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U.S. EPA Ambient Air Monitoring Protocol Gas
Verification Program
Annual Report CY 2019

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EPA-454/R-21-002
March 2021
U.S. EPA Ambient Air Monitoring Protocol Gas Verification Program
Annual Report CY 2019
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Air Quality Assessment Division
Research Triangle Park, NC

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Table of Contents
Acknowledgements	5
Acronyms and Abbreviations	6
1.0 Introduction	7
3.0 Survey and Verification Results	12
Appendix A QA Reports from Measurement Data Worksheets for 2019	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 SQ2 Verifications	15
Table 5. AA-PGVP NO and NQx Verifications	15
Figures
Figure 1. AA-PGVP Flow Chart
Figure 2. Annual Survey
11
12

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Ac k n o w I e d ge m e nts
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
M o n i t o r i n g 0 rga n i z a t i o n s
EPA acknowledges the monitoring organizations that supported the PGVP Annual Survey. They include:
Kentucky Division for Air Quality
Missouri Laboratory Services Program

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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
coc
Chain of Custody
EPA
Environmental Protection Agency
GMIS
Gas Manufacturer's Internal Standard
MQO
measurement quality objective
NIST
National Institute of Standards and Technology
NMI
Netherlands Measurement Institute
NTRM
NIST Traceable Reference Material
OAQPS
Office of Air Quality Planning and Standards
OAP
Office of Atmospheric Programs
OAR
Office of Air and Radiation
OIG
Office of the Inspector General
ORD
Office of Research and Development
PQAO
Primary Quality Assurance Organization
QA
quality assurance
QAPP
quality assurance project plan
QC
quality control
RAVL
Regional Analytical Verification Laboratory
RO
Reporting Organization (subcomponent of PQAO)
RPD
relative percent difference
SOP
standard operating procedure
SRM
standard reference material

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1.0 Introduction
Background and Program Goals
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 26

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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 Docur i
The purpose of this document is to report the activities that occurred in 2019 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, in 2019 the EPA Region 2
Regional Analytical Verification Laboratory (RAVL) ceased its active participation in the AA-PGVP. During
2019, the AA-PGVP operated 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 and 2021 EPA will begin reengineering the AA-PGVP and
attempt to find an additional EPA regional laboratory to serve as a RAVL in place of EPA Region 2.
The following provides a brief explanation of the 2019 implementation process.
Producer Information Data Collection - 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
5 www.epa.gov/amtic/ambient-air-protocol-eas-verification-program
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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, only two agencies
participating in the survey for 2019. Without the survey results, a systematic selection of producers could
not be performed. The AA-PGVP performed assays on all cylinders submitted by regulatory monitoring
agencies. Representative sampling was not attempted for CY-2019. OAQPS is in the process of developing
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.
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
N/A
N/A
2
No later than June 17
June 24 - July 5
3
No later than Sept 3
Sept 9 - Sept 20
4
No later than Nov 25
Dec 2 - Dec 13
Open
House
TBD
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 2019 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.
Monitoring
Organizations
	—*¦ Planning
— • ~ Data
Standards
Ambic it Cylinders,
COCs, i * Mfr. Certs.

Regional
Verification
Lab
Spec
Gas
Prod
NIST
possible
reanalysis
Technical
Technical
Assistance
Assistance
Audit
Data
Audit
Data
EPA
Web Site
End
User
Audit
Data&
Protocol
Audit
Data
EPA
Figure 1. AA-PGVP Flow Chart
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.
If EPA cannot get a cylinder from the monitoring organization, and that producer is being used, EPA will invite the
producer to send a cylinder directly to an RAVL.
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 OAQ.PS and the monitoring organizations.
5.	OAQPS reviews the data and sends verification results to the specialty gas vendors.
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 annually uses
a web-based survey that each monitoring organization completes. 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. Also, as discussed in Section 2, participation in the annual survey dropped to only
two monitoring programs in 2019.
300
250
200
150
100
50
0
Figure 2. Annual Survey
Page 12 of 26
AA-PGVP Annual Survey
Participation Trend
¦				—- ¦ ¦ ¦


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¦





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p
00
00

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2019

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! ) 1 ¦'i as Standards Sent to RAVLs m <1 i"i .1 ¦ ¦ "i" "
Qtr
Cylinder ID
Pollutant
Lab
Producer
Facility
Agency
2
CC143319
S02
7
Linde
Alpha, NJ
Albuquerque Environmental Health
And Energy Department
2
CC703098*
NO, NOx
7
PraxAir
Los Angeles, CA
San Diego County Air Pollution
Control District
2
CC78206**
CO
7
PraxAir
Los Angeles, CA
(Sent by Producer)
3
CC28869
CO
7
AirGas
Chicago, IL
Missouri Laboratory Services
Program
3
SD10801
NO, NOx
7
Matheson
Waverly, TN
Kansas Department Of Health And
Environment
3
SD15146
NO, NOx
7
Matheson
Waverly, TN
Kansas Department Of Health And
Environment
3
LL126837
S02
7
PraxAir
Toledo, OH
University Hygenic Laboratory
4
FF528545
NO, NOx
7
Tier 5 Labs.
Indianapolis, IN
Wisconsin Dept Of Natural
Resources, Air Monitoring Section
Table 2. Gas Standards Sent to RAVLs
Notes: * Cylinder opened prior to submission to EPA
** Direct submission by producer, assay results not blind to 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 or not an individual protocol gas standard concentration was within ±2% of the certified
value. The Ambient Air Program has never identified an acceptance criterion for the protocol gases. Since
the AA-PGVP has not been established to provide a statistically rigorous assessment of any specialty gas
producer, the RAVLs report all valid results as analyzed, but it is suggested that any 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 the verification results for CO and S02, and Table 5 provides the NOx
results.
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Table 3. MQOs for the AA-PGVP
Requirement
Frequency
Acceptance Criteria
Protocol Gas
Doc. Reference
Comments
Completeness
All standards analyzed
95%

Based on an anticipated 40
cylinders per lab per year.
Quarterly Flow
Calibration
Quarterly-no more than
1 mo. before verification
Calibration flow
accuracy within + 1%
2.3.7
Using flow primary
standard
Calibrator Dilution
Check
Quarterly -within 2 weeks
of assay
+ 1% RD
2.3.5.1
Second SRM. Three or
more discrete
measurements
Analyzer
Calibration
Quarterly-within 2 weeks
of assay
+ 1% RPD (each point)
Slope 0.89-1.02
2.1.7.2
5 points between 50-90%
of upper range limit of
analyzer + zero point
Zero & Span
Verifications
Each day of verification
SE mean < 1% and
accuracy + 5% RD
2.1.7.3, 2.3.5.4
Drift accountability. 3
discrete measurements of
zero and span
Precision Test1
Day of Verification
+ 1% RD standard
error of the mean
2.3.5.4
SRM at conc. >80% of
analyzer URL
Routine Data
Check
Any Standard with Value
>2% Tag Value
NA

Sample run three times to
verify value.
Lab Comparability
2/year
+ 2 % RPD
NA
Sample run three average
value used.
Standards Certification
Primary flow
standard
Annually-Certified by
NVLAP certified lab
1.0 %
NA
Compared to NIST
Traceable
NISTSRMs
Expiration date SRM
pressure > 150 psig


Will follow NIST
recertification
requirements
Table 3. MQOs for AA-PGVP
1 The precision test does not need to be accomplished if analyzer calibrated on same day as analysis.
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Table 4. 2019 AA-PGVP CO and S02 Verifications*
Qtr
Lab
Producer
Facility
Cylinder
ID
Pollutant
Assay
Cone
Producer
Cone
% Bias
95%
Uncertainty
3
7
AirGas
Chicago, IL
CC28869
CO
223.45
223.8
-0.16
0.23
2
7
PraxAir
Los Angeles, CA
CC78206*
CO
3002.28
3002
0.01
0.21
2
7
Linde
Alpha, NJ
CC143319
S02
4.99
4.9
1.91
0.26
3
7
PraxAir
Toledo, OH
LL126837
S02
28.92
29
-0.29
0.14
Table 4. AA-PGVP CO and S02 Verifications
Notes: * Cylinder Sent Directly by Producer
t An Estimate for the national usage for specific protocol gas producers cannot be determined
due to lack of participation in annual survey
Table 5. 2019 AA-PGVP NO and NOx Verifications*
Qtr
Lab
Producer
Facility
; Cylinder ID
Pollutant
Assay
Cone
Producer
Cone
% Bias
95%
Uncertainty
4
7
Tier 5 Labs
Indianapolis, IN
| FF528545
NO
17.9
19.2
6.79
0.39
3
7
Matheson
; Waverly, TN
SD15146
NO
30.06
30.33 :
-0.88
0.36
3
7
Matheson
: Waverly, TN
1 SD10801
NO
30.21
30.38
-0.55
0.36
2
7
PraxAir
Los Angeles CA
CC703098*
NO
18.25
15.78
15.68
0.17
4
7
Tier 5
Labs.
Indianapolis, IN
: FF528545
NOx
19.27
19.4
-0.69
0.29
3
7
Matheson
Waverly, TN
| SD10801
NOx
30.38
30.38
0.01
0.34
3
7
Matheson
Waverly, TN
SD15146
NOx
30.06
30.36 :
-0.97
0.34
2
7
PraxAir
Los Angeles CA
! CC703098*
NOx
18.17
15 78
15.16
0.16
Table 5. AA-PGVP NO and NOx Verifications
Notes: * Cylinder was opened prior to submission to EPA.
t An Estimate for the national usage for specific protocol gas producers cannot be determined
due to lack of participation in annual survey
Eight cylinders were received by the AA-PGVP during calendar year 2019. Seven of these cylinders were
received from regulatory monitoring agencies to support the AA-PGVP. One of the cylinders was directly
submitted from a protocol gas producer. The assay results for all cylinders are included in Tables 4 and 5 but
some are qualified with footnotes to denote that they do not fully meet the assessment requirements for the
AA-PGVP. The CO cylinder directly submitted by Praxair was not blind to the producer. The NO cylinder
provided by San Diego County Air Pollution Control District (SDAPCD) was opened by the agency prior to
shipment to EPA. AA-PGVP requires that cylinders be unopened prior to receipt at the RAVL. While opened
prior to receipt at the RAVL, the Praxair cylinder from SDAPCD is not considered to have been contaminated
or diluted based on a comparison of the assay results to the producer certified concentrations.
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All results for the CO and S02 standards were within the ±2% acid rain criteria acceptance criterion. One of
the three protocol gas cylinder standards assayed for NO/NOx (Cylinder ID: FF528545) did not meet the ±2%
acid rain criteria acceptance criterion and ±4% AA-PGVP action level criteria. The 4th cylinder for NO/NOx
(Cylinder ID CC703098) also did not meet the ±4% AA-PGVP action level criteria and is qualified as being open
prior to the RAVL's assay.
In 2019 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. The Region 7 RAVL assayed its
own internal standard (Praxair Cylinder ID CB11278) and all results were within the ±2% acceptance criteria,
but independent analysis was not performed. Additionally, due to the delay of issuing this annual report, the
opportunity to contact the protocol gas producers to offer confirmatory assay of the cylinders was not
possible. Protocol gas production facilities were notified of the failing verifications by their regulatory
monitoring program customers.
4.0 Summary and Conclusions
General -
The AA-PGVP is implementing a verification process that is blind to the specialty gas producers. One of goals
of the ambient air monitoring rule (published March 28, 2016) was for the verifications performed by the
RAVLs to be focused more on our 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 (blind
verification of gas cylinders provided by monitoring organizations) cannot be accomplished if EPA relies on
the specialty gas producers to submit cylinders for assessment. Of the 8 protocol gas cylinder standards
submitted for analysis only one cylinder was directly submitted by a gas producer.
While the program is successfully implementing a blind verification process, only 8 cylinders were analyzed in
2019 or 10% of the AA-PGVP goal of 80 cylinders annually. One of the 8 cylinders was sent direct from the
producer and another cylinder was opened by the submitting agency before sent to EPA. These eight-
cylinder submissions resulted in only 12 verifications performed in 2019 (some cylinders are a blend of
multiple gas standards). Results show that 3 of the 12 verifications (25%) failed the ±2% Acid Rain Program
criteria and the ±4% AA-PGVP action level. It is difficult to assess the extent to which this issue impacts our
ambient air monitoring networks in 2019 due to the low utilization of the RAVLs by our monitoring programs
and low participation rate in the annual protocol gas questionnaire. In 2019 there were 28 EPA protocol gas
production facilities in operation nationally. It is uncertain how many of these facilities were used in the
ambient air monitoring networks in 2019. Additionally, of the 28 protocol gas production facilities operating,
only 6 were verified by our ambient air monitoring program in calendar year 2019.
Survey Participation Improvement -
Since its inception, the AA-PGVP has relied on an annual survey to determine which gas producers and
facilities are used for generating CO, S02, and N02 test atmospheres from protocol gas cylinder standards.
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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 states using protocol gases were required to complete the survey every year. While it was thought at
the time that this regulatory requirement would increase the participation and create a comprehensive list of
the protocol gas producers used in the national network, the survey participation rate has not improved and
dropped to only 2 monitoring agency participating in the online questionnaire in calendar year 2019. 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 monitoring rule was revised in 2016, the AA-PGVP has made progress in achieving blind
verifications of the protocol gas cylinders used in our ambient air monitoring networks. However, the
program continues to 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 represent the
national ambient air monitoring networks was not achieved in calendar year 2019. Only seven protocol gas
cylinder standards were submitted by six PQAOs in 2019 to support this national program. Region 7 assayed
all the cylinders received in 2019. Four of the six monitoring programs submitting protocol gas cylinders for
the AA-PGVP were clustered in proximity to the Region 7 laboratory. A better national sampling of
monitoring programs and protocol gas producers continues to be needed. Diminished assay capacity was in
part due to the Region 2 laboratory ceasing RAVL operations due to staffing and resource limitations. OAQPS
is working to replace this assay capacity with the Region 4 laboratory.
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.
OAQPS will begin reviewing and revising the QAPP for this program in 2020 with a goal of finalizing the
revised QAPP by the end of 2021. During calendar year 2021, OAQPS will reach out to AA-PGVP stakeholders
in the regulated community and protocol gas producers to solicit feedback on revisions to this program.
In 2019, 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. The Region 4 RAVL is scheduled to
become operational in calendar year 2021.
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
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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. Data entry errors on the annual survey and chain of custody forms and the lack of key
fields impede analysis of the information collected for this program.
OAQPS is actively investigating an AQS database solution to replace some of the data management practices
historically performed in the program. This includes assessing the feasibility of making modifications to the
current AQS "QA-Transaction" file format for the single point quality control checks and annual performance
audits. The proposed modifications being investigated would allow for documenting the protocol gas
producer and 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 36% effective between 2014-2018 and only captured the input of two agencies
in calendar year 2019.
Page 18 of 26

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Appendix A > , orts from Measureme i«' " ita Worksh.v i.."* wV"v
Ambient Air Protocol Gas Verification Program
QA Reports from Measurement Data Worksheets for 2019
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 2019.
Page 19 of 26

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QA Requirements Summary,
Region 7 -
2nd Quarter of 2019

QA 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
1100

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
2050

Dilution check SRM cylinder pressure is OK


High Flow Standard Expiration Date
10-Jan-20

Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20

Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20

Standard OK

Calibrator Flow Calibration within 2 weeks of assay
23-Jun-19
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1.01
0.9999996
High MFC OK

Calibrated Low Flow MFC Slope Range = 0.99 -1.01
0.9999915
Low MFC OK

Analyzer Calibration within 2 week of assay
23-Jun-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1% at point #1 (>80% URL)
0.32%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #2
0.33%
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
0.42%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #5 (~50% URL)
0.76%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9989
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
24-Jun-19
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference <1%
0.017%
Dilution Check RSD is OK
Page 20 of 26

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QA Requirements Summary, Region 7 - 2nd Quarter of 2019
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
1750
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
1750
Dilution check SRM cylinder pressure is OK

High Flow Standard Expiration Date
10-Jan-20
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20
Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20
Standard OK
Calibrator Flow Calibration within 2 weeks of assay	23-Jun-19
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 ~| C	0.9999996
Calibrated Low Flow MFC Slope Range = 0.99 --| 0	0.9999915
Calibrator flow calibration within 2 weeks of assay
High MFC OK
Low MFC OK

Analyzer Calibration within 2 weeks of assay
26-Jun-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1 % at point #1 (>80% URL
0.15%
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
0.15%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 % at point #4
0.20%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1 % at point #5 (~50% URL
0.37%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9964
Analyzer Slope is acceptable

Analyzer Calibration within 2 week of assay
26-Jun-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1 % at point #1 (>80% URL
0.15%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1 % at point #2
0.13%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 % at point #3
0.15%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1 % at point #4
0.20%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1 % at point #5 (~50% URL
0.36%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9980
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
24-Jun-19
Dilution Check Relative % Difference < 1 %
0.017%
Dilution check within 2 weeks of assay
Page 21 of 26

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QA Requirements Summary, Region 7 -
2nd Quarter of 2019

QA Requirement
Result

Status

Primary SRM Cylinder Expiration Date
23-Mar-20

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
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
10-Jan-20

Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20

Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20

Standard OK
Calibrator Flow Calibration within 2 weeks of assay
23-Jun-19
Calibrator flow calibration within 1 month of assay
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 -1.01
0.9999996
High MFC OK
Calibrated Low Flow MFC Slope Range = 0.99 -1.01
0.9999915
Low MFC OK

Analyzer Calibration within 2 weeks of assay
27-Jun-19
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
0.16%
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)
0.35%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
1.0034
Analyzer Slope is acceptable

Dilution Check
Dilution Check Date within 2 weeks of assay
24-Jun-19
Dilution check within 1 month of assay
Dilution Check Relative % Difference < 1%
0.017%
Dilution Check RSD is OK
Page 22 of 26

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QA Requirements Summary,
Region 7
- 3rd Quarter of 2019

QA Requirement
Result

Status

Primary SRM Cylinder Expiration Date
26-Sep-21

Primary SRM Gas Standard OK
SRM Gas Standards
Primary SRM Cylinder Pressure >150 psi
1000

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
2100

Dilution check SRM cylinder pressure is OK


High Flow Standard Expiration Date
10-Jan-20

Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20

Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20

Standard OK

Calibrator Flow Calibration within 2 weeks of assay
7-Sep-19
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1.01
0.9999973
High MFC OK

Calibrated Low Flow MFC Slope Range = 0.99 -1.01
0.9999861
Low MFC OK

Analyzer Calibration within 2 week of assay
7-Sep-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1% at point #1 (>80% URL)
0.25%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #2
0.26%
Assay may be conducted at this concentration
Carbon Monoxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.27%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #4
0.28%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #5 (~50% URL)
0.30%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
1.0023
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
8-Sep-19
Dilution check within 2 weeks of assay
Dilution Check Relative % Difference <1%
0.347%
Dilution Check RSD is OK
Page 23 of 26

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QA Requirements Summary,
Region 7 -
3rd Quarter of 2019

QA 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
1000

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
1000

Dilution check SRM cylinder pressure is OK


High Flow Standard Expiration Date
10-Jan-20

Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20

Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20

Standard OK

Calibrator Flow Calibration within 2 weeks of assay
7-Sep-19
Calibrator flow calibration within 2 weeks of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1.01
0.9999973
High MFC OK

Calibrated Low Flow MFC Slope Range = 0.99 -1.01
0.9999861
Low MFC OK

Analyzer Calibration within 2 weeks of assay
9-Sep-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1°/
at point #1 (>80% URL)
0.42%
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
0.45%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1°/
at point #4
0.48%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1°/
at point #5 (-50% URL)
0.52%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9977
Analyzer Slope is acceptable

Analyzer Calibration within 2 week of assay
9-Sep-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1°/
at point #1 (>80% URL)
0.35%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1°/
at point #2
0.36%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1°/
at point #3
0.37%
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
0.9963
Analyzer Slope is acceptable
..	.	Dilution Check Date within 2 weeks of assay	8-Sep-19	Dilution check within 2 weeks of assay
Dilution Check	y	H	y
Dilution Check Relative % Difference < 1%	0.347% Dilution Check RSD is OK
Page 24 of 26

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QA Requirements Summary, Region 7 - 3rd Quarter of 2019
QA Requirement	Result	Status

Primary SRM Cylinder Expiration Date
23-Mar-20
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
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
10-Jan-20
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20
Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20
Standard OK

Calibrator Flow Calibration within 2 weeks of assay
7-Sep-19
Calibrator flow calibration within 1 month of assay
Calibrator (mass flow controllers)
Calibrated High Flow MFC Slope Range = 0.99 -1.01
0.9999973
High MFC OK

Calibrated Low Flow MFC Slope Range = 0.99 -1.01
0.9999861
Low MFC OK

Analyzer Calibration within 2 weeks of assay
9-Sep-19
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

Estimate of Uncetainty < 1% at point #2
0.21%
Assay may be conducted at this concentration
Sulfur Dioxide Gas Analyzer
Estimate of Uncetainty < 1% at point #3
0.22%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #4
0.23%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #5 (~50% URL)
0.25%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9996
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
8-Sep-19
Dilution check within 1 month of assay
Dilution Check Relative % Difference <1%
0.347%
Dilution Check RSD is OK
Page 25 of 26

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QA Requirements Summary, Region 7 - 4th Quarter of 2019
QA 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
900
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
1500
Dilution check SRM cylinder pressure is OK

High Flow Standard Expiration Date
10-Jan-20
Standard OK
Laboratory Flow Standard
Low Flow Standard Expiration Date
10-Jan-20
Standard OK

Flow Standard Base Unit Expiration Date
10-Jan-20
Standard OK
Calibrator Flow Calibration within 2 weeks of assay	30-Nov-19
Calibrator (mass flow controllers) Calibrated High Flow MFC Slope Range = 0.99 -1.01	0.9999983
Calibrated Low Flow MFC Slope Range = 0.99 - 1.01	0.9999624
Calibrator flow calibration within 2 weeks of assay
High MFC OK
Low MFC OK

Analyzer Calibration within 2 weeks of assay
2-Dec-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1% at point #1 (>80% URL)
0.44%
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
0.48%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #4
0.51%
Assay may be conducted at this concentration

Estimate of Uncetainty < 1% at point #5 (~50% URL)
0.55%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9983
Analyzer Slope is acceptable

Analyzer Calibration within 2 week of assay
2-Dec-19
Analyzer calibration within 2 weeks of assay

Estimate of Uncetainty < 1% at point #1 (>80% URL)
0.36%
Assay may be conducted at this concentration
Oxides of Nitrogen Gas Analyzer
NOx Portion
Estimate of Uncetainty < 1% at point #2
0.37%
Assay may be conducted at this concentration
Estimate of Uncetainty < 1% at point #3
0.38%
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)
0.44%
Assay may be conducted at this concentration

Analyzer slope is within 0.98-1.02
0.9995
Analyzer Slope is acceptable
Dilution Check
Dilution Check Date within 2 weeks of assay
1-Dec-19
Dilution Check Relative % Difference <1%
sP
0s
CO
CD
O
Dilution check within 2 weeks of assay
Page 26 of 26

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United States	Office of Air Quality Planning and Standards	Publication No. EPA-454/R-21-002
Environmental Protection	Air Quality Assessment Division	March 2021
Agency	Research Triangle Park, NC

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