1

6560

- 50

- P

ENVIRONMENTAL PROTECTION AGENCY

40 CFR Part 63 [OAR - 2004
- 0080, FRL
- 7851
- 9 xxxx - x ]

RIN 2060
- AF00
National Emission Standards for Hazardous Air Pollutants: Appendix A - Test Methods; Metho d 301 for the

- Field Validation of Pollutant Measurement Methods from
Various Waste Media
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed Final rule.
SUMMARY: Thi s a ction 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 spikin g as an option even when there is an existing test method. amends2

EPA’s Method 301, Field Validation of Pollutant Measurement Methods from Various Waste Media. We revised the procedures in Method 301 based on our experience in applying the method
and to co rrect errors that were brought to our attention.
T his action finalizes a mendments to Method 301 after considering comments rece ived on the proposed rule published in the Federal Register on December 22, 2004. Changes made to the Method 301 protocol under this action apply only to methods submitted to the EPA for approval after the effective date of this action.
DATES: Comments . Comments must be received on or before [INSERT DATE 60 DA YS AFTER PUBLICATION IN THE FEDERAL
REGISTER ]. Public Hearing . If anyone contacts the EPA requesting a public hearing by [INSERT DATE 20 DAYS AFTER PUBLICATION IN THE FEDERAL REGISTER], a public hearing will be held on [INSERT DATE 30 DAYS AFTER DATES: This final rule is effective on [Insert date of publication in the Federal Register ].
ADDRESSES: Comments . Submit your comments, identified by
EPA has established a docket for this action under Docket ID
No. OAR

- 2004

- 0080, by one of the following methods.

· Federal eRulemaking Portal:3
http:///www.regulations.gov. Follow the on

- line instructions for submitting comments.

· Agency Website: http://www.epa.gov/edocket. EDOCKET, EPA’s electronic public docket and comment system, is EPA’s preferred method for receiving comments. Follow
the on

- line instructions for submitting comments.

· Mail: Air and Radiation Docket and Information Center (Mail Code 6102T), Attention Docket Number EPA

- HQ

- OAR

2004

- 0080 , Room B108, U.S. EPA, 130 1 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 informati on (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 Off icer, 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, 13014
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 FURTH ER 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 yo u consider to be CBI or otherwise protected through EDOCKET, regulations.gov websites, or e

mail. The EPA EDOCKET and the Federal regulations.gov websites are “anonymous access” systems, which means the EPA will not know your identity or contact informati on unless you provide it in the body of your comment. If you send an

e - mail comment directly to the EPA without going through EDOCKET OR regulations.gov, your e

- mail address will be5

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 cann ot 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/edoc ket on the http://www.regulations.gov
web site . Although listed in the index, some information is not publicly available, i. e .g ., CBI or other information whose disclosure is restricted by statute. Certain other material, such as copyrighted material, is not place d on the Internet and will be publicly available only in hardcopy hard
copy form. Publicly available docket materials are available either electronically in EDOCKET through6

http://www.regulations.gov or in hard copy at the EPA Docket Center ( Air Docket ), , EPA/DC, EPA West, Room B

- 108 3334 , 1301 Constitution Avenue, NW ., , Washington, DC 20004.

. The Docket Center is Facility and the Public Reading Room are 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 pr esenting oral testimony or inquiring as to whether a hearing is to be held
should contact FOR FURTHER INFORMATION CONTACT: M s. Corlis McCormick, Source Lula H. Melton , Office of Air Quality Planning and Standards , Air Quality Assessment Division, Measurement Technology Group , Emission Measurement Center (D243 (E143

- 02), U.S. Environmental Protection Agency, Research Triangle Park, NC, North Carolina 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 at7

10:00 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

- 2910 ; fax number: (919) 541

- 1062, electronic 0516; e

- mail address: mcalister.gary melton.lula @epa.gov.
SUPPLEMENTARY INFORMATION:
Preamble Outline The information in this preamble is organized as
follows. Table of Contents
I. General Information A. Does this A ction A pply to M e?
B. What Should Where Can I Consider as I Prepare My Obtain a Copy of This Action? C. Judicial Review
II. Background
III. Summary of the Final Method
IV. Significant Comments for the EPA? C. Availability of Received on the Proposed Rule8

II. Introduction III. What changes Are We Proposing? A. Use Plain Language B. Reorganize Amendments to Method 301 C. Correct Technical Errors D. Make Technical Revisions IV. What are the Administrative Requirements?
A. Applicability
B. Reference Material
C. Validat ion Testing Over a Broad Range of Concentrations and Extended Period of Time
D. Performance Audit
E. Sample Stability Procedures
F. Bias and Precision
G. Limit of Detection
H. Critical Values of t for the Two

- Tailed 95% Confidence Limit
I. Paired Sam pling Procedure
J. Standard Deviation
V. Statutory and Executive Order Reviews A. Executive Order 12866

- – Regulatory Planning and Review B. Paperwork Reduction Act9
C. Regulatory Flexibility A ct (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 J. Executive Order 12898

– Federal Actions to Address Environmental Justice in Minority Populati ons and
Low

- income Populations K. Congressional Review Act I. General Information
A. Does this Action Apply to Me? Method 301 affects/ applies to you if you want to
propose a new or alternative test method to meet an EPA compliance requirement in absence of a validated method.
. B. What Should I Consider as I Prepare My Comments for the
EPA Where Can I Obtain a Copy of this Action ?10

1. Submitting CBI . Do not submit this information to the EPA through EDOCKET, regulations.gov, or e

- mail.
Clea rly 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 i nformation 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; suggest11

alternatives and provide substitute language for your requested changes. iv. Describe any assumptions and provide any technical information and/or data that you use d. 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 cl early 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 ina dvertently 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 CBI12

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. Availabil ity of the Proposed Rule In addition to being available in the d ocket, an electronic copy of the proposed changes to Method 301 is this rule will also be available on the Internet Worldwide Web (www) through the Technology Transfer Network (TTN). Following the Administrator’s signature, a copy of Method 301 the final rule will be posted plac ed on the TTN’s policy and guidance page for newly proposed or promulgated rules http://www.epa.gov/ttn/oarpg

. at 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; C. Judicial Review We are deeming this a 307 rule under section 307(d)(v).
Under s ection 307(b)(1) of the Clean Air Act (CAA) , judicial13

review of this final rule is available by filing a petition for review in the U.S. Court of Appeals for the District of Columbia by [Insert date 60 days after publication in the Federal Register ]. Any such judicial review is limited to only those objections that are raised with reasonable specificity in timely comments. Under section 307(b)(2) of th e Act, the requirements of thi s final action may not be challenged later in civil or criminal proceedings brought by us to enforce these requirements. II. Background
Thi s action amends EPA’ s Method 301, Field Validation
of Pollutant Measurement Met hods from Various Waste Media. Method 301 can be found was originally promulgated 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, on June 13 3 , 1991 ) pursuant to Section 112 of the Clean Air Act (as am ended in 1990). . We proposed amendments to Method 301 on December 22, 2004 (69 FR 76642). This action responds to comments received on that proposal an d corrects errors found in the

m ethod. III. Summary of the Final Method14
You would use Method 301 whenever you propose to use a
test method to meet an EPA compliance requirement in absence
of other than a validated method that is required under a 40 CFR Part 63 rule . The m ethod specifies procedures for determining and documenti ng 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
refere nce 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.15

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

m ust 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 necessary16

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 Meth od 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 th e 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 sp iking 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.17

Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.
Proposed New Section Promulgated Method Section

Using Method 301

1.0 What is the purpose of Method 301? 1.1 Applicability

2.0 When must I use Method 301? None 3.0 What does Method 301 include? 1.1.2

4.0 How do I perform Method 301? 1.2 Principle

Reference Materials and
Performance Audits

5.0 What reference materials
must I use? 3.0 Reference Materials

6.0 How do I conduct the performance audit? 4.0 EPA Performance Audit Materials
Sampling Procedures

7.0 What sampling procedures
must I use? 5.0 Procedure for Determination of Bias and Precision in the Field18

Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.
Proposed New Section Promulgated Method Section

8.0 How do I ensure sample stability? 8 Procedure for Sample Stability in Bias and Precision Evaluations

Bias and Precision

9.0 What are the requirements for bias? 1.2.1 Bias

10.0 What are the requirements for precision? 1.2.2 Precision

11.0 What calculations must I perform for isotopic sampling? 6.1 Isotopic Sampling

12.0 What calculations must I perform for comparison with a validated method if I am using paired sampling systems? 6.2.1 Comparison with a validated method: Paired Sampling Systems

13.0 What calculations must I perform for comparison with a validated method if I am using quadruplet replicate 6.2.2 Comparison with a validated method: Quadruplet Replicate Sampling Systems19

Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.
Proposed New Section Promulgated Method Section
sampling systems?

14.0 What calculations must I perform for analyte spiking? 6.3 Analyte Spiking

15.0 How do I conduct followup
tests? 11 Followup Testing

Optional Requirements

16.0 How do I use and conduct ruggedness testing? 7 Ruggedness Testing

17.0 What detection limits must
I use? 9 Practical Limit of Quantitation
Other Requirements and
Information

18.0 How do I apply for approval to use an alternative method? 10 Field Validation Report Requirements

19.0 How do I request a waiver? 1.1.1 and 12 Procedure for Obtaining a

Waiver20

Table 1. Comparison of Sections in Proposed Method 301.

to Those in Promulgated Method 301.
Proposed New Section Promulgated Method Section

20.0 What definitions apply to this method? 2 Definitions

21.0 Where can I find additional information? 13 Bibliography21

Table 2. Equations in Proposed Method 301
The following equation in proposed
Method 301. . . is... The following equation in promulgated
Method
301...

301

- 1 Difference in Sample Results new

301

- 7 Relative Magnitude of Bias new

301

- 9 Relative Magnitude of Bias

for Comparing Against Validated Methods Using Paired Sampling Systems new

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 Paired22

Sampling Systems

301

- 2 Standard Deviation for paired sampling systems, a replacement for 301

- 2

301

- 3 t Test the same as 301

- 9

301

- 10 Variance a replacement for 301

- 7

301

- 11 Pooled Variance new

301

- 12 Alternative Test Method Variance a replacement for 301

- 9a

301

- 13 F test the same as 301

- 8
Equations When Comparing Against Validated Method Using Quadruplet Replicate Sampling Systems

301

- 14 Bias the same as 301

- 12

301

- 15 Alternative Test Method Variance the same as 301

- 11
Equations When Using Analyte Spiking

301

- 16 Bias the same as 301

- 14

301

- 17 t Test a replacement for 301

- 423

301

- 18 Standard Deviation for Spiked

Samples a revision of 301

- 13

301

- 19 Standard Deviation for Unspiked

Samples a replacement for 301

- 13 and

301

- 6

301

- 20 F test new

301

- 21 Pooled Standard Deviation a replacement for 301

- 1524

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 equation s 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 un spiked samples). These changes were editorial/defining changes and not technical changes. For example, we added or changed subscripts or redefined a variable. We added Equations 301

- 1, 301

- 7, and 301

- 9. Equation 301

- 1 is used to calculate the differenc e 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 Equations25

301

- 12, 301

- 17, 301

- 18, and 301

- 19 to correct tec hnical 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 var iance. 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 tha t 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 com paring 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 by26

substituting d m (mean of the paired sample differences) and
d i (standard deviatio n of the differences) for S i and S m 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: IV. Significant Comments Received on the Proposed Amendments to Method 301 We proposed five major technical changes to Method 301. These technical changes include the following: (1) Replacing the P ractical Limit of Quantitation (PLQ) with a procedure to determine the Limit of Detection , (LOD), (2) Revising the bias acceptance criteria and eliminating correction factors, (3) Revising precision acceptance criteria when using analyte spiking, (4) A llowing analyte spiking even when there is an existing test method, and (5) Establishing new procedures for ensuring sample stability.27

1. Practical Limit of Quantitation . We are proposing to replace the determination of the PLQ with a procedure to
dete rmine 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 con centration 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 fo r 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 c oncentration 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 mea sured increases. However, for most environmental measurements, it appears that the precision is a function of the concentration of the28

analyte being measured. The following section provides our response to significant comments received on the proposed technical changes and some inadvertant errors that occurred with the restructuring of, and addition of , components to the m ethod.
A. Applicability A couple of commenters requested clarification that the final rule changes made to Method 301 only apply to methods submitted to EPA after promulgation of the changes and that Method 301 can be used whether or not a validated method exists. We are clarify ing in this final rule that
amendments to Method 301 do not apply to methods submitted for approval prior to promulgation. Also, Method 301 can be
used whether or not a validated method exists. This action clarifies the effective date of the amended M eth od 301 , and Section 1.0 of the final m ethod clarifies that Method 301 can be used whether or not a validated method exists.
B. Reference Material One commenter provided that, as written, reference material is analogous to analyte. Inadvertantly, in Section 5 of Method 301, “reference materials” was followed by “(analytes).” This paranthetical was modified for clarification purposes as noted below.29

A few commenters expressed concern that the standard against which precision and bias are compared is not required to be compared against a true value, usually a traceable standard (e.g., NIST). We agree that the reference material should be compared to a traceable
standard. We have amended Section 5 of the final m ethod to state the following:
You must use reference materials (a material or substance whose one or more properties are sufficiently homogenous to the analyte) that are traceable to a national standards body (e.g., National Institute of Standards and Technology (NIST)) at the level of the app licable emission limitation or standard that the subpart in 40 CFR Part 63 requires.

C. Validation Testing Over a Broad Range of Concentrations and Extended Period of Time One commenter requested that validation testing over a broad range of concentra tions and/or over an extended period of time be allowed and mention ed that they had developed technology that could test over a br oad range of concentrations for an extended time

- period . The commenter argued that if the accuracy and precision requirements can be demonstrated with sequential sampling procedures, the EPA should allow it. We agree with the commenter. In fact, we have approved methods demonstrated with sequential sampling30

to determine the precision of a proposed alternative method in the past . The final m ethod explicitly states that sequential sampling procedures are allowed.
D. Performance Audit One commenter stated that they do not agree that the performance audit requirements in Section 6 of the proposed rule should be included in Method 301. The commenter supported their position by stating that the audit material may not correspond to the matrix for which the alternate
test method was designed, and it is similar to having to ask EPA permission to use a metho d that has passed Method 301 validation criteria. In addition, the commenter stated that the 30

- day lead time for requesting the performance audit material reduces an affected parties’ flexibility in meeting performance testing timing requirements.
The function of an audit sample is to allow a tester to demonstrate that their measurement system using a well

established measurement method is operating within established quality assurance limits. If the alternative method is being compared to a validated test method as part of the Method 301 validation and an audit sample for the validated method exists, then an audit should be used for the validated method. Since the amendments to Method 30131

were proposed on December 22, 2004, we promulgated a rule on
Se ptember 13, 2010 that moves all discussion of audits fr om the individual rules to the General P rovisions of Part 63. Therefore, we have removed the proposed Section 6 whi ch discussed performance audits
. E Thus, the relative imprecision will not decrease a s 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 to32

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 me thod 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 b urden 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 attem pt to compensate for the poorer precision of some candidate alternative test methods by33

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 crit eria 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 prev iously 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 analyte34

spiking procedure and that this is a reasonable alternative to direct comparison.
5
. Sample Stability . Finally, we are propo sing Procedures We proposed 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 We revised Section 8 7 .4 includes to include 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 calcu lating 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

cr itical value of the t

- statistic. These procedures are necessary to ensure sample stability and should have been included in promulgated Method 301. Several commenters provided comments on the minimum and maximum storage holding time limits specified in Section 7 .0 of Method 301. Commenters recommended that either the minimum and maximum holding times be removed and that35

holding time s should be defined by the data or that they be liberalized (e.g., increase the minimum hold time to 48 to 72 hours from 24 hours). We agree with the commenters and are revising the minimum hold time to be seven days. The method will also require tha t the samples be analyzed again at the proposed maximum storage tim e or two weeks after the initial analysis.
F. Bias and Prec ision We proposed 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 provided that 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. One commenter stated that they did not believe that bias acceptance criteria should be changed unless uncertainties in the reference value are included in determining the significance of differences.
O ne commenter provided that the proposed reduction of bias from ± 30 to ± 10 percent is too stringent. One commenter suggested allowing a bias of ± 15 percent with no36

correction factors, while continuing to allow a bias of ± 30 percent with the use of corr ection factors for bias values between 15 and 30 percent. The commenter provided a summary of EPA Method 301 validations of several methods to support their position. We agree that reducing the acceptable bias to ± 10 percent may be too stringent becau se there may be testing situations that are so difficult that there are no methods readily available that could meet this requirement. We believe that a reasonable solution is to allow methods that have a bias greater than 10 percent if the results from
t hese methods are corrected to account for that bias. However, we believe that we should not approve the use of methods with greater than 30 percent bias even if the user were wil l ing to co r r e ct the results. W e ha ve changed the final method to allow a bias of ± 10 per cent with no correction factors and allow a bias of ± 30 percent with the use of correction factors for bias values between 10 and 30 percent. We proposed to change the acceptance criteria for method p recision when using analyte spiking from ± 50% to
± 20%. In addition, we proposed to eliminate the requirement for different numbers of replicate samples3 7

depending on the method’s relative precision. We also proposed to tighten the acceptance criteria fo r the precision of candidate alternative test methods. One commenter stated that the proposed reduction of precision criteria from ± 50 percent to ± 20 percent is too stringent. The commenter suggested allowing a precision of
± 30 percent with no use of replicate runs and the continued allowance of a precision of ± 50 percent with the use of additional sample runs for precision v alues between 30 and 50 percent. The commenter provided a summary of EPA Method 301 validations of several methods to support t heir position. Based on our evaluation of the summary provided by the commenter and their suggestion, we have changed the final method. The method will continue to require a precision of
± 20 percent when only the required three runs per test are performed. However, we have added an option to allow test methods with a precision greater than ± 20 percent but less
than ± 50 percent provided that the user collect nine sample runs per test dur ing any compliance testing where the method is used.
G. Limit of Detection We proposed to replace the determination of the38

practical limit of quant itation ( PLQ ) with a procedure to determine the limit of detection ( LOD )
. The purpose of establishing a m easurement limit is to ensure that a test method is appropriate for its intended use. The LOD is a better parameter for this purpose. We provided that for most environmental measurements, it appears that precision is a function of the concentration of th e analyte being
measured. Thus, the relative imprecision will not decrease as the quantity measured increases. III. What Are The Administrative Requirements ?

In this case, we stated that the PLQ has no meaning. Several commenters disagreed that the PLQ is a meaningless concept and that there are instances that substituting the LOD for the PLQ is not always appropriate. Some of these commenters stated that the Office of Water formed a FACA to

con sider alternative approaches to similar procedures they proposed (40 CFR 136 Appendix B) and that Method 301 should be deferred until after those discussions have concluded and that consistent application be applied across the Agency based on those discuss ions. The PLQ is a limit determined by the standard deviation of an estimate of a concentration; if the standard deviation39

of the estimate exceeds a threshold, then that estimate is unacceptable. The LOD is a limit determined by the estim ate of the concen tration itself. I f this estimate possesses a value that cannot be distinguished from an estimate resulting from a blank sample with a stated level of confidence, then this estimate is unacceptable. The LOD is clearly a threshold th at should be used in Me thod 301 since an estimate that cannot be distinguished from one resulting from a blank sample is unlikely to provide meaningful
results. The PLQ does not appear to have any relevance for Method 301. There does not appear to be a good reason for a
metho d that produces a standard deviation that exceeds an established threshold not to go through the full rigor of the bias and precision tests prescribed in Method 301. For these reasons, Method 301 retains the use of the LOD in lieu of the PLQ.
One commente r provided that the proposed LOD determination does not appear appropriate for radiochemical methods and suggest ed that the content of the Multi

- Agency Radiological Laboratory Analytical Protocols Manual (MARLAP) be used. We agree with the commenter and have amended Method 301 to allow for the use of the MARLAP for40

radiochemical methods. A few commenters requested th at the calulation of the LOD be better defined a nd clarified in Table 4 of the

m ethod. One commenter expressed that the description of the procedures used for estimating S 0 in Table 4 need to be clarified. The LOD is defined as the lowest quantity of a

su bstance that can be distinguished from the absence of that substance (i.e., blank value) with a stated level of confidence. For example, suppose blank samples are normally distributed , and S 0 represents the standard deviation of the blank samples (i.e., t he standard deviation of pure “noise”). Then a sample value larger than 3S 0 will have a probability of not being a blank of at least 99% if S 0 is estimated with at least 14 degrees of freedom (or at least 7 degrees of freedom if a 1

- sided alt ernative hypo thesis is assumed). I f S 0 is “known”, then the probability will be 99.74%, but this is often truncated to 99 %
. The method for obtaining S 0 has been clarified to proceed as follows: (1) Pick a concentration level that you think should approximate the LOD and call this level LOD 1 . Prepare seven samples of a standard set at a concentration of LOD 1 .41

Estimate t he standard deviation of these seven samples, and call it S 1 . (2) Define LOD 0 = 3S 1 . (3) If LOD 1 ≤ 2LOD 0 , then define S 0 = S 1 . (4) If LOD 1 > 2LOD 0 , then proceed as follows: a. Prepare two additional standards at concentrations lower than LOD 1 , and call these LOD 2 and LOD 3 . Prepare seven samples of each of these
two standards and estimate their standard deviations
and call them S 2 and S 3 , respective ly. b. Plot S 1, S 2, and S 3 as a function of concentration , draw a best

- fit straight line through
them , and extrapolate to zero concentration. c. Define S 0 as the extrapolation of the standard deviation at zero concentration.
H. Critical Values of t for the Two

- Tailed 95% Confidence Limit A couple of commenters provided that the values of t
for the two

- tailed 95% confidence limit are wrong s ince they reflected an 8 0% confidence limit and there a re some apparent typesetting errors. We corrected these val ues to reflect the 95% confidence l imit and eliminated the typesetting errors in the final method.42

I. Paired Sampling Procedure A couple of commenters pointed out several errors and expressed concerns with the methods to a scertain and test precision in S ection 12. Upon evaluat ion, we have decided to re v is e S ection 12.2 in Method 301. We are deleting the comparison of the precision of the alternative method to that of the validated
method. This decision was made because the paired sampling
method de scribed in it does not allow for the estimation of the within

- sample standard deviation for either the alternative or validated methods.
J. Standard Deviation One commenter expressed that the precision is a
fu nction of concentration; in other words , as the concentration level increases, so does the standard deviation of the estimate of that concentration. This could render the relative standard deviation (Eq. 301

- 8 in Section 10.4) meaningless
. A second commenter also expressed that the standard d eviation is a function of concentration. This commenter noted that pollutant concentrations from an emission source are variable, resulting in a range of possible concentration values being measured. The commenter suggested that the43

appropriate procedure to compare two methods under these circumstances is to compare the regression lines of the two methods across a range of concentrations. We agree that this could be a potentially serious concern, if there is little control over the concentrations being measured. However, if there is an appropriate level of control, then the procedures given in Method 301 are sufficient. In most situations, we believe that an appropriate level of control exists. For example, consider the case where an alternative method is compared against a validated method, using quadruple samples. We believe that an appropriate level of control exists if the following four conditions are met: (1) there is positive correlation between the estimates within both alternative and validate d pairs in the quadruple samples , and the respective correlation coefficients are reasonably constant as a function of concentration, (2) there is positive correlation between the alternative and validated estimates in the quadruple samples and the correla tion coefficient is reasonably constant as a function of concentration, (3) the within

- quadruple sample concentrations are reasonably similar; and (4) if the between

- quadruple sample concentrations vary greatly, then the functional44

relationship between the standard deviation and concentration is reasonably similar for both the alternative and validated methods. We believe that these four conditions hold for most cases , and an appropriate level of control exists. If one or more of these conditions is violat ed, then the user may request that they be allowed to
compare the regression lines resulting from the alternative and validated estimates as a function of concentration as an alternative to the requirements in Method 301.

V. Statutory and Executive Or der Reviews
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,45

local, or tri bal 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 This action is not a "significant regulatory action" under the terms of Executive Order (EO) 12866 (58 FR 51735, October 4, 1993) and is, therefore, not subject to
OMB review
. under the EO.
B. Paperwork Reduction Act This action does not impose or change the an 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 and46

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 is defined at 5 CFR 1320.3(b). We are not promulgating any new paperwork requirements ; train personnel to be able to respond to a coll ection 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 (e.g., monitoring, reporting, recordkeeping) as part of today’s final action. This final rule amends Method 301 which may be used to validate test da ta or a new test method. Method 301 has been part of our regulations are listed in 40 CFR Part 9 and 48 CFR Chapter 15. for many years , and the amendments that we are making would not add any new paper work requirements.
C. Regulatory Flexibility Act (RFA) Analysis The RFA generally requires an agency to prepare a regulatory flexibility analysis of any rule subject to47

notice and comment rulemaking requirements under the Administrative Procedure Act or any other statute statue unless the a gency 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 th i s action on small entities, a small entity is defined as: (1) a small business that meets the definitions for is a small business based on the industrial entity as defined in the U.S. Small Business Association Administration (SBA) size standards which, for this proposed action, are operations that have fewer than 1,000 employees; ( see 13 CFR 121.201); (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 or (3) a small organization that is any not

- for

- profit enterprise which that is independently owned and operated and is not dominant in its field. After considering the economic impacts of today’s proposed final rule on small entities, I certify that this proposed action will not have a significant economic impact48

on a substantial number of small entities. In determining whether a rule has significant economic impact on a substantial number of small entities, th e 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
prop osed 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 economi c effect on all of the small entities subject to the rule. This proposed rule will not This final rule does not impose any requirements on small entities. This rule establishes procedures for using alternative methods. As such, Small entities and other

sources may chose to use this regulatory option of validating their own new or alternative compliance test method, but they are not required to comply with choose this proposed rule, but may elect to use option. Method 301 . The proposed rule offers addition al flexibility to all sources, including will not impose any significant impact on small entities that may be subject . Any small entity choosing to use49

Method 301 to requirements under the CAA. Additionally, this proposed amended rule clarifies and simpl ifies the procedures for using validate a new or alternative methods. We continue to be interested test method would likely do so because this option is less burdensome than the original method in
the potential impacts of the proposed rule on small entities and welcome comments on issues related to such impacts. regulations.
D. Unfunded Mandates Reform Act This action contains no Federal mandates under the provisions of Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), Public Law 1044, establishes requirements 2 U.S.C. 1531

- 1538 for Federal agencies to assess the effects of their regulatory actions on State, local, and or tribal governments and or the private sector. Under Section 202 of the UMRA, the EPA generally must prepare a written

s tatement, including cost

- benefit analysis, for proposed and final rules with "Federal mandates" that may result in expenditures to This action imposes no enforceable duty on
any State , local , and tribal governments, in the aggregate, or to the private sect or, 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 reasonable50

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 uniquel y affect small governments, including tribal governments, it must have developed under Section 203 of the UMRA a small government agency plan. The plan must provide for notifying potentially affected small governments, enabling official of affected small governments to have meaningful and timely input in the development of EPA regulatory proposals with significant Federal intergovernmental mandates, and informing, educating, and advising small governments on compliance with the regulatory 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 action is not subject to the requirements of section s 202 and 205 of the UMRA. or 205 of the UMRA. This action is also not subject to the requirements of section 203 of UMRA because it contains no regulatory requirements that might significantly or u niquely51

affect small governments. Any small entity that chooses to use Method 301 would likely do so because this option is
less burdensome.
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 federali sm 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 dist ribution 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 b y 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 not52

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 ame nded rule will not have federalism implications. They This action does not have federalism implications. It will not have substantial direct effects on the States, on the relationship between the national government and the States, or on the distribution of power and responsibilities among the various levels of government, 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 E xecutive Order do not apply This final rule simply amends Method 301 which may be used to validate
test data or a new test method
. 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 polic ies that53

have tribal implications.” The proposed amended rule This action does not have tribal implications, as specified in Executive Order 13175 . The proposed action serves to clarify and simplify procedures for using (65 FR 67429, November 9, 2000). This final rule amends Method 301 which can be used to validate a new or alternative methods. Therefore, Executive Order compliance test method. It does not add any new requirements and does not affect pollutant emissions or air quality. Thus, Executive Order 13175 does not apply to this action. Although EO 13175 does not apply to the proposed amended rule. this proposed rule, EPA specifically solicited comment on the proposed rule from tribal officials. No comments were received.
G. Executive Order 13045

- Protection of Children from Environmental Health Risks and Safety Risks Executive Order EPA interprets EO 13045 , “Protection of Children from Environmental Health Risks and Safety Risks” (62 FR F.R. 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 eff ect on54

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

reasona ble alternatives considered by the EPA. The EPA interprets Executive Order 13045 ) as applying only to those regulatory actions that are based

on concern health or safety risks, such that the analysis required under section 5

- 501 of the Executive
Order EO has the potential to influence the regulation. The proposed amended rule This action is not subject to Executive Order EO 13045 because it is does not economically significant as defined in Executive Order 12866, and because this proposed amended rule is not
ba sed on establish an environmental standard intended to mitigate 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 S upply, Distribution, or
Use This rule action is not subject to Executive Order 13211, “Actions Concerning Regulations That Significantly Affect Energy Supply, Distribution, or Use”55

(66FR28355(May22 (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 I. National Technology Transfer and Advancement
Act Section 12 (d) of the National Technology Transfer and Advancement Act of 1995 (NTTAA), Public Law No. 104

- 113, Section 12(d) 915 (15 U.S.C. 272 note ), ) directs all Federal agencies EPA to use voluntary consensus standards instead of government unique

Method 301
- Page 24 of 62
standards in their its regulatory activities unless to do so would be inconsistent with applicable law or otherwise impractical. Voluntary consensus standards are technical standards (for example, materials specifications, test methods, sampling procedures, and business practices) that are developed or adopted by voluntary consensus standards bodies. The NTTAA directs EPA to provide Congress, through OMB, explanations when the Agency decides not to use available and applicable voluntary consensus standards. Voluntary consensus standards are technical standards56

(e.g., materials specificat ions, 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 Am erican 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 operator s of sources regulated by Part 63 standards the flexibility and option to use alternative standards. Today’s proposed amended rule is57

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. This rulemaking involves technical standards. While the Age ncy has identified ASTM D4855

- 97 as being potentially applicable, we have decided not to use it in this rulemaking. The use of this voluntary consensus standard would have been impractical as the ASTM standard is less prescriptive than Method 301 for many procedures. For example, the ASTM standard does not require the use of a t

-58

test explicitly to test the precision of an alternative method, but instead states than a t

- test or F

- test should be used, as appropriate. The primary difference between the
ASTM standard and EPA Method 301 is that the ASTM standard addresses the testing of “materials” rather than environmental samples. Therefore, we believe the ASTM is impractical as an alternative to Method 301.
J. Executive Order 12898

- Federal Actions to Address Environmental Justice in Minority Populations and Low

- income Populations Executive Order (EO) 12898 (59 FR 7629 (Feb. 16, 1994) establishes federal executive policy on environmental justice. Its main provision directs Federal agencies, to the grea test extent practicable and permitted by law, to make environmental justice part of their mission by identifying and addressing, as appropriate, disproportionately high and adverse human health or environmental effects of their programs, policies, and acti vities on minority populations and low

- income populations in the United States. EPA has determined that this final rule will not have disproportionately high and adverse human health or environmental effects on minority or low

- income populations59

because it does not affect the level of protection provided to human health or the environment. This action amend s a method for validating new or alternative compliance test methods. It does not change any existing rules that limit air pollution emission limits.
K. Congressional Review Act The Congressional Review Act, 5 U.S.C. 801 et seq. , as added by the Small Business Regulatory Enforcement Fairness Act of 1996, generally provides that before a rule may take effect, the agency promulgating the rule must submi t a rule report, which includes a copy of the rule, to each House of the Congress and to the Comptroller General of the United States. EPA will submit a report containing this rule and other required information to the U.S. Senate, the U.S. House of Repre sentatives, and the Comptroller General of the United States prior to publication of the rule in the Federal Register. A major rule cannot take effect until 60 days after it is published in the Federal Register. This action is not a “major rule” as defin ed by 5 U.S.C. 804(2). This rule will be effective [Insert date of publication in
the Federal Register ]
.60

Method 301
- Field Validation of Pollutant Measurement

Methods from Various Waste Media
List of Subjects in 40 CFR Part 63 Environmental protection, Alternative test method, Air pollution control, Field validation, Hazardous air pollutants, Method 301.

________________________ Dated: December 16, 2004.

Michael O. Leavitt,

_________________________ Lisa P. Jackson , Administrator.61

For the reasons stat ed in the preamble, title 40,

c hapter 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. Part 63 Appendix A is a mended by revisi ng Appendix A Method 301 to read as follows: Appendix A to Part 62 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 Procedures62

7 6 .0 What sampling procedures must I use? 8 7 .0 How do I ensure sample stability? Bias and Precision
8.0 What are the requirements for bias? 9.0 What are the requirements for bias precision ? 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 met hod if I am using paired sampling systems? 13 11 .0 What calculations must I perform for comparison with a validated method if I am using quadruplet replicate sampling systems?
14 12 .0 What calculations must I perform for analyte spiking? 15 13 .0 How do I c onduct tests at similar sources? Optional Requirements
16 14 .0 How do I use and conduct ruggedness testing? 17.0 What detection limits must I use? 15.0 How do I determine the L imit of Detection (LOD) for the alternative method? Other Requirements and Information
18 16 .0 How do I apply for approval to use an alternative
test method?63

19 17 .0 How do I request a waiver? 20.0 What definitions apply to this method?
21 18 .0 Where can I find additional information? Using Method 301
1.0 What is the purpose of Method 301? This method describes the minimum The purpose of Method 301 is to provide a set of procedures that you, the owner or operator of an affected source subject to requirements under 40 CFR Part 63 , must can use to validate an alterna tive test method to a test method required in 40 CFR part 63
. , or to validate a stand

- alone alternative test method based on established precision and bias criteria. If you use Method 301 to validate your proposed alternative method, you must
use th e procedures described in this m ethod. This method describes t he minimum procedures that you must use to validate an alternative test method to meet 40 CFR Part 63 compliance requirements. If you choose to propose a validation method other than Method 301, you must submit and obtain the Administrator’s approval for the alternative validation method. 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 63,64

you must can use Method 301 to validate the alternative test method. You must request approval to use the this alternative test method according to the procedures in Section 18 Section s 16 and § 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
. for alternative test methods. Section 19 17 describes the requirements for obtaining a waiver. 3.0 What does Method 301 include? 3.1 Procedures. 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. 3.2 Definitions.
Affec ted 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 and65

analytical methodology selected for field validation using the method described in this appendix.
P aired 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 replic ate 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). T he model can be distinguished by the method from the compounds being analyzed. 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 th e alternative test method's bias. Then, you collect multiple, collocated simultaneous samples to determine the alternative test method's precision. Alternatively, though it is not required, we allow validation testing over a broad range of concentrations over an extended time period to determine66

precision of a proposed alternative method. Sections 5.0 through 17.0 describe these the procedures in de tail. Reference Materials and Performance Audits
5.0 What reference materials must I use? You must use reference materials ( a material or substance whose one or more properties are sufficiently homogenous to the analyte) that is, analytes) are traceable
to a national standards body (e.g., National Institute of Standards and Technology (NIST)) at the level of the applicable emission limitation or standard that the subpart in 40 CFR Part 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 You must obtain information about your analyte according to
th e procedures in 5.1 through 5.4. 5.1 Exhaust Gas Tests Concentration . 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 certification for the analyte concentration and recommendations for67

recertification stability
. 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 di luted 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 to xic 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.68

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 repo rt. 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 i n evaluating the measured emissions.69

Sampling Procedures
7 6 .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
. (or the equivalent). Isotopic sampling can only be used for procedures requiring mass spectrometry or radiological procedures . You must collect samples according to the requirements in Table 1. You must perform the sampling according to the procedures in Sections
7 6 .1 thro ugh 7.5 6.4
. 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
. 6.1 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 6.3 .1 through 7.4 6.3 .2 for the applicable waste medium. 7.3 6.2 Analyte Spiking . In each quadruplet set, spike half of the samples (two out of the four) with the analyte70

according to the app licable procedure in Section 7.4 6.3
. 7.4 6.3 Spiking Procedure
. 7.4 6.3 .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 ti me. 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 sam pled at the same time. The analyte must be introduced as close to the tip of the sampling train as possible.
7.4 6.3 .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 would be approximately equal to the level of the emission analyte71

concentration in the stack
. plus the applicable emission standard (corrected for spike volume). The volume amount of analyte shall be less than 10 percent of the sample volume.
7.4 6.3 .3 Liquid and Solid Analyte with Sorbent or Impinger Trains . Spike the trains with an amou nt 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 6.3 .4 Liquid and Solid Analyte with Sample Container (Bag or Canister) . Spike the containers at the completion of each test run with an amount equal to t he 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 6.4 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. this subsection. You must place the probes in the same horizontal plane.
7.5 6.4 .1 Paired Sampling Probes
. For paired72

Sample sampling 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 (where required) are used. 7.5.2 6.4.2 Quadruplet Sampling Probes
. 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 , where required, in the center or two pitot tubes , where required, 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 o r more of the stack or duct cross

sectional area. 8 7 .0 How do I ensure sample stability? 8 7 .1 Developing Storage and Analysis Procedures . If the alternative test method includes well

- established procedures supported by experimental data fo r 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 not73

required to conduct the procedures in Section 8 7 .2 or 8 7 .3.
If the alter native 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 7 .2 or 8 7 .3. The minimum storage time should be as soon as possible, but no longer than 24 72 hours after collection of the sample. The maximum storage time should
be four no longer than two weeks or less
. 8 7 .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 7 .3 Storage and Sampling Procedures for Testing Other Waste Media
. (e.g., Soil/Sed iment, Solid Waste, Water/Liquid)

. You must analyze half of the replicate samples at the proposed minimum storage time and the other half at the proposed maximum storage time or within two weeks of the initial analysis to identify the effect of storage ti mes on analyte samples. The minimum storage time should be as soon as possible, but no longer than 24
hours seven days after collection of the sample. The74

maximum storage time should be two weeks or less. 8 7 .4 Sample Stability . After you h ave conducted sampling and analysis according to 8 7 .2 or 8 7 .3, compare the results at the minimum and maximum storage times. Calculate the difference in the results using Equation 301

- 1.

d i = R mini - R maxi Eq. 301

- 1
Where : d i = difference between the results of the i th

sample.
R min i = results from the i th sample at the minimum storage time
R max i = results from the i th sample at the maximum storage time.

8 7 .4.1 Standard Deviation . Determine the standard deviation, SD d , of the differences, d i 's, of the paired

samples using Equation 301

- 2. SD d = N

i ( d i - d

m ) 2

n - 1

Eq. 301

- 2

Where:
V m = validated method Field Code Changed75

P m = proposed alternative test method
d i = The difference between the i

- th pair of samples, V m - P m results of the i th sample,
R mini - R maxi d m = The mean of the paired sample differences
. , n = total number of paired samples 8 7 .4.2 T Test . Test the difference in the results for statistical significance by calculating the t

- statistic and determining if the mean of the differences between the initial results and the results after storage is significant at the 95 percent confidence level
. and n

– 1 degrees of
freedom. C alculate the value of the t

- statistic using Equation 301

- 3.

t = d

m SD d n
Eq. 301

- 3

Where: n is the total number of paired samples. Compare the calculated t

- statistic with the critical
value of the t

- statistic from Table 2. If the calculated t

value is less than the critical value, the difference is not Field Code Changed76

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 7 .2 or 8 7 .3 with new samples using shorter proposed maximum storage tim es. Bias and Precision
9 8 .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% without the use of correction factors, and no more than ± 30% with the use of correction factors for bias values between 10 and 30 percent for the alternative test method to be acceptable. 10 9 .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

re lative standard deviation (RSD ), ) of the alternative test method at the level of the applicable emissio n limitation or standard in the subpart of 40 CFR Part 63 must be less than77

or equal to 20 percent. For samples with a precision greater than 20 percent but less than 50 percent, a minimum of nine sample runs will be required. 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
. (Section 11.2.2).
11 10 .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 10 .1 through
11 10 .3.
11 10 .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.
B = S m - CS

Eq. 301

- 4 Field Code Changed78

Where:
B = Bias at the spike level.
S m = Mean of the measured values of the isotopically spiked samples.
CS = Calculated value of the isotopically labeled spike.
11 10 .2
. Standard Deviation . Calculate the standard deviation of the S i values according to Equation 301

- 5.

SD = ( S i - S m ) 2

( n - 1 )

Eq. 301

- 5

Where:
S i = Measured value of the isotopically labeled analyte in the i

- th field sample,

n = Number of isotopically spiked samples, 12.
11 10 .3 T Test . Test the bias for statistical significance by calculating the t

- - statistic using Equation 301

- 6. Use the standard deviation determined in section
11 10 .2 and the numerical bias determined in section 11 10 .1.

t = B SD n Field Code Changed79

Eq. 301

- 6

Compare the calculated t

- value with the critical value
of the two

- - sided t

- - distribution at the 95 percent confidence level and n

- - 1 degrees of freedom. When spiking is conducted according to the procedures specified in sections 7 6 .2 and 7 6 .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 bias of the candidate test method is acceptable. If the calculated t

value is greater than the critical value, the bias is statistically significant and you must evaluate the relative magnitude of the bias using Equation 301

- 7.

Eq. 301

- 7

Where:
B R = Relative bias. If the relative bias is less than or equal to 10 percent , then the data are the bias of the candidate test method is acceptable
. and no correction factors are Field Code Changed80

required. If the relative bias is greater than 10 percent but less than 30 percent , and if you correct all futu re data collected with the method for the magnitude of the bias, the bias of the candidate test method is acceptable. If either of the preceding two cases applies, you may proceed continue
to evaluate the method by calculating its precision. If
not , the c andidate method will not meet the requirements of Method 301.
11 10 .4 Relative Standard Deviation. Calculate the RSD according to Equation 301

- 8

RSD = SD

S m 100

where Eq. 301

- 8

Where:
S m 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 11 .0 What calculations must I perform for comparison with a validated method if I am using paired quadruplet replicate sampling systems? If you are using quadruplet replicate sampling systems Field Code Changed81

to compare an alternative test method to a validated method, then you must analyze the data according to the provisions in this section. If the data from t he 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 additi onal precision checks. 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 a lternative test method fail either the bias or precision test, the data and the alternative test method are unacceptable. 12 11 .1 Bias Analysis
. 12.1.1 Standard Deviation . Determine the standard deviation, SD d , of the differences, d i 's, of the paired samples using Equation 301

- 2. 12.1.2 t Test
. Test the bias for statistical significance at the 95 percent confidence level by calculating the t

- statistic and determine if the
. 11.1.1 Bias . Determine the bias, which is defined as82

the mean of the differences between the alternative test method and the validated method is significant at the 95 percent confidence level. (d m ). Calculate the d i according to Equation 301

- 9.
Eq. 301

- 9

Where:
V 1i = First measured value with the validated method in the i

- th sample.
V 2i = Second measured value with the validated method in the i

- th sample.
P 1i = First measured value with the alternative test method in the i

- th sample.
P 2i = Second measured value with the alternative test method in the i

- th sample. 11.1.2 Standard Deviation of the Differences
. Calculate the standard deviation of the differences, SD d , using Equation 301

- 2. 11.1.3 T Test . Calculate the t

- statistic using Equation 30 1

- 3
. , where n is the total number of test sample differences (d i ). For the spiking quadruplet sampling system Field Code Changed83

procedure for paired sampling systems, according to in Section 7 6 .1 and Table 1, n equals nine.
four. Compare the calculated t

- statist ic with the critical value of the t

- statistic
. , and determine if the bias is significant at the 95 percent confidence level.
When nine four runs are conducted, as specified in Section 7.1 6.2 and Table 1, the critical value of the t

- - statistic is 1.397 3.1 82 for eight 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 statisticall y 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.
.

B R = X 100% Eq. 301

- 9 10

Where: B = Bias = – mean of the d i ’s
. VS = mean measured by the validated method
. 12 If the relative bias is less than or equal to 1084

percent, the bias of the candidate test method is acceptable and no correction factors are required. If the relative bias is greater than 10 percent but less than 30 percent and if you correct all future data collected with the method for the magnitude of the bias, the bias of the candidate test method is acceptable. If either of the preceding two cases applies, you may continu e to evaluate the method by calculating its precision. If not, the candidate method will not meet the requirements of Method 301.
11 .2
. Precision . Compare the estimated variance (or standard deviation) of the alternative test method to that of the valid ated 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 proc edure requires that you know the standard deviation of the validated method, SD v . Use the value furnished with the method. If Calculate the standard deviation estimated variance of the validated method is not available, the paired replicate sampling proced ure may not be used. using Equation 301

- 11. 12 11 .2.1 Alternative Test Method Variance . Calculate the estimated variance of the validated alternative test85

method, S v 2 , using Equation 301

- 10.

S 2
v = SD 2

v Where:
SD v = Standard deviation provided with the validated method. 12.2.2 Pooled Variance . Calculate the pooled variance of both methods, S 2 pooled S p 2 , according to Equation 301

- 11.

S 2 pooled = N

i d i 2 2 ( n - 1 )

Eq. 301

- 11

Where: d i = 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 collected with the alternative test method , S 2 p , from the S 2 pooled using Equation 301

- 12. S 2 p = S 2 pooled - S 2
v . (If S 2 v > S 2 pooled , let S 2 p = S 2 pooled /2).

12.2.4 n = number of samples and the degrees of freedom. Field Code Changed86

11.2.2 The F test . Determine if the estimated variance of the alternative test method is significantly different from greater than that of the validated method by performing calculating the F test. Calculate the experimental F

- value us ing Equation 301

- 13. 12.

F = S

p 2 S v 2

Eq. 301

- 12

Where:
S p 2 = The estimated variance of the alternative method.
S v 2 = The estimated variance of the validated method. Compare the experimental F value with the critical range of F at a 95 percent one - sided confidence level
. for F. The one

- sided co nfidence level of 95% for F is 6.388 when the procedure specified in Section 7 6 .1 and Table 1 for paired quadruplet 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 the candidate test method are unacceptable. 13 12 .0 What calculations must I perform for comparison with87

a validated method if I am using quadruplet replicate sampling systems analyte spiking ? 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 Administrato r may require additional precision checks. 13 You must analyze the data for analyte spike testing according to this section.
1 2 .1 Bias Analysis . Test the bias for statistical significance at the 95 percent confidence level by calculating the t

- statistic. 13 12 .1.1 Bias . Determine the bias , which is defined

as using the mean results from the analysis of the differences between the alternative test method spiked field samples, the unspiked field samples, and the validated method (d m ). Calculate d i according to calculated value of the spike using Equation 301

- 14 13
.88

d i = ( V

1 i + V

2 i ) 2 - ( P 1 i + P 2 i )

2
Eq. 301

- 13

Where: V 1i =

S 1i = First measured value with of the validated method in the i

- th ith spiked sample.
V 2i = S 2i = Second measured value with the validated method in of the i

- th ith spiked sample.
P 1i = M 1i = First measured value with of the alternative test method in the i

- th ith unspiked sample.
P 2i = Second measured value with the alternative test method in the i

- th sample. 13 M 2i = Second measured of the ith unspiked sample. CS = Calculted value of the spiked level.
12 .1.2 Standard Deviation of the Differences
. Calculate the standard deviation of the differences, SD d , using Equation 301

- 2. Field Code Changed89

13 12 .1.3 T Test . Calculate the t

- statistic using Equation 301

- 3, where n is the total number of test sample differences (d i ). For the quadruplet sampling syste m procedure in Section 7.1 and Table 1, n equals four six
. Compare the calculated t

- statist ic with the critical value
from of the t

- statistic , and determine if the bias is significant at the 95 percent confidence level. When
four six runs are conducted, as specified in Section 7.2 and Table 1, the 2

- sided confidence level critical value of the
t

- statistic is 1.638 2.571 for three the five degrees of freedom. If the calculated t

- value is less than the critical value, the bias is not sta tistically 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 with no correction factors, or the bias is greater than 10 percent but less than 30 percent with the use of correction factors , then the data are acceptable. Proceed to evaluate precision of the alternative candidate test method. 13.2 Precision . Compare the variance of the alternative test method to that of the validated method. If90

a significant difference is determined using the F test, the alternative test method and the results are rejected. If
the F test does not sh ow a significant difference, then the alternative test method has acceptable precision. This procedure requires the standard deviation of the validated method, SD v , 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, S p 2 , according to Equation 301

- 15.

S 2 p = d 2

i 2 n
Where: d i = 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 metho d 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 in91

Section 7.1 and Table 1 for quadrup let 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 anal yze 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 th e calculated value of the spike using Equation 301

- 16.
B = S m - M

m - CS
Where:
B = Bias at the spike level.
S m = Mean of the spiked samples.
M m = 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 2.22892

for the ten degrees of freedom.

t = B S 2
u + S 2

s 12

B R = X 100% Eq. 301

- 10

Where:
S 2 u = (SD u ) 2 , SD u is calculated in Equation 301

- 19.

S 2 s = (SD s ) 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 statist ically 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 B = Bias

– mean of the d i ’s. VS = mean measured by the validated method.
12 .2 Precision . Calculate the standard deviation and
the RSD relative standard deviation of the alternative candidate test method. 14.2.1 Spiked Samples . Calculate the difference, d i , Field Code Changed93

between the pairs of the spiked alternative test method measurements for each replicate sample set. Determine the standard deviation (SD s ) of the spiked values using Equation 301

- 18.

SD s = d is 2

2 n
Where: d is = Difference between the i

- th pair of spiked samples. n = Number of paired samples. 14.2.2 Unspiked Samples . Calculate the The relative standard deviation of the unspiked values using Equation 301

- 19.

SD u = d iu 2

2 n Where: d iu = 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.

F = S u 2 S s 2

Where S u 2 and S s 2 are defined in Equation 301

- 17.94

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 (SD pooled ) using Equation 301

- 21.

SD pooled = S s 2 + S u 2

2 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 candidate test method can be calculated 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, S m is the mean of the unspiked samples. If the standard deviation of the spiked samples is used, S m is the mean of the spiked samples. The data and alternative test method are unacceptable if the RSD is greater than 20 percent.
. 15 13 .0 How do I conduct tests at similar sources? If the Administrator has approved the use of an alternative test method to a test method required in 40 CFR Part 63 for an affected source, and the Administrator has95

approved the use of the alternative test method at your similar source according to the pr ocedures in 19 17 .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 concentratio n. Optional Requirements
16 14 .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 C FR 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 procedu res in Citation 10 18.16 of Section 18 .0 and submit a request for a waiver according to 19 17 .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 samp le 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 variables96

in eight experiments instead of one. (W.J. Youde n, Statistical Manual of the Association of Official Analytical Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33

- 36).
17 15 .0 How do I determine the Limit of Detection for the alternative method?
17 15 .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
p rotocol, the LOD is defined as 3 three times the standard deviation, S o , at the blank level. This LOD corresponds to an uncertainty of ±30% at the 99 percent confidence
level.
17 15 .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 calcula ted LOD, use Procedure I in Table 4 to determine S o . If the LOD is greater than twice the calculated LOD, use Procedure II in Table 4 to determine
S o . For radiochemical methods, use the Multi

- Agency Radiological Laboratory Analytica l Protocols (MARLAP) Ma nual (i.e ., uses the minimum detectable conce ntration (MDC) and not the LOD) available at http://www.epa.gov/radiation/docs/marlap/402

- b

- 04

- 001c

-97

20_final.pdf
. Other Requirements and Information
18 16 .0 How do I apply for approval of to use an alternative
test method? 18 16 .1 Submitting Requests . You must request to use an alternative test method according to the procedures in § Section 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 incl ude a field validation reporting report containing the information in 18 Section 16 .2. The request must be submitted to the Director, Emissions Monitoring and Analysis Air Quality Assessment Division, U.S. Environmental Protection Agency, C304

- 02, Research Triangle Park, NC 27711. 18 16 .2 Field Validation Report . The field validation report must contain the information in 18 16 .2.1 through 18 16 .2. 9 8
. 18 16 .2.1 Regulatory objectives for the testing, including a description of the reasons for the test, applicable emission limits, and a description of the source. 18 16 .2.2 Summary of the results a nd calculations shown in Sections 7 6 .0 through 17 16 , as applicable.98

18 16 .2.3 Analyte certification and value(s). 18 16 .2.4 Laboratory demonstration of the quality of the spiking system. 18.2.5 Discussion of laboratory evaluations. 18 16.2.5 Discussion of field sampling. 16 .2.6 Discussion of field sampling. 18.2.7 Discussion of sample preparations and analysis. 18 16 .2. 8 7 Storage times of samples (and extracts, if applicable). 18 16 .2. 9 8 Reasons for eliminating any results. 19 17 .0 How do I request a waiver? 19 17 .1 Conditions for Waivers. If you meet one of the criteria in 19 17 .1.1 through 19 17 .1. 3 2 , the Administrator may waive the requirement to use the procedures in this method to validate an alternative test method. In addition, if the EPA curre ntly 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 17 .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 the99

Administrator’s Administrator = s satisfaction that your affected source is similar to that source, then the Administrato r 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 14 .0. 19 17 .1.2 Documented M ethods . 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. You100

can find a list of conditional test methods at http://www.epa.gov/ttn/emc/ctm.html.
19 17
. 2 Submitting Applications for Waivers . You must sign and submit each request for a waiver from the requirements in this method in writing. The request must be submitted to the Director, Emissions Monitoring and Analysis Air Quality Assessment Division, U .S. Environmental Protection Agency, C304

- 02, Research Triangle Park, NC 27711. 19 17 .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 vali dation or other supporting documents. The request for a waiver must contain, at a minimum, the information in 19 17 .3.1 through 19 17 .3.4. The Administrator may request additional information if necessary to determine whether this method can be waived for a particular application. 19 17 .3.1 A Clearly Written Test Method . The method should be written preferably in the format of 40 CFR Part 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.101

19 17 .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 17 .3.3 Ruggedness Testing Results. You must submit results of ruggedness testing conducted according to Section 16 14 .0 , sample stability conducted according to Section 8 7 .0 , and detection limits conducted according to Section
17 15 .0 , 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 17 .3.4 Applicability Statement and Arguments Basis for Waiver Approval. Discussion of t he applicability
statement and arguments basis 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 and102

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 th at 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 18 .0 Where can I find additional information?
You c an find additional information in the references in paragraphs 21 Section s 1 8 .1 through 21.12 1 8 .16
. 21 18 .1 Albritton, J.R., G.B. Howe, S.B. Tompkins, R.K.M. Jayanty, and C.E. Decker. 1989. Stability of Parts

Per

- Million Organic Cylinder Gases and Results of Source Test Analysis Audits, Status Report No. 11. Environmental Protection Agency Contract 68

- 02

- 4125. Research Triangle Institute, Research Triangle Park, NC. September. 21.2 18.2 ASTM Standard E 1169

- 89 (current version),103

“Standard Guide for Conducting Ruggedness Tests,” available from ASTM, 100 Barr Harbor Drive, West Conshohoken, PA 19428. 18.3 DeWees, W.G., P.M. Grohse, K.K. Luk, and F.E. Butler. 1989. Laboratory and Field Evaluation of a Methodology for Speciating Nickel Emissions f rom 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 18.4 International Conference on Harmonization of Technical Requirements for the Registration of Pharmaceuticals for Human Use, ICH

- Q2A, “Text on Validation of Analytical Procedures,” 60 FR 11260 (March 1995). 18.5 International Conference on Ha rmonization of Technical Requirements for the Registration of Pharmaceuticals for Human Use, ICH

- Q2b, “Validation of Analytical Procedures: Methodology,” 62 FR 27464 (May 1997) 18.6 Keith, L.H., W. Crummer, J. Deegan Jr., R.A. Libby, J.K. Taylor, and G. Wentler. 1983. Principles of Environmental Analysis. American Chemical Society, Washington, DC. 21.4 18.7 Maxwell, E.A. 1974. Estimating variances104

from one or two measurements on each sample. Amer. Statistician 28:96

- 97. 21.5 18.8 Midgett, M. R. 1977. How EPA Validates NSPS Methodology. Environ. Sci. & Technol. 11(7):655

- 659. 21.6 18.9 Mitchell, W.J., and M.R. Midgett. 1976. Means to evaluate performance of stationary source test methods. Environ. Sci. & Technol. 10:85

- 88. 21.7 18.10 Plackett, R.L., and J.P. Burman. 1946. The design of optimum multifactorial experiments. Biometrika, 33:305. 21.8 18.11 Taylor, J.K. 1987. Quality Assurance of Chemical Measurements. Lewis Publishers, Inc., pp. 79

- 81. 21.9 18.12 U.S. Environmental Protection Agency. 1978. Quality Assurance Handbook for Air Pollution Measurement Systems: Volume III. Stationary Source Specific Methods. Publication No. EPA

- 600/4

- 77

- 027b. Office of Research and Development Publications, 26 Wes t St. Clair St., Cincinnati, OH 45268.21.10 18.13 U.S. Environmental Protection Agency.

1981. A Procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards Standard Reference Materials. Publication N o. EPA

- 600/7

- 81

- 010. Available from the U.S. EPA, Quality Assurance Division (MD

77), Research Triangle Park, NC 27711. 21.11 18.14 U.S. Environmental Protection Agency. 1991. Protocol for The Field Validation of Emission Concentrations From Station ary 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 18.15 Wernimont, G.T., “Use of Statistics to
De velop and Evaluate Analytical Methods,” AOAC, 1111 North 19 th Street, Suite 210, Arlington, VA 22209. USA, 78

- 82 (1987). 18.16 Youden, W.J. Statistical techniques for collaborative tests. In: Statistical Manual of the Association of Official Analytica l Chemists, Association of Official Analytical Chemists, Washington, DC, 1975, pp. 33

- - 36.Page 106 of 111

Table 1 of Appendix A. Sampling Procedures If you are... You must collect... comparing against a validated method nine sets of replicate samples using a paired sampling system (a total of 18 samples) or four sets of replicate samples using a quadruplet sampling system (a total of 16 samples). In each sample set, you must use the validated test method to collect and analyze half of the samples. using isotopic spiking (can only be used for procedures requiring mass spectrometry) a total of 12 replicate samples. You may collect the samples either by obtaining six sets of paired samples or three sets of quadruplet samples. using analyte spiking a tot al of 24 samples using the quadruplet sampling system (a total of 6 sets of replicate samples). Formatted TablePage 107 of 111

Table 2. of Appendix A. Critical Values of t for the Two Tailed 95 Percent Confidence L imit Degrees of freedom t 95

1 3=078 12.706
2 1=886 4.303
3 1=638 3.182
4 1=533 2.776
5 1=476 2.571
6 1=44 2.447
7 1=415 2.365
8 1=397 2.306
9 1=383 2.262
10 1=372 2.228Page 108 of 111

Table 3 of Appendix A. Storage and Sampling Procedures for Stack Test Emissions If you are... With... Then you must... using isotopic or analyte spiking procedures sample container (bag or canister) and impinger sampling systems analyze six of the samples at the proposed minimum storage time within seven days and then analyze the same six samples at the proposed maximum storage time or two weeks after the initial analysis
. sorbent and impinger sampling systems that require extraction or digestion extract or digest six of the samples at the proposed minimum storage time within seven days and extract or digest six other samples at the proposed maximum storage time

. or two weeks after the first extraction or digestion. Analyze an aliquot of the first six extracts (digestates) at both the proposed minimum within seven days and proposed maximum storage times

. or two weeks after the initial analysis. This will allow analysis of extract storage impacts. Formatted TablePage 109 of 111

Table 3 of Appendix A. Storage and Sampling Procedures for Stack Test Emissions If you are... With... Then you must...
sorbent sampling systems that require thermal desorption analyze six samples at the proposed minimum storage time. within seven days. Analyze another set of six samples at the proposed maximum storage time or within two weeks of the initial analysis
. comparing an alternative test method against a validated test method sampling method that does not include sorbent and impinger sampling systems that require extraction or digestion analyze half of the samples (8 or 9) at the proposed minimum storage time within seven days and ha lf of the samples (8 or 9) at the proposed maximum storage time or within two weeks of the initial analysis
. Formatted TablePage 110 of 111

Table 3 of Appendix A. Storage and Sampling Procedures for Stack Test Emissions If you are... With... Then you must...
sorbent and impinger sampling systems that require extraction or digestion extract or digest six of the samples at the proposed minimum storag e time within seven days and extract or digest six other samples at the proposed maximum storage time

. or within two weeks of the first extraction or digestion. Analyze an aliquot of the first six extracts (digestates) at both the proposed minimum within se ven days and at the proposed maximum storage times or within two weeks of the initial analysis . This will allow analysis of extract storage impacts. Formatted TablePage 111 of 111

Table 4 . to of Appendix A. Procedures for Estimating S o If the estimated LOD (LOD 1 , expected approximate LOD concentration level) is no more than twice the calculated LOD, use Procedure I as follows. If the LOD estimated LOD (LOD 1 , expected approximate LOD concentration level) is greater than twice the calculated LOD, use Procedure II as follows. Estimate the LOD (LOD 1 ) and prepare a test standard at this level. The test standard could consist of a dilution of the analyte described in Section 5.0. Prepare two additional standards (LOD 2 and LOD 3 ) at concentration levels lower than the standard used in Procedure I

. (LOD 1 ). Using the normal sampling and analytical procedures for the method, sample and analyze this standard at least seven times in the laboratory. Sample and analyze each of these standards (LOD 2 and LOD 3 ) at least seven times.

Calculate the standard deviation, S o S 1 , of the measured values. Calculate the standard deviation (S 2 and S 3 ) for each concentration level. Calculate the LOD LOD 0 (referred to as the calculated LOD)as 3 times S o S 1 , where S 0 = S 1 . Plot the standard deviations of the three test standards (S 1 , S 2 and S 3 ) as a function of the standard concentrations concentration
. Draw a best

- - fit straight line through the data points and extrapolate to zero concentration. The standard deviation at ze ro concentration is S o . Calculate the LOD LOD 0 (referred to as the calculated LOD)as 3 times S o .