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U.S. EPA
Ambient Air Protocol Gas Verification Program
Annual Report CY 2021
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EPA-454/R-22-004
June 2022
U.S. EPA Ambient Air Protocol Gas Verification Program
Annual Report CY 2021
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Air Quality Assessment Division
Research Triangle Park, North Carolina
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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 2020 19
Tables
Table 1. RAVL Verification Dates 10
Table 2. Gas Standards Sent to RAVLs 13
Table 3. MQOs for the 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
Figure 2 Annual Survey
11
12
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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
Michael Davis 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:
Forsyth County Environmental Affairs Department
Kentucky Division for Air Quality
Maryland Department of the Environment
North Carolina Dept of Environmental Quality
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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
COC Chain of Custody
CONC Concentration
COVID-19 Coronavirus Disease 2019
EPA Environmental Protection Agency
GMIS Gas Manufacturer's Internal 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
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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
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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
expected to ensure that producers selling EPA Protocol Gases participate in 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 29
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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. It will not 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
participating in the program and with information that may be helpful when selecting a producer.
Purpose "" " lis Document
The purpose of this document is to report the activities that occurred in 2021 and provide the results of the
verifications performed.
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) that can be found on the AA-PGVP Web Page on the
Ambient Monitoring Technology Information Center (AMTIC)5.
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. During 2020 the AA-PGVP began transitioning Region 2 operations to the Region 4 laboratory.
However, during 2020 and 2021 the AA-PGVP continued to operate with only the Region 7 RAVL. Operations
with only a single RAVL resulted in the AA-PGVP unable to swap internal quality control samples and
cylinders needing confirmatory assay between two independent RAVLs. During 2020 through 2021 EPA
began reengineering the AA-PGVP. As part of that process, EPA began assisting the EPA Region 4 laboratory
to serve as a replacement RAVL.
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
5 www.epa.gov/amtic/ambient-air-protocol-gas-verification-program
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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 2021 only 4 agencies participated in the survey. With only limited survey results, a systematic selection
of producers could not be performed. For calendar year 2021 the AA-PGVP performed assays on all cylinders
submitted by regulatory monitoring agencies. Representative sampling was not attempted for CY-2021.
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. At the time of this report, Oracle tables and a cylinder metadata entry form to support the
AA-PGVP are now created in AQS and are in testing. EPA anticipates that in CY-2022 that cylinder usage data
that was historically collected via the annual survey will begin to be collected via AQS.
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 10
Feb 15 - Feb 26
2
No later than May 5
May 10 - May 21
3
No later than Aug 18
Aug 23 - Sept 3
4
No later than Nov 3
Nov 8 - Nov 19
Open
House
December 16, 2021
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 2021 no specialty gas producers visited
the Region 7 RAVL.
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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.
1. EPA sends e-mails to the monitoring organization's points of contact to complete the AA-PGVP Survey. EPA compiles
information on specialty gas producers and the monitoring organizations that plan to participate. EPA tries to
schedule the monitoring organization in an appropriate verification quarter based on delivery of standards from the
specialty gas producer.
2. The monitoring organizations order gas standards from specialty gas producers during the normal course of business.
3. The monitoring organizations send a new/unused standard, specialty gas certification and chain of custody form to
the RAVLs.
4. The RAVLS analyze the cylinders and provide the validated results to OAQPS and the monitoring organizations.
5. OAQPS reviews the data and sends verification results to the monitoring organizations. Specialty gas vendors are
notified if the certified concentration of their standard is greater than ±4% of EPA's assay verification results, or
greater than ±2% when the expanded measurement uncertainty is included.
6. At the end of the year, OAQPS compiles final results into a report, sends the report out to the specialty gas vendors
and posts it on the AA-PGVP AMTIC web page.
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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
community.
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.
AA-PGVP Annual Survey
Participation Trend
300
250
200
150
100
50
0
86
13
r59
Di
57
r- 7
51
\
67
2011 2012 2013
2014 2015 2016 2017
Year
2018 2019 2020
2021
All AQS Agencies
•Agencies (S02, CO, N02)
¦Surveyed
Figure 2 Annual Survey
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" ¦> - . as Standards Sent to RAVLs > \» ¦ ¦ - »
Qtr
Cylinder ID
Pollutant
Lab
Producer
Facility
Agency
1
EA0027587
CO
7
Airgas
Tooele UT
Oregon DEQ
1
FF19553
S02
7
Airgas
Tooele UT
Oregon DEQ
1
CLM09545
NO,NOX
7
Airgas
Tooele UT
Oregon DEQ
2
BR0011385
CO
7
Global
Calibration
Gases
Sarasota FL
North Carolina DEQ
1
ET0032606
S02
7
Matheson
Waverly TN
Kansas DHE
1
ET0033881
S02
7
Matheson
Waverly TN
Kansas DHE
2
EB0051619
S02
7
Global
Calibration
Gases
Sarasota FL
North Carolina DEQ
1
FF42766
CO
7
Linde
Los Angeles CA
Oregon DEQ
2
DT00084710
CO,NO,NOX,
S02
7
Linde
Los Angeles CA
National Park Service
1
FF524605
CO
7
Linde
Toledo OH
Indiana DEM
1
FF64232
S02
7
Linde
Toledo OH
Indiana DEM
1
FF625910
NO NOX
7
Linde
Toledo OH
Indiana DEM
4
LL23399
CO, NO, NOX
7
Airgas
Los Angeles CA
South Coast AQMD
Table 2, Gas Standards Sent to RAVLs
Notes: £2 NOx concentration provided by Producer as "informational only"; concentration not certified by Producer.
Verification Results
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 the criteria 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.
The Ambient Air Protocol Gas Verification Program has never identified an acceptance criterion for the
protocol gases. Since the AA-PGVP does not sample enough cylinder standards 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 observed assay verification results with a difference greater than ±4% is cause for concern. Information
related to the analytical reference standards, analytical instruments and methods used, the data reduction
procedures and the data assessment procedures are all found in the AA-PGVP QAPP and SOP and are not
repeated in this report. 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
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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 certified lab
Traceable
NISTSRMs
Expiration date SRM
Will follow NIST
pressure > 150 psig
recertification
requirements
Table 3. MQOs fof PGVP
1 The precision test does not need to be accomplished if analyzer calibrated on same day as analysis.
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,-PGVP CO and S02 Verifications*
Producer
Facility
Cylinder ID
Pollutant
Assay
Cone
Producer
Cone
%
Bias
95%
Uncertainty"
Airgas
Tooele UT
EA0027587
CO
100.14
99.01
-1.1
0.36
Global Cal. Gases
Sarasota FL
BR0011385
CO
199.7
198
-0.9
0.37
Linde
Los Angeles CA
1 FF42766
CO
19.48
19.51
0.2
0.21
Linde
Los Angeles CA
DT0008471
CO
160.9
160.6
-0.2
0.36
Linde
Toledo OH
FF524605
CO
2026.52
2025
-0.1
0.21
Airgas
Los Angeles CA
LL23399
CO
913.7
912.9
-0.1
0.24
Matheson
i WaverlyTN
ET0032606
so2
9.94
10.2
2.6
0.16
Matheson
Waverly TN
ET0033881
so2
10.02
10.2
1.8
0.13
Global Cal. Gases
I Sarasota FL
1 EB0051619
so2
19.67
20
1.7 1
0.16
Linde
Los Angeles CA
DT0008471
so2
24.44
24.1
-1.4
0.15
Airgas
Tooele UT
FF19553
so2
10
10.07
0.7
0.16
Linde
Toledo OH
FF64232
so2
50.39
50.4
0
0.12
Table 4. AA-PGVP CO and S02 Verifications
Notes: * Table grouped by Pollutant and sorted by absolute Bias
** Analytical measurement uncertainty of the RAVL. This 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
1 o: ¦ 11 .V.-PGVP I id Mfix Verifications*
Producer
Facility
Cylinder ID
Pollutant
Assay
Cone
Producer
Cone
%
Bias
95%
Uncertainty"
Linde
i Toledo OH
FF62591
NO
45.22
45.7
1.1
0.33
Airgas
Tooele UT
CLM09545
NO
20.35
20.31
-0.2
0.33
Airgas
( Los Angeles CA
LL23399
NO ,
44.92
, 45.03
0.2
0.23
Linde
Los Angeles CA
DT0008471
NO
37.21
37.2
0
0.28
Linde
Toledo OH
FF625910
NOx
45.3
46.1
1.8
0.33
Linde
Los Angeles CA
DT00084710
NOx
37.21
37.3
0.2
0.36
Airgas
Tooele UT
CLM09545
NOx
20.35
20.38
0.1
0.33
Airgas
Los Angeles CA
LL23399
NOx
45.09
45.1
0
0.22
Table 5. AA-PGVP NO and NOx Verifications
Notes: * Table grouped by Pollutant and sorted by absolute Bias
** Analytical measurement uncertainty of the RAVL. This 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.
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The AA-PGVP received 13 cylinders for assay verification during calendar year 2021. The assay results for
these cylinders are included in Tables 4 and 5.
All but one of the results for the CO and S02 standards were within the ±2% acid rain criteria acceptance
criterion. None of the CO and S02 standards were outside of the ±2% criteria when the expanded uncertainty
is included. Additionally, none of the CO and S02 standards were outside of the ±4% criteria that the AA-
PGVP considers a cause for concern. All results for the NO and NOx standards were within the ±2% acid rain
criteria acceptance criterion.
In 2021 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.
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)
was for the verifications performed by the RAVLs to be focused more 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 13 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 13 cylinders were analyzed
in 2021 or 15% of the AA-PGVP goal of 80 cylinders annually. These 13-cylinder submissions resulted in only
20 verifications performed in 2021 (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%). It is difficult to assess
whether these results are representative of the quality of the standards used in the national ambient air
monitoring networks during 2021 due to the low utilization of the RAVL by the monitoring programs and low
participation rate in the annual protocol gas questionnaire. In 2021 there were 23 commercially operated
EPA protocol gas production facilities. It is uncertain how many of these facilities were used in the ambient
air monitoring networks in 2021. Additionally, of the 23 protocol gas production facilities operating, only five
were verified by EPA's ambient air protocol gas verification program during calendar year 2021.
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
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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 2021 participation in the annual questionnaire was about 3% of the
monitoring agencies that operate CO, S02, and N02 ambient air analyzers. The limited utilization of the
annual questionnaire in 2021 was in part due to EPA contractual issues that resulted in a work stoppage by
EPA's contractor that hosts the website and database for the annual questionnaire. OAQPS is actively
assessing 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
measurement data for the national ambient air monitoring networks was not achieved in calendar year 2021.
Only twelve protocol gas cylinder standards were submitted by six PQAOs in 2021 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 2021 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 2022 and 2023 by using the Region 4 laboratory as an additional RAVL.
OAQPS is also investigating the feasibility of obtaining primary reference materials (PRM) from the
Netherland's National Metrology Institute; Dutch Von Swinden Laboratorium (VSL) for low concentration
Primary Reference Materials (PRMs).
Quality System Improvement -
The Quality Assurance Project Plan (QAPP) has not been updated since the inception of the program in 2010.
Since calendar year 2010, changes to the program have occurred, including regulatory changes in 2016.
These documents need to be reconciled with current program practices and regulatory requirements. During
calendar year 2022 EPA intends to begin updating the analytical SOP for the assay verification.
In 2021, 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.
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Data Management Improvement-
The AA-PGVP has 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. Additionally, data
validation and data entry business rules are needed to ensure the accuracy of the data submitted for both
portions of this program (protocol gas survey and RAVL analytical results). Once accomplished this will
enable both datasets to be readily assessed with respect to monitoring organization, PQAO, and producer
production facility. Historically data entry errors on the annual survey and chain of custody forms and the
lack of key fields between these systems have impeded analysis of the information collected for this program.
During calendar 2021, a revised spreadsheet based COC form was used that incorporated basic data
validation for these key fields. Since the adoption of the revised COC, data entry errors for agency name,
PQAO, and Protocol Gas Producers have ceased.
During calendar 2021 OAQPS continued to actively pursue an AQS database solution to replace some of the
data management practices historically performed by EPA's contractor. This includes modifications to the
current AQS "QA-Transaction" file format for the single point quality control checks and annual performance
audits. The modifications being developed would 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 would 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
22% effective between 2016-2021. To facilitate these enhancements, a beta AQS entry form for submission
of cylinder metadata was developed in calendar year 2021 and is being tested internally by OAQPS. AQS now
has the capability to track the active protocol gas production facilities that are managed by the Clean Air
Markets Division. During Calendar Year 2022 SLT monitoring programs should begin utilizing this new AQS
capability to track EPA protocol gas pollutant cylinder standards. Progress continues with merging the
cylinder metadata with the data stream containing the single point quality control checks and annual
performance audits that are submitted by SLT monitoring programs to AQS. EPA's goal is to have both these
new AA-PGVP systems operational in AQS during calendar 2022.
Page 18 of 29
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Appendix A ¦ orts from Measureme >" ¦ >ta Workshi ¦ ¦¦ ¦¦ ¦ 1 ¦1"
Ambient Air Protocol Gas Verification Program
QA Reports from Measurement Data Worksheets for 2021
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 2021.
Page 19 of 29
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QA Requirements Summary
OA Requirement
Result
Status
Primary SRM Cylinder Expiration Date
7-Jul-22
Primary SRM Gas Standard OK
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
1050
Primary SRM cylinder pressure is OK
SRM Dilution Check Cylinder Expiration Date
26-Sep-21
Dilution Check SRM Gas Standard OK
Dilution Check SRM Cylinder Pressure >150 psi
1825
Dilution check SRM cylinder pressure is OK
High Flow Standard Expiration Date
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Standard Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
28-Feb-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 - 1.0
0.9999919
Low MFC OK
Analyzer Calibration within 2 week of assay
28-Feb-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.34%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #2
0.35%
Assay may be conducted at this concentration
Carbon Monoxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.36%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.39%
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
1.0007
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
1-Mar-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
0.119%
Dilution Check RSD is OK
Day of Assay Zero/Span Check
Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay.
Day of Assay Zero Check - Relative Difference < 5°/> 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°A 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.
0.07%
Challenge Standard #1 Std. Error is OK
Challenge Std. #1 vendor certificate bias < 2%
.. . Challenge Standard #2 Std. Error < 1%
Challenge Standard #2 Assay
Challenge Standard #2 vendor certificate bias
The standard error is okay.
Challenge Standard #2 Std. Error is OK
-0.16%
Challenge Std. #2 vendor certificate bias < 2%
Page 20 of 29
-------
QA Requirements Summary
OA Requirement
Result
Status
Primary SRM Cylinder Expiration Date
13-Apr-24
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
20-Sep-21
Dilution Check SRM Gas Standard OK
Dilution Check SRM Cylinder Pressure >150 psi
550
Dilution check SRM cylinder pressure is OK
High Flow Standard Expiration Date
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Standard Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
28-Feb-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999919
Low MFC OK
Analyzer Calibration within 2 week of assay
1-Mar-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.33%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #2
0.34%
Assay may be conducted at this concentration
Carbon Monoxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.35%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.38%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.41%
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
2-Mar-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
-0.155%
Dilution Check RSD is OK
Day of Assay Zero/Span Check
Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay.
Day of Assay Zero Check - Relative Difference < 5°/> 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°A 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.
1.14%
Challenge Standard #1 Std. Error is OK
Challenge Std. #1 vendor certificate bias < 2%
Page 21 of 29
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QA Requirements Summary
OA Requirement
Result
Status
Primary SRM Cylinder Expiration Date
8-Aug-23
Primary SRM Gas Standard OK
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
375
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
800
Dilution check SRM cylinder pressure is OK
High Flow Standard Expiration Date
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
28-Feb-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1 .C
0.9999994
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999919
Low MFC OK
Analyzer Calibration within 2 weeks of assay
7-Mar-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.43%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NO Portion
Estimate of Uncetainty < 1% at point #2
0.44%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #3
0.46%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.49%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.54%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
0.9966
Analyzer Slope is acceptable
Analyzer Calibration within 2 week of assay
7-Mar-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.49%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1% at point #2
0.51%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #3
0.53%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.57%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.62%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
0.9952
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
1-Mar-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
0.119%
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°/
-------
QA Requirements Summary
OA 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
1200
Primary SRM cylinder pressure is OK
SRM Dilution Check Cylinder Expiration Date
5-Apr-22
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
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Standard Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
28-Feb-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999919
Low MFC OK
Analyzer Calibration within 2 weeks of assay
2-Mar-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.14%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #2
0.15%
Assay may be conducted at this concentration
Sulfur Dioxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.15%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.16%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.18%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
1.0003
Analyzer Slope is acceptable
.. , Dilution Check Date within 2 weeks of assay
Dilution Check
Dilution Check Relative % Difference < 1%
1-Mar-21
Dilution check within 2 weeks of assay
0.119%
Dilution Check RSD is OK
Day of Assay Zero/Span Check
Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay.
Day of Assay Zero Check - Relative Difference < 5°/> 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°A 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.
-0.02%
Challenge Standard #1 Std. Error is OK
Challenge Std. #1 vendor certificate bias < 2%
rh,llon„0 5(,nH,rH Challenge Standard #2 Std. Error < 1%
Challenge Standard #2 Assay
Challenge Standard #2 vendor certificate bias
The standard error is okay.
Challenge Standard #2 Std. Error is OK
-1.77%
Challenge Std. #2 vendor certificate bias < 2%
Page 23 of 29
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QA Requirements Summary
OA Requirement Result Status
Primary SRM Cylinder Expiration Date
27-Jun-23
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
1200
SRM Dilution Check Cylinder Expiration Date
5-Apr-22
Dilution Check SRM Cylinder Pressure >150 psi
1625
High Flow Standard Expiration Date
30-Dec-21
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Ultra Low Flow Standard Expiration Date
6-Jan-22
Calibrator Flow Calibration within 2 weeks of assay
28-Feb-21
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999919
Analyzer Calibration within 2 weeks of assay
2-Mar-21
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.14%
Estimate of Uncetainty < 1% at point #2
0.15%
Sulfur Dioxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.15%
Estimate of Uncetainty < 1% at point #4
0.16%
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.18%
Analyzer slope is within 0.98-1.02
1.0003
Dilution Check
Dilution Check Date within 2 weeks of assay
1-Mar-21
Dilution Check Relative % Difference < 1%
0.119%
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°/iRD 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°XRD is okay.
Span Gas RD is OK
Challenge Standard #1 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
-2.57%
Challenge Std. #1 vendor certificate bias between 2-4%
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
-0.71%
Challenge Std. #2 vendor certificate bias < 2%
Page 24 of 29
-------
QA Requirements Summary
OA Requirement Result Status
Primary SRM Cylinder Expiration Date
13-Apr-24
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
1900
SRM Dilution Check Cylinder Expiration Date
20-Sep-21
Dilution Check SRM Cylinder Pressure >150 psi
550
High Flow Standard Expiration Date
30-Dec-21
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Ultra Low Flow Standard Expiration Date
6-Jan-22
Calibrator Flow Calibration within 2 weeks of assay
9-May-21
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999997
Calibrated Low Flow MFC Slope Range = 0.99 - 1.C
0.9999821
Analyzer Calibration within 2 week of assay
9-May-21
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.47%
Estimate of Uncetainty < 1% at point #2
0.48%
Carbon Monoxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.51%
Estimate of Uncetainty < 1% at point #4
0.54%
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.59%
Analyzer slope is within 0.98-1.02
1.0071
Dilution Check
Dilution Check Date within 2 weeks of assay
10-May-21
Dilution Check Relative % Difference < 1%
-0.701%
Dilution Check RSD is OK |
Day of Assay Zero/Span Check
Day of Assay Zero Check - Std. Error < 1 % Std. Error is okay.
Day of Assay Zero Check - Relative Difference < 5°/> 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.
0.20%
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
0.84%
Challenge Std. #2 vendor certificate bias < 2%
Page 25 of 29
-------
QA Requirements Summary
OA Requirement
Result
Status
Primary SRM Cylinder Expiration Date
1-Feb-24
Primary SRM Gas Standard OK
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
500
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
500
Dilution check SRM cylinder pressure is OK
High Flow Standard Expiration Date
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
9-May-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999997
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999821
Low MFC OK
Analyzer Calibration within 2 weeks of assay
12-May-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1°/
at point #1 (>80% URL
0.45%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NO Portion
Estimate of Uncetainty < 1
at point #2
0.46%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1
at point #3
0.49%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1
at point #4
0.52%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 °/
at point #5 (-50% URL
0.57%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
0.9979
Analyzer Slope is acceptable
Analyzer Calibration within 2 week of assay
12-May-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1°/
at point #1 (>80% URL
0.58%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1
at point #2
0.59%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1
at point #3
0.62%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1
at point #4
0.66%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 °/
at point #5 (-50% URL
0.72%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
0.9965
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
10-May-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
-0.701%
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°A RD is okay.
Zero Gas RD is OK
NO Portion
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
Day of Assay Zero Check - Relative Difference < 5°A RD is okay.
Zero Gas RD is OK
NOx Portion
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 NO Assay
Challenge Standard #1 vendor certificate bias
The standard error is okay.
Challenge Standard #1 Std. Error is OK
0.02%
Challenge Std. #1 vendor certificate bias < 2%
. . „. . Challenge Standard #1 Std. Error < 1%
Challenge Standard #1 NOx Assay _ -
Challenge Standard #1 vendor certificate bias
The standard error is okay.
Challenge Standard #1 Std. Error is OK
-0.25%
Challenge Std. #1 vendor certificate bias < 2%
Page 26 of 29
-------
QA Requirements Summary
OA 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
1050
Primary SRM cylinder pressure is OK
SRM Dilution Check Cylinder Expiration Date
5-Apr-22
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
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Standard Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
9-May-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1 .C
0.9999997
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999821
Low MFC OK
Analyzer Calibration within 2 weeks of assay
11-May-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.22%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 % at point #2
0.22%
Assay may be conducted at this concentration
Sulfur Dioxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.23%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.25%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 % at point #5 (-50% URL
0.27%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
1.0018
Analyzer Slope is acceptable
.. „ , Dilution Check Date within 2 weeks of assay
Dilution Check
Dilution Check Relative % Difference < 1%
10-May-21
Dilution check within 2 weeks of assay
-0.701%
Dilution Check RSD is OK
Day of Assay Zero/Span Check
Day of Assay Zero Check - Std. Error < 1% Std. Error is okay.
Day of Assay Zero Check - Relative Difference < 5°^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°XRD 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.
1.40%
Challenge Standard #1 Std. Error is OK
Challenge Std. #1 vendor certificate bias < 2%
.. . Challenge Standard #2 Std. Error < 1%
Challenge Standard #2 Assay
Challenge Standard #2 vendor certificate bias
The standard error is okay.
Challenge Standard #2 Std. Error is OK
-1.63%
Challenge Std. #2 vendor certificate bias < 2%
Page 27 of 29
-------
QA Requirements Summary
OA Requirement Result Status
Primary SRM Cylinder Expiration Date
7-Feb-28
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
2100
SRM Dilution Check Cylinder Expiration Date
30-Sep-27
Dilution Check SRM Cylinder Pressure >150 psi
1800
High Flow Standard Expiration Date
30-Dec-21
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Ultra Low Flow Standard Expiration Date
6-Jan-22
Calibrator Flow Calibration within 2 weeks of assay
6-Nov-21
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
Calibrated Low Flow MFC Slope Range = 0.99 -1 .C
0.9999846
Analyzer Calibration within 2 week of assay
8-Nov-21
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.23%
Estimate of Uncetainty < 1% at point #2
0.25%
Carbon Monoxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.26%
Estimate of Uncetainty < 1% at point #4
0.28%
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.30%
Analyzer slope is within 0.98-1.02
1.0000
Dilution Check
Dilution Check Date within 2 weeks of assay
8-Nov-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
0.293%
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.
-0.32%
Challenge Standard #1 Std. Error is OK
Challenge Std. #1 vendor certificate bias < 2%
. Challenge Standard #2 Std. Error < 1%
Challenge Standard #2 Assay
Challenge Standard #2 vendor certificate bias
The standard error is okay.
Challenge Standard #2 Std. Error is OK
-1.39%
Challenge Std. #2 vendor certificate bias < 2%
.. . Challenge Standard #3 Std. Error < 1%
Challenge Standard #3 Assay
Challenge Standard #3 vendor certificate bias
The standard error is okay.
Challenge Standard #3 Std. Error is OK
-0.08%
Challenge Std. #3 vendor certificate bias < 2%
Page 28 of 29
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QA Requirements Summary
OA Requirement
Result
Status
Primary SRM Cylinder Expiration Date
1-Feb-24
Primary SRM Gas Standard OK
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
450
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
30-Dec-21
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
30-Dec-21
Standard OK
Ultra Low Flow Expiration Date
6-Jan-22
Standard OK
Calibrator Flow Calibration within 2 weeks of assay
6-Nov-21
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 - 1.C
0.9999994
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.0
0.9999846
Low MFC OK
Analyzer Calibration within 2 weeks of assay
10-Nov-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.24%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NO Portion
Estimate of Uncetainty < 1% at point #2
0.25%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #3
0.27%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.29%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.31%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
1.0047
Analyzer Slope is acceptable
Analyzer Calibration within 2 week of assay
10-Nov-21
Analyzer calibration within 2 weeks of assay
Estimate of Uncetainty < 1% at point #1 (>80% URL
0.21%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1% at point #2
0.22%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #3
0.24%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.25%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #5 (-50% URL
0.28%
Assay may be conducted at this concentration
Analyzer slope is within 0.98-1.02
1.0019
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
8-Nov-21
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference < 1%
0.293%
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°A RD is okay.
Zero Gas RD is OK
NO Portion
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
Day of Assay Zero Check - Relative Difference < 5°A RD is okay.
Zero Gas RD is OK
NOx Portion
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 NO Assay
Challenge Standard #1 vendor certificate bias
The standard error is okay.
Challenge Standard #1 Std. Error is OK
0.24%
Challenge Std. #1 vendor certificate bias < 2%
.. . . „. . Challenge Standard #1 Std. Error < 1%
Challenge Standard #1 NOx Assay _ „ -
Challenge Standard #1 vendor certificate bias
The standard error is okay.
Challenge Standard #1 Std. Error is OK
0.01%
Challenge Std. #1 vendor certificate bias < 2%
Page 29 of 29
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United States Office of Air Quality Planning and Standards Publication No. EPA-454/R-22-004
Environmental Protection Air Quality Assessment Division June 2022
Agency Research Triangle Park, NC
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