Source: https://www.federalregister.gov/documents/2016/12/02/2016-27544/revisions-to-method-301-field-validation-of-pollutant-measurement-methods-from-various-waste-media
Timestamp: 2017-09-20 08:39:52
Document Index: 34680001

Matched Legal Cases: ['art 2', 'art 63', 'art 63', 'art 136', 'art 136', 'art 136', 'art 136', 'art 136', 'art 63', 'art 65', 'arts 63', 'arts 63', 'art 59', 'art 60', 'art 61', 'arts 63', 'art 59', 'arts 60', 'art 136', 'art 63', 'arts 59', 'art 63', 'art 59', '§\u200959', '§\u200959', '§\u200960', '§\u200961', '§\u200963', '§\u200965', 'art 59', 'art 136', '§\u200963', 'arts 59', '§\u200959', '§\u200959', '§\u200960', '§\u200961', '§\u200965', 'art 136']

A Proposed Rule by the Environmental Protection Agency on 12/02/2016
Comments. Comments must be received on or before January 31, 2017.
87003-87016 (14 pages)
4. Bias Criteria for Multi-Source Versus Source-Specific Validation
2.0 What approval must I have to use Method 301?
11.0 What calculations must I perform for comparison with a validated method if I am using quadruplicate replicate sampling systems?
15.0 How do I determine the Limit of Detection for the candidate test method?
16.0 How do I apply for approval to use a candidate test method?
https://www.federalregister.gov/d/2016-27544 https://www.federalregister.gov/d/2016-27544
In this action, the Environmental Protection Agency (EPA) proposes editorial and technical revisions to the EPA's Method 301 “Field Validation of Pollutant Measurement Methods from Various Waste Media” in order to correct and update the method. In addition, the EPA is clarifying the applicability of Method 301 as well as its utility to other regulatory provisions. The proposed revisions include ruggedness testing for validation of test methods for application at multiple sources, determination of limit of detection for all method validations, incorporating procedures for determining the limit of detection, revising the sampling requirements for the comparison procedure, adding storage and sampling procedures for sorbent sampling systems, and clarifying acceptable statistical results for candidate test methods. We also propose to clarify the applicability of Method 301 to our regulations and to add equations to clarify calculation of the correction factor, standard deviation, estimated variance of a validated test method, standard deviation of differences, and t-statistic for all validation approaches.
Changes made to the Method 301 field validation protocol under this proposed action would apply only to methods submitted to the EPA for approval after the effective date of this action.
Public Hearing. If anyone contacts the EPA requesting a public hearing by December 12, 2016, the EPA will hold a public hearing on January 3, 2017 from 1:00 p.m. (Eastern Standard Time) to 5:00 p.m. (Eastern Standard Time) at the U.S. Environmental Protection Agency building located at 109 T.W. Alexander Drive, Research Triangle Park, NC 27711. Information regarding a hearing will be posted at http://www3.epa.gov/​ttn/​emc/​methods/​.
Submit your comments, identified by Docket ID No. EPA-HQ-OAR-2016-0069, to the Federal eRulemaking Portal: http://www.regulations.gov. Follow the online instructions for submitting comments. Once submitted, comments cannot be edited or withdrawn. The EPA may publish any comment received to its public docket. Do not submit electronically any information you consider to be Confidential Business Information (CBI) or other information whose disclosure is restricted by statute.
Multimedia submissions (audio, video, etc.) must be accompanied by a written comment. The written comment is considered the official comment and should include discussion of all points you wish to make. The EPA will generally not consider comments or comment contents located outside of the primary submission (i.e., on the Web, Cloud, or other file sharing system). For additional submission methods, the full EPA public comment policy, information about CBI or multimedia submissions, and general guidance on making effective comments, please visit http://www2.epa.gov/​dockets/​commenting-epa-dockets.
For information concerning this proposal, contact Ms. Kristen J. Benedict, Office of Air Quality Planning and Standards, Air Quality Assessment Division (E143-02), Environmental Protection Agency, Research Triangle Park, NC 27711; telephone number: (919) 541-1394; fax number: (919) 541-0516; email address: benedict.kristen@epa.gov.
H. Executive Order 13211: Actions That Significantly Affect Energy Supply, Distribution, or UseStart Printed Page 87004
Method 301 affects/applies to you, under 40 CFR 63.7(f) or 40 CFR 65.158(a)(2)(iii), when you want to use an alternative to a required test method to meet an applicable requirement or when there is no required or validated test method. In addition, the validation procedures of Method 301 are an appropriate tool for demonstration of the suitability of alternative test methods under 40 CFR 59.104 and 59.406, 40 CFR 60.8(b), and 40 CFR 61.13(h)(1)(ii). If you have any questions regarding the applicability of the proposed changes to Method 301, contact the person listed in the preceding FOR FURTHER INFORMATION CONTACT section.
Submitting CBI: Clearly mark the part or all of the information that you claim to be CBI. For CBI information in a disk or CD-ROM that you mail to the EPA, mark the outside of the disk or CD-ROM as CBI and then identify electronically within the disk or CD-ROM the specific information that is claimed as CBI. In addition to one complete version of the comment that includes information claimed as CBI, a copy of the comment that does not contain the information claimed as CBI must be submitted for inclusion in the public docket. Information marked as CBI will not be disclosed except in accordance with procedures set forth in title 40 CFRpart 2.
Do not submit information that you consider to be CBI or otherwise protected through http://www.regulations.gov or email. Send or deliver information identified as CBI to: OAQPS Document Control Officer (Room C404-02), U.S. EPA, Research Triangle Park, NC 27711, Attention Docket ID No. EPA-HQ-OAR-2016-0069.
Docket: All documents in the docket are listed in the http://www.regulations.gov index. Although listed in the index, some information is not publicly available, e.g., CBI or other information whose disclosure is restricted by statute. Certain other material, such as copyrighted material, will be publicly available only in hard copy. Publicly available docket materials are available either electronically in http://www.regulations.gov or in hard copy at the EPA Docket Center, EPA/DC, EPA WJC West Building, Room 3334, 1301 Constitution Ave. NW., Washington, DC. This Docket Facility is open from 8:30 a.m. to 4:30 p.m., Monday through Friday, excluding legal holidays. The telephone number for the Public Reading Room is (202) 566-1744, and the telephone number for the Air Docket is (202) 566-1742.
In addition to being available in the docket, an electronic copy of the proposed method revisions is available on the Technology Transfer Network (TTN) Web site at http://www3.epa.gov/​ttn/​emc/​methods/​. The TTN provides information and technology exchange in various areas of air pollution control.
The EPA originally published Method 301 (appendix A to 40 CFR part 63, Test Methods) on December 29, 1992 (57 FR 61970), as a field validation protocol method to be used to validate new test methods for hazardous air pollutants in support of the Early Reductions Program of Part 63 when test methods were unavailable. On March 16, 1994, the EPA incorporated Method 301 into 40 CFR 63.7 (59 FR 12430) as a means to validate a candidate test method as an alternative to a test method specified in a standard or for use where no test method is provided in a standard. To date, subsequent revisions of Method 301 have not distinguished requirements for source-specific applications of a candidate method versus application of a candidate test method at multiple sources. The EPA's Method 301 specifies procedures for determining and documenting the bias and precision of a test method that is a candidate for use as an alternative to a test method specified in an applicable regulation, or for use as a means for showing compliance with a regulatory standard in absence of a validated test method. Method 301 is required for these purposes under 40 CFR 63.7(f) and 40 CFR 65.158(a)(2)(iii), and would be considered an appropriate tool for demonstration and validation of alternative methods under 40 CFR 59.104 and 59.406, 40 CFR 60.8(b), and 40 CFR 61.13(h)(1)(ii). The procedures specified in Method 301 are applicable to various media types (e.g., sludge, exhaust gas, wastewater).
Additionally, the EPA recognized that there were a number of ways Method 301 could be clarified while reviewing submitted data and answering questions from facilities, environmental labs, and technology vendors on the application and requirements of the method.
In this action, we propose clarifications to the applicability and utility of Method 301 to additional regulatory provisions, and propose technical revisions and editorial changes intended to clarify and update the requirements and procedures specified in Method 301.
In the current version of Method 301, the procedures for conducting ruggedness testing in sections 3.1 and 14.0, and for determining the limit of detection (LOD) in sections 3.1 and 15.0, are optional procedures that are not required for validation of a candidate test method. In this action, we propose to amend sections 3.1 and 14.0 to require ruggedness testing when using Method 301 to validate a candidate test method intended for application to multiple sources. Ruggedness testing would continue to be optional for validation of methods intended for source-specific applications. We also propose to amend sections 3.1 and 15.0 to require determination of the LOD for validation of all methods (i.e., those intended for both source and multi-source application). Additionally, we propose clarifications to the LOD definition in section 15.1.Start Printed Page 87005
Ruggedness testing of a test method is a laboratory study to determine the sensitivity of the method by measuring its capacity to remain unaffected by small, but deliberate variations in method parameters such as sample collection rate and sample recovery temperature to provide an indication of its reliability during normal usage. Requiring ruggedness testing and determination of the LOD for validation of a candidate test method that is intended for use at multiple sources will further inform the EPA's determination of whether the candidate test method is valid across a range of source emission matrices, varying method parameters, and conditions. Additionally, conducting an LOD determination for source-specific validations will account for the sensitivity of the candidate test method to ensure it meets applicable regulatory requirements.
The EPA proposes revisions to the requirements for determining the LOD specified in section 15.2 and Table 301-5 (Procedure I) to incorporate procedures of the EPA's proposed revisions to 40 CFR part 136, appendix B (80 FR 8955). The proposed revisions address laboratory blank contamination and account for intra-laboratory variability, consistent with the proposed changes to 40 CFR part 136. We propose to require Procedure I of Table 301-5 for determining an LOD when an analyte in a sample matrix is collected prior to an analytical measurement or the estimated LOD is no more than twice the calculated LOD.
For the purposes of this proposed rule, LOD would be equivalent to the calculated method detection limit (MDL) determined using the procedures specified in proposed 40 CFR part 136, appendix B. Through this proposed change, laboratories would be required to consider media blanks when performing LOD calculations. If the revisions to 40 CFR part 136, appendix B are finalized as proposed prior to a final action on this proposal, we will cross-reference appendix B. If appendix B is finalized before this action and the revisions do not incorporate the procedures as described above, the EPA intends to incorporate the specific procedures for determining the LOD in the final version of Method 301 consistent with this proposal. If appendix B is not finalized before these proposed revisions, the EPA also intends to incorporate the specific procedures directly into Method 301. Other than the proposed revisions to 40 CFR part 136, appendix B, as discussed above, changes addressed under that rulemaking are outside the scope of this proposed action.
Currently, the number of samples required by Method 301 when using a quadruplicate sampling system for conducting the analyte spiking procedure and for conducting the comparison procedure is not consistent. In this action, we propose revisions to section 11.1.3 and Table 301-1 to require six sets of quadruplicate samples (a total of 24 samples for the analyte spiking or comparison procedures) rather than four sets. This proposed revision will ensure the bias and precision requirements are consistent in the method and decrease the amount of uncertainty in the calculations for bias and precision when comparing an alternative test method with a validated method. Bias and precision (standard deviation and variance) are all inversely related to the number of sampling trains (sample results) used to estimate the difference between the alternative test method and the validated method. As the number of trains goes up, the bias and precision estimates go down. Larger data sets provide better estimates of the standard deviation or variance and the distribution of the data. The proposed revision to collect a total of 24 samples when using the analyte spiking approach is also consistent with the number of samples required for the isotopic spiking approach. The 12 samples collected when conducting the isotopic spiking approach are equivalent to the 24 samples collected using the analyte spiking approach because the isotopic labelling of the spike allows each of the 12 samples to yield two results, one for an unspiked sample and one for a spiked sample.
In this action, we also propose revisions to section 9.0 to specify that either paired sampling or quadruplicate sampling systems may be used for isotopic spiking, while only quadruplicate sampling systems may be used to establish precision for analyte spiking or when comparing an alternative method to a validated method.
For validations conducted by comparing the candidate test method to a validated test method, we propose to add: (1) Storage and sampling procedures for sorbent systems requiring thermal desorption to Table 301-2; and (2) a new Table 301-4 to provide a look-up table of F values for the one-sided confidence level used in assessing the precision of the candidate test method. We also propose an amendment to the reference list in section 18.0 to include the source of the F values.
In this action, we propose clarification to sections 8.0, 10.3, and 11.1.3 to specify that candidate test methods intended for use at multiple sources must have a bias less than or equal to 10 percent. We propose that candidate test methods with a bias greater than 10 percent, but less than 30 percent, apply only at the source at which the validation testing was conducted and that data collected in the future be adjusted for bias using a source-specific correction factor. A source-specific correction factor is not necessarily appropriate for use at multiple sources. This proposed change provides flexibility for source-specific Method 301 application while limiting the acceptance criteria for use of the method at multiple sources. We believe that the Method 301 results from a single source are not sufficient to allow us to establish a correction factor that can be applied at multiple sources.
In this action, we propose amendments to sections 9.0 and 12.2 to clarify the interpretation of the relative standard deviation (RSD) when determining the precision of a candidate test method using the analyte spiking or isotopic spiking procedures. For a test method to be acceptable, we propose that the RSD of a candidate test method must be less than or equal to 20 percent. Accordingly, we propose to remove the sampling provisions for cases where the RSD is greater than 20 percent, but less than 50 percent. Poor precision makes it difficult to detect potential bias in a test method. For this reason, we are proposing an acceptance criteria of less than or equal to 20 percent for analyte and isotopic spiking sampling procedures.
Currently, Method 301 states that it is applicable for determining alternative test methods for standards under 40 CFR part 63 (National Emission Standards for Hazardous Air Pollutants for Source Categories). Although 40 CFR 65.158(a)(2)(iii) specifically cross-references Method 301, Method 301 has not previously been revised to reference Part 65. For parts 63 and 65, Method 301 must be used for establishing an alternative test method. In this action, we propose revisions clarifying that Method 301 is applicable to both parts 63 and 65 and that Method 301 is also Start Printed Page 87006appropriate for validating alternative test methods for use under the following parts under title 40 of the Clean Air Act:
Part 59 (National Volatile Organic Compound Emission Standards for Consumer and Commercial Products)
Part 60 (Standards of Performance for New Stationary Sources)
Part 61 (National Emission Standards for Hazardous Air Pollutants)
We believe that the Method 301 procedures for determining bias and precision provide a suitable technical approach for assessing candidate or alternative test methods for use under these regulatory parts as the testing provisions are very similar to those under parts 63 and 65. To accommodate the expanded applicability and suitability, we propose to revise the references in sections 2.0, 3.2, 5.0, 13.0, 14.0, and 16.1 to refer to all five regulatory parts.
In this action, we propose to clarify the procedures in Method 301 by adding the following equations:
Equation 301-8 in section 10.3 for calculating the correction factor
Equation 301-11 in section 11.1.1 and Equation 301-19 in section 12.1.1 for calculating the numerical bias
Equation 301-12 in section 11.1.2 and Equation 301-20 in section 12.1.2 for determining the standard deviation of differences
Equation 301-13 in section 11.1.3 and Equation 301-21 in section 12.1.3 for calculating the t-statistic
Equation 301-15 in section 11.2.1 to estimate the variance of the validated test method
Equation 301-23 in section 12.2 for calculating the standard deviation
We also propose revisions to the denominator of Equation 22 to use the variable “CS” rather than “VS.” Additionally, we propose revisions to the text of Method 301, where needed, to list and define all variables used in the method equations. These proposed changes are intended to improve the readability of the method and ensure that required calculations and acceptance criteria for each of Method 301's three validation approaches are clear.
In this action, we propose minor edits throughout the text of Method 301 to clarify the descriptions and requirements for assessing bias and precision, to ensure consistency when referring to citations within the method, to renumber equations and tables (where necessary), and to remove passive voice.
We propose edits to clarify several definitions in section 3.2. In the definition of “Paired sampling system,” we propose a minor edit to note that the system is collocated. For the definition of “Quadruplet sampling system,” we propose to replace the term “Quadruplet” with “Quadruplicate” and to add descriptive text to the definition to provide examples of replicate samples. We are also proposing companion edits throughout the method text to reflect the change in terminology from “quadruplet” to “quadruplicate.” Additionally, we propose clarifying edits to the definition of “surrogate compound.”
We also propose replacing the term “alternative test method” with “candidate test method” in section 3.2 and throughout Method 301 to maintain consistency when referring to a test method that is subject to the validation procedures specified in Method 301.
Additionally, the EPA proposes the following updates and corrections by:
Adding the t-value for 11 degrees of freedom to Table 301-2.
Correcting the t-value for four degrees of freedom in Table 301-2.
The EPA specifically requests public comments on the expanded applicability of Method 301 to 40 CFR part 59 and to note the suitability of Method 301 for validation of alternative test methods under 40 CFR parts 60 and 61. In addition, we specifically request comment on the following proposed technical amendments to Method 301:
(A) Requiring ruggedness testing and determination of LOD for validation of test methods intended for multi-source and source-specific applications.
(B) Incorporating the procedures specified in the proposed revisions to 40 CFR part 136, appendix B, into the Method 301 procedures for determining LOD.
(C) Revising the sampling requirements for the method comparison procedure to require six sets of quadruplicate samples rather than four sets, and adding storage and sampling procedures for sorbent systems that require thermal desorption.
(D) Clarifying that candidate test methods that are intended for use at multiple sources must have a bias less than or equal to 10 percent and that test methods, where the bias is greater than 10 percent but less than to 30 percent, are applicable only on a source-specific basis with the use of a correction factor.
(E) Clarifying that the RSD of a candidate test method validated using the analyte spiking or isotopic spiking procedure must be less than or equal to 20 percent for the method to be acceptable.
(F) Adding equations to calculate the: (1) Correction factor (if required) when using isotopic spiking; (2) standard deviation when using the analyte spiking procedure; (3) estimated variance of validated test method when using the comparison procedure; and (4) standard deviation of differences and t-statistic when using the analyte spiking or comparison procedures.
This proposed action does not impose an information collection burden under the PRA. The revisions being proposed in this action to Method 301 do not add information collection requirements, but make corrections and updates to existing testing methodology.
I certify that this proposed action will not have a significant economic impact on a substantial number of small entities under the RFA. This action will not impose any requirements on small entities. The proposed revisions to Method 301 do not impose any requirements on regulated entities beyond those specified in the current regulations, nor do they change any emission standard. We have therefore concluded that this proposed action will have no net regulatory burden for all directly regulated small entities.
This proposed action does not contain any unfunded mandate of $100 million or more as described in UMRA, 2 U.S.C. 1531-1538. The proposed action imposes no enforceable duty on any state, local or tribal governments or the private sector.
This proposed action does not have federalism implications. It will not have substantial direct effects on the states, on the relationship between the national government and the states, or on the distribution of power and Start Printed Page 87007responsibilities among the various levels of government.
This proposed action does not have tribal implications, as specified in Executive Order 13175. This proposed action would correct and update the existing procedures specified in Method 301. Thus, Executive Order 13175 does not apply to this proposed action.
This proposed action involves technical standards. The agency previously identified ASTM D4855-97 (Standard Practice for Comparing Test Methods) as being potentially applicable in previous revisions of Method 301, but determined that the use of ASTM D4855-97 was impractical (Section V in 76 FR 28664).
For the reasons stated in the preamble, the EPA proposes to amend title 40, chapter I of the Code of the Federal Regulations as follows:
Method 301 provides a set of procedures for the owner or operator of an affected source, to validate a candidate test method as an alternative to a required test method based on established precision and bias criteria. These validation procedures are applicable under 40 CFR part 63 or 65 when a test method is proposed as an alternative test method to meet an applicable requirement or in the absence of a validated method. Additionally, the validation procedures of Method 301 are appropriate for demonstration of the suitability of alternative test methods under 40 CFR parts 59, 60, and 61. If, under 40 CFR part 63 or 60, you choose to propose a validation method other than Method 301, you must submit and obtain the Administrator's approval for the candidate validation method.
If you want to use a candidate test method to meet requirements in a subpart of 40 CFR part 59, 60, 61, 63, or 65, you must also request approval to use the candidate test method according to the procedures in Section 16 of this method and the appropriate section of the part (§ 59.104, § 59.406, § 60.8(b), § 61.13(h)(ii), § 63.7(f), or § 65.158(a)(2)(iii)). You must receive the Administrator's written approval to use the candidate test method before you use the candidate test method to meet the applicable federal requirements. In some cases, the Administrator may decide to waive the requirement to use Method 301 for a candidate test method to be used to meet a requirement under 40 CFR part 59, 60, 61, 63, or 65 in absence of a validated test method. Section 17 of this method describes the requirements for obtaining a waiver.
3.1 Procedures. Method 301 includes minimum procedures to determine and document systematic error (bias) and random error (precision) of measured concentrations from exhaust gases, wastewater, sludge, and other media. Bias is established by comparing the results of sampling and analysis against a reference value. Bias may be adjusted on a source-specific basis using a correction factor and data obtained during the validation test. Precision may be determined using a paired sampling system or quadruplicate sampling system for isotopic spiking. A quadruplicate sampling system is required when establishing precision for analyte spiking or when comparing a candidate test method to a validated method. If such procedures have not been established and verified for the candidate test method, Method 301 contains procedures for ensuring sample stability by developing sample storage procedures and limitations and then testing them. Method 301 also includes procedures for ruggedness testing and determining detection limits. The procedures for ruggedness testing and determining detection limits are required for candidate test methods that are to be applied to multiple sources and optional for Start Printed Page 87008candidate test methods that are to be applied at a single source.
You must determine bias and precision by comparison against a validated test method, using isotopic spiking, or using analyte spiking (or the equivalent). Isotopic spiking can only be used with candidate test methods capable of measuring multiple isotopes simultaneously such as test methods using mass spectrometry or radiological procedures. You must collect samples according to the requirements specified in Table 301-1 of this method. You must perform the sampling according to the procedures in Sections 6.1 through 6.4 of this method.
6.4 Probe Placement and Arrangement for Stationary Source Stack or Duct Sampling. To sample a stationary source, you must place the paired or quadruplicate probes according to the procedures in this subsection. You must place the probe tips in the same horizontal plane.
6.4.1 Paired Sampling Probes. For paired sampling probes, the first probe tip should be 2.5 centimeters (cm) from the outside edge of the second probe tip, with a pitot tube on the outside of each probe. Section 17.1 of Method 301 describes conditions for waivers. For example, the Administrator may approve a validation request where other paired arrangements for the pitot tubes (where required) are used.
6.4.2 Quadruplicate Sampling Probes. For quadruplicate sampling probes, the tips should be in a 6.0 cm x 6.0 cm square area measured from the center line of the opening of the probe tip with a single pitot tube, where required, in the center of the probe Start Printed Page 87009tips or two pitot tubes, where required, with their location on either side of the probe tip configuration. Section 17.1 of Method 301 describes conditions for waivers. For example, you must propose an alternative arrangement whenever the cross-sectional area of the probe tip configuration is approximately five percent or more of the stack or duct cross-sectional area.
7.1 Developing Sample Storage and Threshold Procedures. If the candidate test method includes well-established procedures supported by experimental data for sample storage and the time within which the collected samples must be analyzed, you must store the samples according to the procedures in the candidate test method and you are not required to conduct the procedures specified in Section 7.2 or 7.3 of this method. If the candidate test method does not include such procedures, your candidate method must include procedures for storing and analyzing samples to ensure sample stability. At a minimum, your proposed procedures must meet the requirements in Section 7.2 or 7.3 of this method. The minimum time period between collection and storage must be as soon as possible, but no longer than 72 hours after collection of the sample. The maximum storage duration must not be longer than 2 weeks.
7.3 Storage and Sampling Procedures for Testing Other Waste Media (e.g., Soil/Sediment, Solid Waste, Water/Liquid). You must analyze one of each pair of replicate samples (half the total samples) at the minimum storage duration and the other replicate (other half of samples) at the maximum storage duration or within two weeks of the initial analysis to identify the effect of storage duration on analyte samples. The minimum time period between collection and storage should be as soon as possible, but no longer than 72 hours after collection of the sample.
7.4 Sample Stability. After you have conducted sampling and analysis according to Section 7.2 or 7.3 of this method, compare the results at the minimum and maximum storage durations. Calculate the difference in the results using Equation 301-1 of this method.
7.4.1 Standard Deviation. Determine the standard deviation of the paired samples using Equation 301-2 of this method.
7.4.2 T Test. Test the difference in the results for statistical significance by calculating the t-statistic and determining if the mean of the differences between the results at the minimum storage duration and the results after the maximum storage duration is significant at the 95 percent confidence level and n-1 degrees of freedom. Calculate the value of the t-statistic using Equation 301-3 of this method.
You must determine bias by comparing the results of sampling and analysis using the candidate test method against a reference value. The bias must be no more than ±10 percent for the candidate test method to be considered for application to multiple sources. A candidate test method with a bias greater than ±10 percent and less than or equal to ±30 percent can only be applied on Start Printed Page 87010a source-specific basis at the facility at which the validation testing was conducted. In this case, you must use a correction factor for all data collected in the future using the candidate test method. If the bias is more than ±30 percent, the candidate test method is unacceptable.
10.1 Numerical Bias. Calculate the numerical value of the bias using the results from the analysis of the isotopic spike in the field samples and the calculated value of the spike according to Equation 301-4 of this method.
10.2 Standard Deviation. Calculate the standard deviation of the Si values according to Equation 301-5 of this method.
10.3 T Test. Test the bias for statistical significance by calculating the t-statistic using Equation 301-6 of this method. Use the standard deviation determined in Section 10.2 of this method and the numerical bias determined in Section 10.1 of this method.
Compare the calculated t-value with the critical value of the two-sided t-distribution at the 95 percent confidence level and n-1 degrees of freedom (see Table 301-3 of this method). When you conduct isotopic spiking according to the procedures specified in Sections 6.1 and 6.3 of this method as required, this critical value is 2.201 for 11 degrees of freedom. If the calculated t-value is less than or equal to the critical value, the bias is not statistically significant, and the bias of the candidate test method is acceptable. If the calculated t-value is greater than the critical value, the bias is statistically significant, and you must evaluate the relative magnitude of the bias using Equation 301-7 of this method.
If the relative bias is less than or equal to 10 percent, the bias of the candidate test method is acceptable for use at multiple sources. If the relative bias is greater than 10 percent but less than or equal to 30 percent, and if you correct all data collected with the candidate test method in the future for bias using the source-specific correction factor determined in Equation 301-8 of this method, the candidate test method is acceptable only for application to the source at which the validation testing was conducted and may not be applied to any other sites. If either of the preceding two cases applies, you may continue to evaluate the candidate test method by calculating its precision. If not, the candidate test method does not meet the requirements of Method 301.
Start Printed Page 87011
10.4 Precision. Calculate the RSD according to Equation 301-9 of this method.
SD = Standard deviation of the candidate test method calculated in Equation 301-5 of this method.
11.1.1 Bias. Determine the bias, which is defined as the mean of the differences between the candidate test method and the validated method (dm). Calculate di according to Equation 301-10 of this method.
Calculate the numerical value of the bias using Equation 301-11 of this method.
11.1.2 Standard Deviation of the Differences. Calculate the standard deviation of the differences, SDd, using Equation 301-12 of this method.
11.1.3 T Test. Calculate the t-statistic using Equation 301-13 of this method.
Start Printed Page 87012
For the procedure comparing a candidate test method to a validated test method listed in Table 301-1 of this method, n equals six. Compare the calculated t-statistic with the critical value of the t-statistic, and determine if the bias is significant at the 95 percent confidence level (see Table 301-3 of this method). When six runs are conducted, as specified in Table 301-1 of this method, the critical value of the t-statistic is 2.571 for five degrees of freedom. If the calculated t-value is less than or equal to the critical value, the bias is not statistically significant and the data are acceptable. If the calculated t-value is greater than the critical value, the bias is statistically significant, and you must evaluate the magnitude of the relative bias using Equation 301-14 of this method.
B = Bias as calculated in Equation 301-11 of this method.
If the relative bias is less than or equal to 10 percent, the bias of the candidate test method is acceptable. On a source-specific basis, if the relative bias is greater than 10 percent but less than or equal to 30 percent, and if you correct all data collected in the future with the candidate test method for the bias using the correction factor, CF, determined in Equation 301-8 of this method (using VS for CS), the bias of the candidate test method is acceptable for application to the source at which the validation testing was conducted. If either of the preceding two cases applies, you may continue to evaluate the candidate test method by calculating its precision. If not, the candidate test method does not meet the requirements of Method 301.
11.2.1 Candidate Test Method Variance. Calculate the estimated variance of the candidate test method according to Equation 301-15 of this method.
Sp2 = Estimated variance of the candidate test method.
Calculate the estimated variance of the validated test method according to Equation 301-16 of this method.
Sv2 = Estimated variance of the validated test method.
11.2.2 The F test. Determine if the estimated variance of the candidate test method is greater than that of the validated method by calculating the F-value using Equation 301-17 of this method.
Sp2 = The estimated variance of the candidate test method.
Compare the calculated F value with the one-sided confidence level for F from Table 301-4 of this method. The upper one-sided confidence level of 95 percent for F(6,6) is 4.28 when the procedure specified in Table 301-1 of this method for quadruplicate Start Printed Page 87013sampling trains is followed. If the calculated F value is greater than the critical F value, the difference in precision is significant, and the data and the candidate test method are unacceptable.
12.1.1 Bias. Determine the bias, which is defined as the mean of the differences between the spiked samples and the unspiked samples in each quadruplicate sampling train minus the spiked amount, using Equation 301-18 of this method.
Calculate the numerical value of the bias using Equation 301-19 of this method.
12.1.2 Standard Deviation of the Differences. Calculate the standard deviation of the differences using Equation 301-20 of this method.
12.1.3 T Test. Calculate the t-statistic using Equation 301-21 of this method, where n is the total number of test sample differences (di). For the quadruplicate sampling system procedure in Table 301-1 of this method, n equals six.
Compare the calculated t-statistic with the critical value of the t-statistic, and determine if the bias is significant at the 95 percent confidence level. When six quadruplicate runs are conducted, as specified in Table 301-1 of this method, the 2-sided confidence level critical value is 2.571 for the five degrees of freedom. If the calculated t-value is less than the critical value, the bias is not statistically significant and the data are acceptable. If the calculated t-value is greater than the critical value, the bias is statistically significant and you must evaluate the magnitude of the relative bias using Equation 301-22 of this method.
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B = Bias at the spike level from Equation 301-19 of this method.
If the relative bias is less than or equal to 10 percent, the bias of the candidate test method is acceptable. On a source-specific basis, if the relative bias is greater than 10 percent but less than or equal to 30 percent, and if you correct all data collected with the candidate test method in the future for the magnitude of the bias using Equation 301-8, the bias of the candidate test method is acceptable for application to the tested source at which the validation testing was conducted. Proceed to evaluate precision of the candidate test method.
12.2 Precision. Calculate the standard deviation using Equation 301-23 of this method.
Calculate the RSD of the candidate test method using Equation 301-9 of this method, where SD and Sm are the values from Equation 301-23 of this method. The data and candidate test method are unacceptable if the RSD is greater than 20 percent.
15.2 Purpose. The LOD establishes the lower detection limit of the candidate test method. You must calculate the LOD using the applicable procedures found in Table 301-5 of this method. For candidate test methods that collect the analyte in a sample matrix prior to an analytical measurement, you must determine the LOD using Procedure I in Table 301-5 of this method by calculating a method detection limit (MDL) as described in proposed 40 CFR part 136, appendix B. For the purposes of this section, the LOD is equivalent to the calculated MDL. For radiochemical methods, use the Multi-Agency Radiological Laboratory Analytical Protocols (MARLAP) Manual (i.e., use the minimum detectable concentration (MDC) and not the LOD) available at http://www2.epa.gov/​radiation/​marlap-manual-and-supporting-documents.
16.1 Submitting Requests. You must request to use a candidate test method according to the procedures in § 63.7(f) or similar sections of 40 CFR parts 59, 60, 61, and 65 (§ 59.104, § 59.406, § 60.8(b), § 61.13(h)(ii), or § 65.158(a)(2)(iii)). You cannot use a candidate test method to meet any requirement under these parts until the Administrator has approved your request. The request must include a field validation report containing the information in Section 16.2 of this method. You must submit the request to the Group Leader, Measurement Technology Group, U.S. Environmental Protection Agency, E143-02, Research Triangle Park, NC 27711.
17.1 Conditions for Waivers. If you meet one of the criteria in Section 17.1.1 or 17.1.2 of this method, the Administrator may waive the requirement to use the procedures in this method to validate an alternative or other candidate test method. In addition, if the EPA currently recognizes an appropriate test method or considers the candidate test method to be satisfactory for a particular source, the Administrator may waive the use of this protocol or may specify a less rigorous validation procedure.
17.1.2 Documented Methods. If the bias and precision of the alternative or other candidate test method that you are proposing have been demonstrated through laboratory tests or protocols different from this method, and you can demonstrate to the Administrator's satisfaction that the bias and Start Printed Page 87015precision apply to your application, then the Administrator may waive the requirement to use this method or to use part of this method.
You can find additional information in the references in Sections 18.1 through 18.17 of this method.
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Table 301-3—Critical Values of t for the Two-Tailed 95 Percent Confidence Limit
Table 301-4—Upper Critical Values of the F Distribution for the 95 Percent Confidence Limit
1,1 161.4
2,2 19.0
3,3 9.3
If the estimated LOD (LOD1, expected approximate LOD concentration level) is no more than twice the calculated LOD or an analyte in a sample matrix was collected prior to an analytical measurement, use Procedure I as follows. If the estimated LOD (LOD1, expected approximate LOD concentration level) is greater than twice the calculated LOD, use Procedure II as follows
Procedure I Procedure II
Determine the LOD by calculating a method detection limit (MDL) as described in proposed 40 CFR part 136, appendix B Prepare two additional standards (LOD2 and LOD3) at concentration levels lower than the standard used in Procedure I (LOD1).
[FR Doc. 2016-27544 Filed 12-1-16; 8:45 am]