
----------------------------------
                  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      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.
------------------------------------------------------------------------

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