* x> PRO^ U.S. EPA Ambient Air Protocol Gas Verification Program Annual Report CY 2022 ------- ------- EPA-454/R-23-005 May 2023 U.S. EPA Ambient Air Protocol Gas Verification Program Annual Report CY 2022 U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Air Quality Assessment Division Research Triangle Park, NC ------- Table of Contents Acknowledgements 5 Acronyms and Abbreviations 6 1.0 Introduction 7 2.0 Implementation Summary 9 3.0 Survey and Verification Results 12 4.0 Summary and Conclusions 16 Appendix A QA Reports from Measurement Data Worksheets for 2022 19 Tables Table 1. RAVL Verification Dates 10 Table 2. Gas Standards Sent to RAVLs 13 Table 3. MQOsforthe AA-PGVP 14 Table 4. AA-PGVP CO and S02 Verifications 15 Table 5. AA-PGVP NO and NOx Verifications 15 Figures Figure 1. AA-PGVP Flow Chart 11 Figure 2 Annual Survey 12 Figure 3 Verification Trend 13 ------- Acknowledgements The following individuals and organizations are acknowledged for their contributions to this project: US EPA, Office of Air Quality Planning and Standards Douglas Jager US EPA, Office of Research and Development Bob Wright US EPA Region 7 Thien Bui James Regehr IV1 o n 11 o r i n g 0 r ga n I z a t i o n s EPA acknowledges the monitoring organizations that supported the AA-PGVP Annual Survey. They include: Albuquerque Environmental Health Department, AQD Arizona Department of Environmental Quality Broward County Environmental Protection Department California Air Resources Board Cherokee Nation, Oklahoma Clark County, NV DES Connecticut Department of Environmental Protection Florida Dept of Environmental Protection, Northwest District Forsyth County Environmental Affairs Department Idaho Department of Health and Welfare-Environment Div. Indiana Depart of Environ Management Kentucky Division for Air Quality Maricopa County Air Quality Maryland Department of the Environment Mass Dept Environmental Protection (DAQC) Miami-Dade County (DERM) Michigan Dept of Environment, Great Lakes, and Energy Mississippi DEQ Missouri Laboratory Services Program Monterey Bay Unified APCD New Hampshire Air Resources Agency New Jersey State Department of Environmental Protection New Mexico Environment Department North Carolina Dept of Environmental Quality North Dakota DEQ Ohio EPA, Central District Office Oregon Department of Environmental Quality Polk County Physical Planning Rhode Island DEM and DOH Sacramento County APCD San Luis Obispo County APCD South Carolina Department Health and Environ. Control South Coast Air Quality Management District South Dakota (DANR) State of Louisiana Texas Commission on Environmental Quality University Hygienic Laboratory (University of Iowa) Virginia Department of Environmental Quality Washington State Department of Ecology Washoe County District Health Department West Virginia Northern Panhandle Regional Office Wisconsin Dept of Natural Resources, Air Monitoring Section ------- Acronyms and Abbreviations AA-PGVP Ambient Air Protocol Gas Verification Program AMTIC Ambient Monitoring Technology Information Center AQS Air Quality System CFR Code of Federal Regulations CO Carbon Monoxide CONC Concentration DoE Declaration of Equivalence with the National Institute of Standards and Technology EPA Environmental Protection Agency GMIS Gas Manufacturer's Intermediate Standard ID Identification MFC Mass Flow Controller NIST National Institute of Standards and Technology NMI National Metrology Institute N02 Nitrogen Dioxide NOx Nitrogen Oxides MQO Measurement Quality Objective NTRM NIST Traceable Reference Material NVLAP National Voluntary Laboratory Accreditation Program OAQPS Office of Air Quality Planning and Standards OAR Office of Air and Radiation OIG Office of the Inspector General ORD Office of Research and Development PQAO Primary Quality Assurance Organization PRM Primary Reference Material PSI Pounds per Square Inch PSIG Pounds per Square Inch Gauge QA Quality Assurance QAPP Quality Assurance Project Plan QC Quality Control QTR Quarter RAVL Regional Analytical Verification Laboratory RD Relative Difference RPD Relative Percent Difference SI International System of Units S02 Sulfur Dioxide SOP Standard Operating Procedure SRM Standard Reference Material URL Upper Range Limit VSL Netherland's National Metrology Institute; Dutch Von Swinden Laboratorium ------- 1 n Background a > ¦ , ogre i ¦ a Is The basic principles of the U.S. Environmental Protection Agency's (EPA) Traceability Protocol for the Assay and Certification of Gaseous Calibration Standards (EPA, 2012)1 were developed jointly by EPA, the National Bureau of Standards (now National Institute of Standards and Technology [NIST]), and specialty gas producers over 40 years ago. At the time, commercially prepared calibration gases were perceived as being too inaccurate and too unstable for use in calibrations and audits of continuous source emission monitors and ambient air quality monitors2. The protocol was developed to improve the quality of the gases by establishing their traceability to NIST Standard Reference Materials (SRMs) and to provide reasonably priced products. This protocol established the gas metrological procedures for measurement and certification of these calibration gases for EPA's Acid Rain Program under 40 Code of Federal Regulations (CFR) Part 75, for the Ambient Air Quality Monitoring Program under 40 CFR Part 58, and for the Source Testing Program under 40 CFR Parts 60, 61, and 68. EPA required monitoring organizations implementing these programs ("the regulated community") to use EPA Protocol Gases as their calibration gases. EPA revised the protocol to establish detailed statistical procedures for estimating the total uncertainty of these gases. EPA's Acid Rain Program developed acceptance criteria for the uncertainty estimate3. Specialty gas producers prepare and analyze EPA Protocol Gases without direct governmental oversight. In the 1980s and 1990s, EPA conducted a series of EPA-funded accuracy assessments of EPA Protocol Gases sold by producers. The intent of these audits was to: • increase the acceptance and use of EPA Protocol Gases as calibration gases, • provide a quality assurance (QA) check for the producers of these gases, and • help users identify producers who can consistently provide accurately certified gases. Either directly or through third parties, EPA procured EPA Protocol Gases from the producers, assessed the accuracy of the gases' certified concentrations through independent analyses, and inspected the 1 EPA-600/R-12/531 2 Decker, C.E. et al., 1981. "Analysis of Commercial Cylinder Gases of Nitric Oxide, Sulfur Dioxide, and Carbon Monoxide at Source Concentrations," Proceedings of theAPCA Specialty Conference on Continuous Emission Monitoring-Design, Operation, and Experience, APCA Publication No. SP-43. 3 "Continuous Emission Monitoring," Code of Federal Regulations, Title 40, Part 75 Page 7 of 26 ------- accompanying certificates of analysis for completeness and accuracy. The producers were not aware that EPA had procured the gases for these audits. The accuracy of the EPA Protocol Gases' certified concentrations was assessed using SRMs as the analytical reference standards. If the difference between the audit's measured concentration and the producer's certified concentration was more than ±2.0 percent or if the documentation was incomplete or inaccurate, EPA notified the producer to resolve and correct the problem. The results of the accuracy assessments were published in peer-reviewed journals and were posted on EPA's Technology Transfer Network website. The accuracy assessments were discontinued in 1998. In 2009, the Office of the Inspector General (OIG) published the report EPA Needs an Oversight Program for Protocol Gases4. One of the report's findings suggested that EPA "does not have reasonable assurance that the gases that are used to calibrate emissions monitors for the Acid Rain Program and continuous ambient monitors for the nation's air monitoring network are accurate". OIG recommended that the Office of Air and Radiation (OAR) implement oversight programs to assure the quality of the EPA Protocol Gases that are used to calibrate these monitors. It also recommended that EPA's Office of Research and Development (ORD) update and maintain the document Traceability Protocol for Assay and Certification of Gaseous Calibration Standards to ensure that the monitoring programs' objectives are met. In order to address the OIG findings for ambient air monitoring, the Office of Air Quality Planning and Standards (OAQPS), in cooperation with two EPA Regional Offices, developed an Ambient Air Protocol Gas Verification Program (AA-PGVP). The program established two gas metrology laboratories to verify the certified concentrations of EPA Protocol Gases used to calibrate ambient air quality monitors. The program is designed to ensure that producers selling EPA Protocol Gases are evaluated by the AA-PGVP and provides end users with information about participating producers and verification results. The EPA Ambient Air Quality Monitoring Program's QA requirements, as described in Section 2.6.1 of 40 CFR Part 58, Appendix A, include: Gaseous pollutant concentration standards (permeation devices or cylinders of compressed gas) used to obtain test concentrations for CO, S02, NO, and N02 must be traceable to either a National Institute of Standards and Technology (NIST) Traceable Reference Material (NTRM) or a NIST- certified Gas Manufacturer's Internal Standard (GMIS), certified in accordance with one of the procedures given in reference 4 of this appendix. Vendors advertising certification with the procedures provided in reference 4 of this appendix and distributing gases as "EPA Protocol Gas" for ambient air monitoring purposes must participate in the EPA Ambient Air Protocol Gas Verification Program or not use "EPA" in any form of advertising. Monitoring organizations must provide information to the EPA on the gas producers they use on an annual basis and those POAOs purchasing standards will be obligated, at the request of the EPA, to participate in the program at least once every 5 years by sending a new unused standard to a designated verification laboratory. 4 https://www.epa.gov/office-inspector-general/report-epa-needs-oversight-program-protocol-gases-09-P-0235.pdf Page 8 of 26 ------- This program is considered a verification program because its current level of evaluation does not allow for a large enough sample of EPA Protocol Gases from any one specialty gas producer to yield a statistically rigorous assessment of the accuracy of the producer's gases. As indicated in 40 CFR Part 75 Appendix A, EPA Protocol Gases must have a certified uncertainty (95 percent confidence interval) that must not be greater than plus or minus 2 percent (±2.0%) of the certified concentration (tag value) of the gas mixture. This acceptance criterion is for the Acid Rain Program. The AA-PGVP adopted this criterion as its data quality objective and developed a quality system to allow the RAVLs to determine whether an individual protocol gas standard concentration was within ±2% of the certified value. Purpose "" " lis Document The purpose of this document is to report the activities that occurred in 2022 and provide the results of the verifications performed. Since the AA-PGVP does not sample enough cylinder standards annually to provide a statistically rigorous assessment of any specialty gas producer, the RAVLs report all valid results as analyzed without declaring a pass or fail determination for individual specialty gas producers. However, it is suggested that any assay verification results with a difference greater than ±4% is cause for concern. The AA-PGVP assay verifications are not intended to provide end users with a scientifically defensible estimate of whether gases of acceptable quality can be purchased from a specific producer. Rather, the results provide information to end users that the specialty gas producer is evaluated by the program and with information that may be helpful when selecting a producer. This document will not explain the implementation of the AA-PGVP, the quality system or the verification procedure. That information has been documented in the Implementation Plan, Quality Assurance Project Plan (QAPP) and standard operating procedures (SOPs). These documents can be found on the AA-PGVP section on the Ambient Monitoring Technology Information Center (AMTIC)5 website. The AA-PGVP SOPs are located in the AA-PGVP QAPP as an appendix. 2.0 Implementation Summary Since the program implementation started in 2010, when most of the initial preparation work took place, no major new implementation activities took place. However, EPA regional realignments and aging infrastructure reduced the capabilities of this program. Due to these constraints, the EPA Region 2 Regional Analytical Verification Laboratory (RAVL) ceased its active participation in the AA-PGVP in calendar year 2019. Since 2020 EPA began reengineering the AA-PGVP and transitioning Region 2 operations to the Region 4 laboratory. However, during 2022 the AA-PGVP continued to operate with only the Region 7 RAVL. 5 www.epa.gov/amtic/ambient-air-protocol-gas-verification-program Page 9 of 26 ------- Operations with only a single RAVL resulted in the AA-PGVP unable to swap internal quality control samples (cylinder standards) between two independent RAVLs. The following provides a brief overview of the ambient air protocol gas verification program. Producer Information Data Collection - Beginning in 2010, EPA sent out an Excel spreadsheet to each monitoring organization to obtain information on the gas standard producers being used by the monitoring organization and to determine their interest in participating in the program. In 2011, EPA began work with Research Triangle Institute to develop a web-based survey that one point of contact for each monitoring organization could access. The intent was to make recording and evaluation of the survey information easier for the monitoring organizations and EPA. This contracted survey work has since migrated to Battelle. Based on the information obtained from monitoring organization surveys, EPA would develop a list of the specialty gas producers being used by the monitoring organizations. From this list, EPA would attempt to perform representative sampling of the standards from protocol gas production facilities by identifying regulatory monitoring agencies that use standards from each of these producers. However, for calendar year 2022 only 42 agencies participated in the survey. With only limited survey results, a systematic selection of producers could not be performed. During calendar year 2022 the AA-PGVP performed assays on all cylinders submitted by regulatory monitoring agencies. OAQPS continues to develop an Air Quality System (AQS) database solution to upgrade and replace the specialty gas usage information that is currently acquired through the contractor based annual questionnaire. During CY-2022 a cylinder metadata entry form to support the AA-PGVP was created in AQS. Cylinder usage data that was historically collected via the annual survey began to be collected via AQS. Both North Dakota DEQ and the California Air Resources Board used AQS to report the specialty gas producers used for their calibration standards while the remaining 40 agencies used EPA's deprecating annual survey system. AA-PGVP Verification Dates - OAQPS worked with the Region 7 Regional Analytical Verification Laboratory (RAVL) to establish verification dates as indicated in Table 1. Table 1. RAVL Verification Dates Quarter Region 7 Cylinder Receipt Analysis 1 No later than Feb 23 Feb 28-Mar 11 2 No later than Jun 1 Jun 5-Junl7 3 No later than Aug 24 Aug 29 - Sept 9 4 No later than Dec 1 Dec 5 - Dec 16 Open House December 19, 2022 Table 1. RAVL Verification Dates Table 1 RAVL Open House - During Open House the RAVL allows specialty gas producers to visit and ask questions regarding the laboratory processes and operations. During 2022 no specialty gas producers visited the Region 7 RAVL. Page 10 of 26 ------- Flow of the AA-PGVP Figure 1 provides a flow diagram of the implementation activities of the AA-PGVP. The major activities in these steps are explained below. More details of these steps are found in the AA-PGVP Implementation Plan, QAPP and SOPs. © Figure 1. AA-PGVP Flow Chart 0. Specialty Gas Producers procure standards from NIST, or an NMI with a DoE with NIST, to establish traceability of their EPA Protocol Gas Standards to the SI. RAVLs also procure NIST standards as part of the AA-PGVP. 1. Monitoring organizations order EPA Protocol Gas Standards as a normal course of business. 2. EPA sends reminder e-mails to the monitoring organization's points of contact to enter cylinder metadata in AQS or complete AA-PGVP's Survey. Based on an annual assessment of this information, monitoring organizations are selected to send cylinder standards to EPA for assay verification. Through consultation with the participating monitoring organization, EPA schedules the assay verifications. 3. The participating monitoring organizations send a new/unused standard, certificate of analysis, and chain of custody form to the RAVLs for the assay verification. Standards are returned to the monitoring organization along with the verification results for their standards. 4. The RAVLs provide the validated results to OAQ.PS. 5. When the assay verification results are greater than ±4% of the certified concentration, or greater than ±2% when the expanded measurement uncertainty is included, specialty gas producers are notified by OAQ.PS. 6. GAQPS compiles the year's verification results into an annual report and posts it to the AMTIC website. Page 11 of 26 ------- 3.0 Survey and Verification Results Monitoring Organization Survey Based upon the maximum capability of 40 gas cylinders per RAVL per year, the AA-PGVP selection goal, in the following order, is: 1) At least one gas standard from every specialty gas producer being used by the monitoring 2) If all specialty gas producers have been assessed at least once, then attempt to verify three standards per specialty gas producer. 3) If all specialty gas producers have been assessed three times, weigh additional verifications by producer market share in the ambient air monitoring community. In order to assess which specialty gas producers are used by the monitoring organizations, EPA uses a web- based survey that each monitoring organization completes annually. Since 2016, EPA regulations found in 40 CFR Part 58 Appendix A §2.6.1 require monitoring organizations to annually provide this information. However, as can be seen from Figure 2, participation in the annual survey has not improved since the 2016 monitoring rule revisions. community. AA-PGVP / Survey Participation Trend 300 250 200 100 150 50 0 2011 2012 2013 2014 2015 Year .»• All AOS Agencies Agencies (S02, CO, N02) \ Surveyed Figure 2 Annual Survey Page 12 of 26 ------- Verification Results The AA-PGVP received 7 cylinders for assay verification during calendar year 2022. The 7 cylinders received are listed in Table 2. As can be seen from Table 2, some cylinders contain more than a single calibration gas standard. A summary of the assay results for these cylinders are provided in Tables 4 and 5. Table 2. Gas Standards Sent to RAVLs in Calendar Year 2022 Qtr Cylinder ID Pollutant Lab Producer Facility Agency 3 ET0033566 NO,NOx 7 Airgas Chicago IL Utah DEO 3 LL40977 CO,NO,NOx 7 Airgas Los Angeles CA South Coast AQMD 3 LL71616 CO 7 Linde Los Angeles CA Utah DEQ 3 LL81350 CO 7 Linde Los Angeles CA Utah DEQ 3 LL23589 so2 7 Linde Los Angeles CA Utah DEQ 3 LL1051310 NO,NOx 7 Linde Los Angeles CA Utah DEQ 2 LL123954 n NO,NOx 7 Linde Toledo OH Hygienic Lab (University of Iowa) Table 2. Gas Standards Sent to RAVLs Notes: O NOx concentration provided by Producer as "informational only"; concentration not certified by Producer. All standards verified in calendar year 2022 were within the ±2% acid rain criteria acceptance criterion, and less than the AA-PGVP action level for concern. Figure 3 below provides a historical trend showing the improvement in the quality of EPA Protocol Gas Standards from the inception of the program to present. Figure 3 Verification Trend Page 13 of 26 ------- Information related to the analytical reference standards, analytical instruments and methods used, the data reduction procedures, and the data assessment procedures are found in the AA-PGVP QAPP and SOP. The AA-PGVP QAPP is located on EPA's AMTIC website. The SOP can be found as an appendix in the QAPP. Table 3 provides the measurement quality objectives (MQOs) that are included in the AA-PGVP QAPP (Table 7-1 of the QAPP). The acceptance criteria in Table 3 were met for each day of verification. In addition, conformance to these requirements can be found in the measurement data worksheets that are generated for each comparison run and are available upon request. Appendix A provides a report of the quality control (QC) checks associated with each verification run. Table 4 provides the verification results for CO and S02, and Table 5 provides the NO and NOx verification results. Tables 4 and 5 are grouped by pollutant standard and then sorted by absolute Bias of the assay result. Table 3. MQOs for the AA-PGVP Requirement Frequency Acceptance Criteria Protocol Gas Comments Doc. Reference Completeness All standards analyzed 95% Based on an anticipated 40 cylinders per lab per year. Quarterly Flow Quarterly -no more than Calibration flow 2.3.7 Using flow primary Calibration 1 mo. before verification accuracy within +1% standard Calibrator Dilution Quarterly -within 2 weeks + 1% RD 2.3.5.1 Second SRM. Three or Check of assay more discrete measurements Analyzer Quarterly-within 2 weeks + 1% RPD (each point) 2.1.7.2 5 points between 50-90% Calibration of assay Slope 0.89-1.02 of upper range limit of analyzer + zero point Zero & Span Each day of verification SE mean < 1% and 2.1.7.3, 2.3.5.4 Drift accountability. 3 Verifications accuracy + 5% RD discrete measurements of zero and span Precision Test1 Day of Verification + 1% RD standard 2.3.5.4 SRM at conc. >80% of error of the mean analyzer URL Routine Data Any Standard with Value NA Sample run three times to Check >2% Tag Value verify value. Lab Comparability 2/year + 2 % RPD NA Sample run three average value used. Standards Certification Primary flow Annually certified by 1.0 % NA Compared to NIST standard NVLAP accredited lab Traceable NISTSRMs Expiration date SRM Will follow NIST pressure > 150 psig recertification requirements Table 3. MQOs fop AA-PGVP 1 The precision test does not need to be accomplished if analyzer calibrated on same day as analysis. Page 14 of 26 ------- >-PGVP CO and S02 Verifications* Producer Facility Cylinder ID Pollutant Assay Cone Producer Cone % Bias* 95% Uncertainty" Airgas Los Angeles CA : LL40977 CO 903.9 907.4 0.4 0.28 Linde Los Angeles CA LL81350 CO 4973.3 4980 0.1 0.20 Linde Los Angeles CA LL71616 CO 4980 4974 -0.1 0.20 Linde Los Angeles CA LL23589 S02 99.72 99.9 0.2 0.16 Table 4. AA-PGVP CO and S02 Verifications Notes: * Table grouped by Pollutant and sorted by absolute Bias ** Analyzer uncertainty, see Quality Assurance Requirements Section 13.7 of SOP. (Analyzer uncertainty value is not the expanded measurement uncertainty) t An Estimate for the national usage for specific protocol gas producers cannot be determined due to lack of participation in annual survey 11 o : ¦ 1 V \-PGVP - id NOx Verifications* Producer Facility I Cylinder ID 1 Pollutant Assay Cone Producer Cone % Bias* 95% Uncertainty" Linde Toledo OH 1 LL123964 NO 25.45 25.3 -0.6 0.18 Linde Los Angeles CA : LL105131 NO 48.85 48.6 -0.5 0.10 Airgas Chicago IL ET0033566 NO 50 50.09 0 7 0.11 Airgas Los Angeles CA LL40977 NO 43.92 43.86 -0.1 0.10 Airgas Los Angeles CA : LL40977 NOx 44.63 44.35 -0.6 0.11 Linde Los Angeles CA : LL1051310 NOx 48.91 48.8 -0.2 0.11 Airgas Chicago IL ! ET0033566 NOx 50.01 50.1 0.2 0.11 Linde Toledo OH ! LL1239640 NOx 25.44 25.5 0.2 0.14 Table 5. AA-PGVP NO and NOx Verifications Notes: * Table grouped by Pollutant and sorted by absolute Bias ** Analyzer uncertainty, see Quality Assurance Requirements Section 13.7 of SOP. (Analyzer uncertainty value is not the expanded measurement uncertainty) t An Estimate for the national usage for specific protocol gas producers cannot be determined due to lack of participation in annual survey CI NOx concentration provided by Producer as "informational only"; concentration not certified by Producer. Page 15 of 26 ------- 4.0 Summary and Conclusions General - The AA-PGVP is successfully implementing a verification process that is blind to the specialty gas producers. One of the goals for the AA-PGVP as defined in the ambient air monitoring rule (published March 28, 2016) is for the verifications performed by the RAVLs to be focused on the ambient air monitoring organizations rather than as a resource to be utilized by specialty gas producers for their own quality assurance. The purpose of the program (verifications of gas cylinders that are blind to the producers) cannot be accomplished if EPA relies on the specialty gas producers to submit cylinders for the assessment. All of the protocol gas cylinder standards submitted for analysis were submitted by SLT ambient air monitoring programs. While the program is successfully implementing a blind verification process only 7 cylinders, or 9% of the AA- PGVP goal of 80 cylinders annually, were analyzed in 2022. These 7-cylinder submissions resulted in only 12 verifications (some cylinders are a blend of multiple gas standards). None of the assay verification results were greater than the AA-PGVP action level for concern (±4%) or the acceptance criterion is for the Acid Rain Program (±2.0%). It is difficult to assess whether these results are representative of the overall quality of the standards used in the national ambient air monitoring networks during 2022 due to the low utilization of the RAVL by the monitoring programs and low participation rate in the annual protocol gas questionnaire. In 2022 there were 26 commercially operated EPA protocol gas production facilities. It is uncertain how many of these facilities were used in the ambient air monitoring networks in 2022. Of the 26 protocol gas production facilities operating, only four were verified by EPA's ambient air protocol gas verification program. Survey Participation Improvement - Since its inception, the AA-PGVP has relied on an annual survey to determine which gas production facilities are used by the SLTs for generating CO, S02, and N02 calibration test atmospheres. Participation in the annual survey was initially voluntary. To improve the participation rate and to more completely document which protocol gas producers are utilized by our ambient air monitoring organizations, in 2016 ambient air monitoring programs using protocol gases were required to annually complete the survey. While it was thought at the time that this regulatory requirement would increase the participation rate and create a comprehensive list of the protocol gas producers used in the national network, the survey participation rate did not improve. In calendar year 2022 participation in the annual questionnaire was about 27% of the monitoring agencies that operate CO, S02, and N02 ambient air analyzers. OAQPS is actively enhancing EPA's AQS database as an alternative solution to gather this information. See Data Management Improvement section below for further details. RAVL Participation Improvement- Since the 2016 revisions of the monitoring rule, the AA-PGVP continues to achieve blind verifications of the protocol gas cylinders used in our ambient air monitoring networks. However, the program still does not achieve its goal of having every Primary Quality Assurance Organization (PQAO) submit an unused cylinder at least once every five years for verification. The AA-PGVP's goal to perform 80 protocol gas verifications each year and to strategically select these protocol cylinders to representatively assess the quality of the routine Page 16 of 26 ------- measurement data for the national ambient air monitoring networks was not achieved in calendar year 2022. Only seven protocol gas cylinder standards were submitted by three PQAOs in 2022 to support this national program. Region 7 assayed all the cylinders received during this calendar year. A better national sampling of monitoring programs and protocol gas producers continues to be needed. The limited verifications performed in 2022 was partially due to the lack of low concentration SRMs currently available from NIST. This has led to cases where the EPA was forced to decline low concentration cylinder standards offered by SLT regulatory ambient air monitoring programs for assay verification. OAQPS is working to add assay capacity in the future by using the EPA Region 4 laboratory as an additional RAVL. OAQPS is also working collaboratively with NIST to develop solutions to this shortage of SRMs available for purchase. OAQPS is also investigating the feasibility of obtaining primary reference materials (PRM) from a NMI that has a DoE with NIST, such as the Netherland's National Metrology Institute; Dutch Von Swinden Laboratorium (VSL), or NIST Traceable Reference Materials (NTRM) to use as a replacement for NIST SRMs. Quality System Improvement - The Quality Assurance Project Plan (QAPP) has not been updated since calendar year 2010. Changes to the program have occurred since 2010, including regulatory changes in 2016. These documents need to be reconciled with current program practices and regulatory requirements. OAQPS is working with Battelle to assist EPA in revising the AA-PGVP QAPP beginning calendar year 2023. In 2022, the AA-PGVP operated with a single RAVL. As such, the quality assurance designated for the laboratory intercomparison of the internal standards could not be performed. OAQPS is currently working with EPA Region 4 to begin using their laboratory as a second RAVL. Once operational, Region 4 RAVL will allow for both increased assay capacity for the AA-PGVP and provide additional internal quality control between the two RAVLs. Data Management Improvement - The AA-PGVP has historically relied solely on the annual survey for determining which protocol gas standard producers are used in the national ambient air monitoring networks. The annual survey was originally a voluntary program and later in 2016 it became a regulatory requirement. Neither implementation of this process has proven to be fully effective. The data management practices for conducting the annual survey and storing its results are not optimized to be readily reconciled with the data produced by the RAVLs. OAQPS continues to actively pursue AQS database solutions to replace the data management practices historically performed by EPA's contractor. This includes the creation of an AQS form for SLT monitoring programs to submit their cylinder metadata and modifications to the current AQS "QA-Transaction" file format for the single point quality control checks and annual performance audits. The modifications being developed will allow for documenting the protocol gas production facility of the protocol gas cylinder used for generating the test atmospheres for each of these checks. Utilizing this modified AQS data submission process will allow EPA to document 100% of the protocol gas production facilities used in the ambient air monitoring networks as opposed to the current process which has only been 17% effective between 2018- 2022. To facilitate these enhancements, an AQS entry form for submission of cylinder metadata was developed and deployed in calendar year 2022. Two monitoring programs utilized the maintain cylinder Page 17 of 26 ------- form in AQS in 2022 with an additional 10 monitoring programs have used this new AQS feature during the first quarter of 2023. New AQS features to merge this cylinder metadata with the data stream containing the single point quality control checks and annual performance audits are currently in stage testing in 2023. EPA's goal is to have both these new AA-PGVP systems fully operational in AQS during calendar 2023. Page 18 of 26 ------- Appendix A ¦ orts from Measureme >" ¦ >ta Workshi ¦ ¦¦ ¦¦ ¦ Ambient Air Protocol Gas Verification Program QA Reports from Measurement Data Worksheets for 2022 During the verification process, the Regional Air Verification Laboratories perform a number of quality control checks that are recorded on the Measurement Data Worksheets. This information is reported and saved along with the verification reports. The following sheets represent the quality control for all verifications that were implemented in 2022. Page 19 of 26 ------- QA Requirements Summary QA Requirement Result Status Primary SRM Cylinder Expiration Date 14-Sep-25 Primary SRM Gas Standard OK SRM Gas Standards Primary SRM Cylinder Pressure >150 psi 1725 Primary SRM cylinder pressure is OK SRM Dilution Check Cylinder Expiration Date 1-Feb-24 Dilution Check SRM Gas Standard OK Dilution Check SRM Cylinder Pressure >150 psi 450 Dilution check SRM cylinder pressure is OK High Flow Standard Expiration Date 8-Feb-23 Standard OK Laboratory Flow Standard Low Flow Standard Expiration Date 8-Feb-23 Standard OK Ultra Low Flow Expiration Date 9-Feb-23 Standard OK Calibrator (mass flow controllers) Calibrator Flow Calibration within 2 weeks of assay 5-Jun-22 Icalibrator flow calibration within 2 weeks of assay Calibrated High Flow MFC Slope Range = 0.99 -1.0 0.9999990 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.0" 0.9999804 Low MFC OK Analyzer Calibration within 2 weeks of assay 6-Jun-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1 % at point #1 (>80% URL) 0.10% Assay may be conducted at this concentration Oxides of Nitrogen Gas Analyzer NO Portion Estimate of Uncetainty < 1 % at point #2 0.10% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #3 0.10% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #4 0.11% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #5 (-50% URL) 0.11% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 0.9990 Analyzer Slope is acceptable Analyzer Calibration within 2 week of assay 6-Jun-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1 % at point #1 (>80% URL) 0.08% Assay may be conducted at this concentration Oxides of Nitrogen Gas Analyzer NOx Portion Estimate of Uncetainty < 1 % at point #2 0.08% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #3 0.09% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #4 0.09% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #5 (-50% URL) 0.09% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 0.9984 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 6-Jun-22 Dilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% 0.116% Dilution Check RSD is OK Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay. Zero Gas Std Error is OK Day of Assay Zero/Span Check NO Portion Day of Assay Zero Check - Relative Difference < 5% RD is okay Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1 % Std. Error is okay. Span Gas Std Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Day of Assay Zero Check - Std. Error < 1% Std. Error is okay. Zero Gas Std. Error is OK Day of Assay Zero/Span Check NOx Portion Day of Assay Zero Check - Relative Difference < 5% RD is okay Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1 % Std. Error is okay. Span Gas Std Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay- Span Gas RD is OK Challenge Standard #1 NO Assay Challenge Standard #1 Std. Error < 1% Challenge Standard #1 vendor certificate bias The standard error is okay. -0.60% Challenge Standard #1 Std. Error is OK Challenge Std #1 vendor certificate bias < 2% Challenge Standard #1 NOx Assay Challenge Standard #1 Std. Error < 1% The standard error is okay. Challenge Standard #1 Std. Error is OK Challenge Standard #1 vendor certificate bias 0.23% Challenge Std #1 vendor certificate bias < 2% Challenge Standard #2 NO Assay Challenge Standard #2 Std. Error < 1% The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias -0.45% Challenge Std. #2 vendor certificate bias < 2% Challenge Standard #2 Std. Error < 1% The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias 0.08% Challenge Std. #2 vendor certificate bias < 2% Page 20 of 26 ------- QA Requirement Result Status Primary SRM Cylinder Expiration Date 7-Feb-28 Primary SRM Gas Standard OK SRM Gas Standards Primary SRM Cylinder Pressure >150 psi 1900 Primary SRM cylinder pressure is OK SRM Dilution Check Cylinder Expiration Date 30-Sep-27 Dilution Check SRM Gas Standard OK Dilution Check SRM Cylinder Pressure >150 psi 1725 Dilution check SRM cylinder pressure is OK High Flow Standard Expiration Date 8-Feb-23 Standard OK Laboratory Flow Standard Low Flow Standard Expiration Date 8-Feb-23 Standard OK Ultra Low Flow Standard Expiration Date 9-Feb-23 Standard OK Calibrator Flow Calibration within 2 weeks of assay 5-Jun-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers] Calibrated High Flow MFC Slope Range = 0.99 -1.0 0.9999990 High MFC OK Calibrated Low Flow MFC Slope Range = 0-99 -1.0 0.9999804 Low MFC OK Analyzer Calibration within 2 week of assay 5-Jun-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1 % at point #1 (>80% URL) 0.30% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #2 0.30% Assay may be conducted at this concentration Carbon Monoxide Gas Analyzer Estimate of Uncetainty < 1 % at point #3 0.31% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #4 0.32% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #5 (-50% URL) 0.33% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 1.0030 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 6-Jun-22 Dilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% 0.116% Dilution Check RSD is OK Day of Assay Zero/Span Check Day of Assay Zero Check - Std. Error < 1 % Day of Assay Zero Check - Relative Difference < 5% Std. Error is okay. RD is okay. Zero Gas Std Error is OK Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK „ Challenge Standard #1 Std. Error < 1% Challenge Standard #1 Assay Challenge Standard #1 vendor certificate bias The standard error is okay. -0.35% Challenge Standard #1 Std Error is OK Challenge Std. #1 vendor certificate bias < 2% Page 21 of 26 ------- QA Requirement Result Status Primary SRM Cylinder Expiration Date 27-Jun-23 Primary SRM Gas Standard OK SRM Gas Standards Primary SRM Cylinder Pressure >150 psi 850 Primary SRM cylinder pressure is OK SRM Dilution Check Cylinder Expiration Date 16-Sep-25 Dilution Check SRM Gas Standard OK Dilution Check SRM Cylinder Pressure >150 psi 1625 Dilution check SRM cylinder pressure is OK High Flow Standard Expiration Date 8-Feb-23 Standard OK Laboratory Flow Standard Low Flow Standard Expiration Date 8-Feb-23 Standard OK Ultra Low Flow Standard Expiration Date 9-Feb-23 Standard OK Calibrator Flow Calibration within 2 weeks of assay 5-Jun-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers) calibrated High Flow MFC Slope Range = 0.99 -1.0 0.9999990 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.0' 0.9999804 Low MFC OK Analyzer Calibration within 2 weeks of assay 8-Jun-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1 % at point #1 (>80% URL) 0.31% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #2 0.32% Assay may be conducted at this concentration Sulfur Dioxide Gas Analyzer Estimate of Uncetainty < 1 % at point #3 0.32% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #4 0.33% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #5 (-50% URL) 0.34% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 1 0013 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 6-Jun-22 Dilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% 0.116% Dilution Check RSD is OK Day of Assay Zero/Span Check Day of Assay Zero Check - Std. Error < 1 % Day of Assay Zero Check - Relative Difference < 5% Std. Error is okay. RD is okay. Zero Gas Std Error is OK Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Challenge Standard #1 Assay Challenge Standard #1 Std. Error < 1% Challenge Standard #1 vendor certificate bias The standard error is okay. -0.84% Challenge Standard #1 Std Error is OK Challenge Std. #1 vendor certificate bias < 2% Page 22 of 26 ------- QA Requirements Summary QA Requirement Result Status SRM Gas Standards Primary SRM Cylinder Expiration Date 30-Sep-27 Primary SRM Gas Standard OK Primary SRM cylinder pressure is OK Primary SRM Cylinder Pressure >150 psi 2000 SRM Dilution Check Cylinder Expiration Date 7-Feb-28 Dilution Check SRM Gas Standard OK Dilution check SRM cylinder pressure is OK Dilution Check SRM Cylinder Pressure >150 psi 1000 Laboratory Flow Standard High Flow Standard Expiration Date 8-Feb-23 Standard OK Standard OK Standard OK Low Flow Standard Expiration Date 8-Feb-23 Ultra Low Flow Standard Expiration Date 9-Feb-23 Calibrator Flow Calibration within 2 weeks of assay 29-Aug-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 • 1.0 0.9999997 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.0' 0.9999993 Low MFC OK Analyzer Calibration within 2 week of assay 30-Aug-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1% at point #1 (>80% URL) 0.38% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #2 0.39% Assay may be conducted at this concentration Carbon Monoxide Gas Analyzer Estimate of Uncetainty < 1 % at point #3 0.40% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #4 0.41% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #5 (—50% URL) 0.42% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 0.9993 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 31-Aug-22 Dilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% -0.033% Dilution Check RSD is OK Day of Assay Zero Check - Std. Error < 1% Std. Error is okay. Zero Gas Std Error is OK Day of Assay Zero/Span Check Day of Assay Zero Check - Relative Difference < 5% RD is okay. Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Challenge Standard #1 Assay Challenge Standard #1 Std. Error < 1% Challenge Standard #1 vendor certificate bias The standard error is okay. 0.39% Challenge Standard #1 Std. Error is OK Challenge Std. #1 vendor certificate bias < 2% Page 23 of 26 ------- QA Requirements Summary QA Requirement Result Status Primary SRM Cylinder Expiration Date 18-Sep-27 Primary SRM Gas Standard OK SRM Gas Standards Primary SRM Cylinder Pressure >150 psi 2000 Primary SRM cylinder pressure is OK SRM Dilution Check Cylinder Expiration Date 19-Sep-29 Dilution Check SRM Gas Standard OK Dilution Check SRM Cylinder Pressure >150 psi 1000 Dilution check SRM cylinder pressure is OK High Flow Standard Expiration Date 8-Feb-23 Standard OK Laboratory Flow Standard Low Flow Standard Expiration Date 8-Feb-23 Standard OK Ultra Low Flow Standard Expiration Date 9-Feb-23 Standard OK Calibrator Flow Calibration within 2 weeks of assay 29-Aug-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99-1.0 0.9999997 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.0' 0.9999993 Low MFC OK Analyzer Calibration within 2 week of assay 29-Aug-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty< 1%atpoint#1 (>80% URL) 0.30% Assay may be conducted at this concentration Estimate of Uncetainty< 1% at point #2 0.30% Assay may be conducted at this concentration Carbon Monoxide Gas Analyzer Estimate of Uncetainty < 1% at point #3 0.31% Assay may be conducted at this concentration Estimate of Uncetainty< 1%atpoint#4 0.32% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #5 (-50% URL) 0.33% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 1.0007 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 29-Aug-22 Dilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% 0.251% Dilution Check RSD is OK Day of Assay Zero/Span Check Day of Assay Zero Check - Std. Error < 1 % Day of Assay Zero Check - Relative Difference < 5% Std. Error is okay. RD is okay. Zero Gas Std Error is OK Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Challenge Standard #1 Assay Challenge Standard #1 Std. Error < 1% Challenge Standard #1 vendor certificate bias The standard error is okay. 0.13% Challenge Standard #1 Std Error is OK Challenge Std. #1 vendor certificate bias < 2% Challenge Standard #2 Assay Challenge Standard #2 Std. Error < 1% The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias -0.12% Challenge Std. #2 vendor certificate bias < 2% Page 24 of 26 ------- QA Requirement Result Status Primary SRM Cylinder Expiration Date 27-Jun-23 Primary SRM Gas Standard OK SRM Gas Standards Primary SRM Cylinder Pressure >150 psi 1675 Primary SRM cylinder pressure is OK SRM Dilution Check Cylinder Expiration Date 16-Sep-25 Dilution Check SRM Gas Standard OK Dilution Check SRM Cylinder Pressure >150 psi 1625 Dilution check SRM cylinder pressure is OK High Flow Standard Expiration Date 8-Feb-23 Standard OK Laboratory Flow Standard Low Flow Standard Expiration Date 8-Feb-23 Standard OK Ultra Low Flow Standard Expiration Date 9-Feb-23 Standard OK Calibrator Flow Calibration within 2 weeks of assay 29-Aug-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 -1.0 0.9999997 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.0' 0.9999993 Low MFC OK Analyzer Calibration within 2 weeks of assay 31-Aug-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1% at point #1 (>80% URL) 0.18% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #2 0.18% Assay may be conducted at this concentration Sulfur Dioxide Gas Analyzer Estimate of Uncetainty < 1% at point #3 0.19% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #4 0.19% Assay may be conducted at this concentration Estimate of Uncetainty* 1% at point #5 (-50% URL) 0.20% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 1.0015 Analyzer Slope is acceptable .. . Dilution Check Date within 2 weeks of assay Dilution Check Dilution Check Relative % Difference < 1 % 29-Aug-22 Dilution check within 2 weeks of assay 0.251% Dilution Check RSD is OK Day of Assay Zero/Span Check Day of Assay Zero Check - Std. Error < 1% Day of Assay Zero Check - Relative Difference < 5% Std. Error is okay. RD is okay. Zero Gas Std Error is OK Zero Gas RD is OK Day of Assay Span Check • Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check • Relative Difference <5% RD is okay. Span Gas RD is OK A Challenge Standard #1 Std. Error < 1% Challenge Standard #1 Assay Challenge Standard #1 vendor certificate bias The standard error is okay. 0.18% Challenge Standard #1 Std. Error is OK Challenge Std #1 vendor certificate bias < 2% Challenge Standard #2 Assay Challenge Standard #2 Std. Error < 1% The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias -0.29% Challenge Std #2 vendor certificate bias < 2% Page 25 of 26 ------- QA Requirements Summary QA Requirement Result Status SRM Gas Standards Primary SRM Cylinder Expiration Date 14-Sep-25 Primary SRM Gas Standard OK Primary SRM cylinder pressure is OK Primary SRM Cylinder Pressure >150 psi 1700 SRM Dilution Check Cylinder Expiration Date 1-Feb-24 Dilution Check SRM Gas Standard OK Dilution check SRM cylinder pressure is OK Dilution Check SRM Cylinder Pressure >150 psi 200 Laboratory Flow Standard High Flow Standard Expiration Date 8-Feb-23 Standard OK Standard OK Standard OK Low Flow Standard Expiration Date 8-Feb-23 Ultra Low Flow Expiration Date 9-Feb-23 Calibrator Flow Calibration within 2 weeks of assay 29-Aug-22 Calibrator flow calibration within 2 weeks of assay Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 -1.0 0.9999997 High MFC OK Calibrated Low Flow MFC Slope Range = 0.99 -1.01 0.9999993 Low MFC OK Analyzer Calibration within 2 weeks of assay 3-Sep-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1% at point #1 (>80% URL) 0.13% Assay may be conducted at this concentration Oxides of Nitrogen Gas Analyzer NO Portion Estimate of Uncetainty < 1 % at point #2 0.13% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #3 0.14% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #4 0.14% Assay may be conducted at this concentration Estimate of Uncetainty < 1 % at point #5 (-50% URL) 0.14% Assay may be conducted at this concentration Analyzer slope is within 0.98-1.02 1.0028 Analyzer Slope is acceptable Analyzer Calibration within 2 week of assay 3-Sep-22 Analyzer calibration within 2 weeks of assay Estimate of Uncetainty < 1 % at point #1 (>80% URL) 0.12% Assay may be conducted at this concentration Oxides of Nitrogen Gas Analyzer NOx Portion Estimate of Uncetainty < 1% at point #2 0.12% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #3 0.12% Assay may be conducted at this concentration Estimate of Uncetainty < 1%atpoint#4 0.12% Assay may be conducted at this concentration Estimate of Uncetainty < 1% at point #5 (-50% URL) 0.13% Assay may be conducted at this concentration Analyzer slope is within 0.98-1,02 1.0018 Analyzer Slope is acceptable Dilution Check Dilution Check Date within 2 weeks of assay 29-Aug-22 iDilution check within 2 weeks of assay Dilution Check Relative % Difference < 1% 0.251% Dilution Check RSD is OK Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay. Zero Gas Std Error is OK Day of Assay Zero/Span Check NO Portion Day of Assay Zero Check - Relative Difference < 5% RD is okay. Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Day of Assay Zero Check - Std. Error < 1% Std. Error is okay. Zero Gas Std Error is OK Day of Assay Zero/Span Check NOx Portion Day of Assay Zero Check - Relative Difference < 5% RD is okay. Zero Gas RD is OK Day of Assay Span Check - Std. Error < 1% Std. Error is okay. Span Gas Std. Error is OK Day of Assay Span Check - Relative Difference <5% RD is okay. Span Gas RD is OK Challenge Standard #1 NO Assay Challenge Standard #1 Std. Error < 1% The standard error is okay. Challenge Standard #1 Std. Error is OK Challenge Standard #1 vendor certificate bias -0.52% Challenge Std #1 vendor certificate bias < 2% Challenge Standard #1 NOx Assay Challenge Standard #1 Std. Error < 1% The standard error is okay. Challenge Standard #1 Std. Error is OK Challenge Standard #1 vendor certificate bias -0.23% Challenge Std. #1 vendor certificate bias < 2% Challenge Standard #2 NO Assay Challenge Standard #2 Std. Error < 1% The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias 0.19% Challenge Std #2 vendor certificate bias < 2% Challenge Standard #2 NOx Assay Challenge Standard #2 Std. Error < 1 % The standard error is okay. Challenge Standard #2 Std. Error is OK Challenge Standard #2 vendor certificate bias 0.17% Challenge Std. #2 vendor certificate bias < 2% Challenge Standard #3 NO Assay Challenge Standard #3 Std. Error < 1% The standard error is okay. Challenge Standard #3 Std. Error is OK Challenge Standard #3 vendor certificate bias -0.15% Challenge Std. #3 vendor certificate bias < 2% Challenge Standard #3 NOx Assay Challenge Standard #3 Std. Error < 1 % Challenge Standard #3 vendor certificate bias The standard error is okay. -0.63% Challenge Standard #3 Std. Error is OK Challenge Std. #3 vendor certificate bias < 2% Page 26 of 26 ------- United States Office of Air Quality Planning and Standards Publication No. EPA-454/R-23-005 Environmental Protection Air Quality Assessment Division May 2023 Agency Research Triangle Park, NC ------- |