Baireiie
The Business of Innovation
Environmental Technology
Verification Program
Advanced Monitoring
Systems Center
Test/QA Plan for Verification of
Semi-Continuous Ambient Air
Monitoring Systems
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TEST/QA PLAN
for
Verification of
Semi-Continuous Ambient Air
Monitoring Systems
Version 1
September 26, 2008
Prepared by
Battelle
505 King Avenue
Columbus, OH 43201-2693
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Test/QA Plan
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SECTION A
PROJECT MANAGEMENT
Al VENDOR APPROVAL PAGE
ETV Advanced Monitoring Systems Center
Draft Test/QA Plan for Verification of
Semi-Continuous Ambient Air Monitoring Systems
Version 1
September 26, 2008
APPROVAL:
Name
Company
Date
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A2 TABLE OF CONTENTS
Section
Semi-Continuous Ambient Air Monitoring Systems
Test/QA Plan
Page2of43
Version 1
September 26, 2008
Page
A PROJECT MANAGEMENT
Al Vendor Approval Page 1
A2 Table of Contents 2
A3 Distribution List 3
A4 Verification Test Organization 4
A5 Background 11
A6 Verification Test Description and Schedule 12
A7 Quality Objectives 15
A8 Special Training/Certification 19
A9 Documentation and Records 19
B MEASUREMENT AND DATA ACQUISITION
Bl Experimental Design 20
B2 Reference Sample Collection 25
B3 Sample Handling and Custody Requirements 27
B4 Laboratory Reference Methods 28
B5 Quality Control Audits and Requirements 29
B6 Instrument/Equipment Testing, Inspection, and Maintenance 31
B7 Instrument Calibration and Frequency 31
B8 Inspection/Acceptance of Supplies and Consumables 32
B9 Non-Direct Measurements 33
BIO Data Management 33
C AS SES SMENT AND OVERSIGHT
Cl Assessments and Response Actions 36
C2 Reports to Management 39
D DATA VALIDATION AND USABILITY
Dl Data Review, Validation, and Verification Requirements 40
D2 Validation and Verification Methods 40
D3 Reconciliation with User Requirements 41
REFERENCES
.43
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A3 DISTRIBUTION LIST
Vendors
John Bowser
Applikon, Inc.
P.O. Box 149
3100 AC SCHIEDAM
The Netherlands
EPA
Lauren Drees
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Mail Code: 208A
Cincinnati, OH 45268
Doug Grosse
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Mail Code: N132C
Cincinnati, OH 45268
Brian Lee
U.S. Environmental Protection Agency
Ariel Rios Building
1200 Pennsylvania Avenue, N.W.
Mail Code: 6204J
Washington, DC 20460
John Walker
U.S. Environmental Protection Agency
National Exposure Research Laboratory
Mail Code: E305-02
Research Triangle Park, NC 27711
Nealson Watkins
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Mail Code: C304-06
Research Triangle Park, NC 27711
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Battelle
Kenneth Cowen
DawnDeojay
Amy Dindal
Bradley Goodwin
Thomas Kelly
Zachary Willenberg
Battelle
505 King Ave.
Columbus, OH 43201
Collaborators
Wayne Robarge
NC State University
Department of Soil Science
3319 Williams Hall, Campus Box 7619
Raleigh, North Carolina, 27695-7619
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A4 VERIFICATION TEST ORGANIZATION
The verification test described in this document will be conducted under the auspices of the U.S.
Environmental Protection Agency (EPA) through the Environmental Technology Verification
(ETV) Program. It will be performed by Battelle, which is managing the ETV Advanced
Monitoring Systems (AMS) Center through a cooperative agreement with EPA. The scope of
the AMS Center covers verification of monitoring technologies for contaminants and natural
species in air, water, and soil.
This verification test will be coordinated and directed by Battelle in cooperation with EPA, with
the support of North Carolina State University (NCSU). A 30-day period of field testing will be
conducted at the Burdens Creek Air Monitoring Site near EPA's Research Triangle Park (RTF)
campus and will involve the evaluation of commercial semi-continuous ambient air monitoring
systems. EPA, which operates and maintains the monitoring site, will provide continuous
ammonia (NH3) and sulfur dioxide (862) measurements for the verification test. Reference
method air sampling and analytical support will be provided by NCSU staff under a purchase
order from Battelle. NCSU will perform the collection and analysis of duplicate denuder/filter
pack samples throughout the verification testing period.
The vendor of the semi-continuous ambient air monitoring systems will install, operate, and
repair or maintain two of their systems during the verification test.
Quality assurance (QA) oversight will be provided by the Battelle AMS Center Quality Manager,
and by the EPA AMS Center Quality Manager at her discretion. The organization chart in
Figure 1 identifies the responsibilities of the organizations and individuals associated with the
verification test. Roles and responsibilities are defined further below.
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Battelle
Manaaement
Battelle AMS Center
Quality Manager
Zachary Willenberg
Battelle AMS
Center Manaaer
Amy Dindal
Verification
Testing Leader
Thomas Kelly
EPA AMS Center
Project Officer
Doug Grosse
EPA AMS Center
Quality Manager
Lauren Drees
EPA Technical
Facilitator
Verification Test
Coordinator
Kenneth Cowen
Vendor Representatives,
EPAandNCSl
Collaborators
Battelle Testing
Staff
Figure 1. Organizational Chart
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A4.1 Battelle
Dr. Kenneth Cowen is the AMS Center Verification Test Coordinator for this test. In this role,
Dr. Cowen will have overall responsibility for ensuring that the technical, schedule, and cost
goals established for the verification test are met. Specifically, he will:
Assemble a team of qualified technical staff to conduct the verification test.
Direct the team (Battelle, EPA, vendor, and NCSU staff) in performing the
verification test in accordance with this test/QA plan.
Ensure that all quality procedures specified in the test/QA plan and in the AMS
Center Quality Management Plan2 (QMP) are followed.
Prepare the draft and final test/QA plan, verification report(s), and verification
statement(s).
Revise the draft test/QA plan, verification report(s), and verification statement(s) in
response to reviewers' comments.
Respond to any issues raised in assessment reports and audits, including instituting
corrective action as necessary.
Serve as the primary point of contact for vendor representatives and collaborators.
Coordinate distribution of the final test/QA plan, verification report(s), and
statement(s).
Establish a budget for the verification test and manage staff to ensure the budget is
not exceeded.
Dr. Thomas Kelly is Battelle's Verification Testing Leader for the AMS Center. Dr. Kelly will:
Support Dr. Cowen in preparing the test/QA plan and organizing the test.
Review the draft and final test/QA plan.
Review the draft verification report(s) and statement(s).
Support Dr. Cowen in responding to any issues raised in assessment reports and
audits.
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Ms. Amy Dindal is Battelle's manager for the AMS Center. Ms. Dindal will:
Review the draft and final test/QA plan.
Review the draft and final verification report(s) and verification statement(s).
Ensure that necessary Battelle resources, including staff and facilities, are committed
to the verification test.
Ensure that confidentiality of sensitive vendor information is maintained.
Maintain communication with EPA's AMS Center Project Officer and Quality
Manager.
Facilitate a stop work order if Battelle or EPA QA staff discovers adverse findings
that will compromise data quality or test results.
Battelle Field Testing Staff will oversee the testing of the semi-continuous ambient air
monitoring systems during the verification test. Battelle staff will be on-site at the EPA air
monitoring facility during the verification test, and will be in daily communication with NCSU
staff responsible for sample collection and analysis, and with technology vendors as needed. The
responsibilities of the field testing staff will be to:
Perform the verification test as described in the test/QA plan.
Communicate with NCSU testing staff on the planning, performance, and reporting of
the reference sampling and analysis.
Record qualitative observations about the maintenance and operation of the semi-
continuous ambient air monitoring system during testing.
Assure that the data from the semi-continuous ambient air monitoring systems are
compiled, recorded, and transmitted to the Verification Test Coordinator on at least a
weekly basis.
Perform analysis of the collected data to carry out the statistical evaluations in
Section B 1.1.
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Provide input on test procedures, technology operation and maintenance, and field
conditions for the draft verification reports.
Mr. Zachary Willenberg is Battelle's Quality Manager for the AMS Center. Mr. Willenberg
will:
Review the draft and final test/QA plan.
Conduct a technical systems audit at least once near the beginning of the verification
test, or designate other QA staff to conduct the audit.
Audit at least 10% of the verification data.
Prepare and distribute an assessment report for each audit.
Verify implementation of any necessary corrective action.
Notify Battelle' s AMS Center Manager to issue a stop work order if audits indicate
that data quality is being compromised.
Provide a summary of the QA/QC activities and results for the verification reports.
Review the draft and final verification report(s) and verification statement(s).
Assume overall responsibility for ensuring that the test/QA plan is followed.
A4.2 Vendors
The responsibilities of the monitoring system vendors are as follows:
Review and provide comments on the draft test/QA plan.
Approve the final test/QA plan prior to test initiation.
Provide duplicate monitoring systems for evaluation during the verification test.
Provide all other equipment/supplies/reagents/consumables needed to operate their
technologies for the duration of the verification test.
Supply a representative to install, operate, and maintain their technologies during the
verification test.
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Provide the data from the two monitoring systems to the Battelle field testing staff
within 1 week of collection.
Provide training to site operator(s) and others associated with supervising and/or
maintaining system operation including during the verification testing period.
Provide written instructions for routine operation of their technologies, including a
daily checklist of diagnostic and/or maintenance activities.
Review and provide comments on the draft verification report and statement for their
monitoring system.
A4.3 EPA
EPA's responsibilities are based on the requirements stated in the "Environmental Technology
Verification Program Quality Management Plan" (EPA QMP). The roles of specific EPA testing
staff are as follows:
Review and provide comments on the draft test/QA plan.
Ensure that the Battelle testing staff, the vendors, and the NCSU staff have
appropriate access to the test site.
Ensure that there is suitable space and electrical power to perform the necessary
testing activities at the test site.
Provide continuous NH3 and 862 reference measurements for the duration of the
verification testing period.
Ms. Lauren Drees is EPA's AMS Center Quality Manager. Ms. Drees will:
Review the draft test/QA plan.
Perform at her option one external technical systems audit during the verification test.
Notify the EPA AMS Center Manager of the need for a stop work order if the
external audit indicates that data quality is being compromised.
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Prepare and distribute an assessment report summarizing results of the external audit.
Review the draft verification report(s) and statement(s).
Mr. Doug Grosse is EPA's Project Officer for the AMS Center. Mr. Grosse will:
Review the draft test/QA plan.
Approve the final test/QA plan.
Review the draft verification report(s) and statement(s).
Oversee the EPA review process for the verification report(s) and statement(s).
Coordinate the submission of verification report(s) and statement(s) for final EPA
approval.
A4.4 NCSU
NCSU personnel are responsible for preparing, collecting and analyzing the denuder/filter pack
reference samples used for comparison with the monitoring systems being tested.
Dr. Wayne Robarge is the NCSU Technical Lead for this verification test. In this role, Dr.
Robarge is responsible for ensuring that the filter pack reference sampling and analysis activities
meet the scheduled milestones agreed upon by Battelle through a purchase order with NCSU.
Dr. Robarge will:
Review the draft test/QA plan.
Be the primary NCSU contact for Battelle's Verification Test Coordinator.
Ensure that designated NCSU staff are available for the verification test.
Coordinate distribution of the test/QA plan to NCSU staff.
Coordinate the filter pack sampling and analysis activities.
Review and approve all data and records related to sampling and analysis activities.
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A5 BACKGROUND
The ETV Program's AMS Center conducts third-party performance testing of commercially
available technologies that detect or monitor natural species or contaminants in air, water, and
soil. Stakeholder committees of buyers and users of such technologies recommend technology
categories, and technologies within those categories, as priorities for testing. Among the
technology categories recommended for testing are semi-continuous ambient air monitoring
systems.
Recent advancements in ambient air measurement instrumentation now provide the capability of
remote access to field instruments to monitor operating status and to allow real-time or near real-
time (within 24 hours) access to measurement data. The advantages of routine operation of such
systems include a much more timely data stream and improved air quality assessment capability.
Real-time, multi-pollutant monitoring in rural areas will help the EPA better characterize the
extent of regional transport of pollutants (i.e., particulate matter and gaseous precursors), provide
improved regional dry deposition estimates, and help in both the development and validation of
air quality models.
EPA's Clean Air States and Trends Network (CASTNET) currently performs ambient air
sampling of particles and selected gases by passing air at a controlled flow rate through an open
face, three-stage filter pack that used four sequential filters (Teflonฎ, Nylonฎ, and dual
Whatmanฎ filters impregnated with potassium carbonate). The filter packs are located at 10
meters from the ground surface and accessed using a tilt-down aluminum tower. The filter packs
are exchanged every week by a site operator and the exposed filter pack is shipped to a central
analytical laboratory for analysis. Although the filter pack is simple to use, reliable, inexpensive,
and provides sensitive measurements, it suffers from long sampling duration (7-day integrated
average) and is subject to bias and uncertainties in species of interest such as gaseous nitric acid
(HNOs) and particle nitrate (N(V) due to reactivity and volatilization issues (Allegrini, et al.,
1987; Sickles et al., 1990; Harrison and Kitto, 1990). In addition, preliminary concentration data
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from a particular network site are typically not available until 4-6 months from the sample
collection date.
The EPA is interested in identifying an advanced monitoring instrument that will meet the rigors
of long-term, routine environmental monitoring in remote locations (such as the CASTNET
program) and will provide high quality data on a more real-time basis. A multi-pollutant
monitoring approach will also allow for continued improvement in source apportionment
analyses and modeling which is necessary for determining the relative contributions of various
emission sources that influence atmospheric chemistry and air quality.
A6 VERIFICATION TEST DESCRIPTION AND SCHEDULE
The purpose of this verification test is to generate performance data on semi-continuous ambient
air monitoring technologies so organizations and users interested in installing and operating these
systems can be assured of their benefit. The test will be conducted over a period of
approximately 30 days and will involve the continuous operation of duplicate monitoring
systems at an existing ambient air monitoring station located near EPA laboratories in Research
Triangle Park, North Carolina. The accuracy of the monitoring systems will be determined
through comparisons to modified EPA methods for individual gaseous and particulate species.
Modifications to the methods primarily involve increasing the sampling flow rate to reduce
overall sampling times and help minimize measurement bias and uncertainties, while still
meeting the data quality objectives of this verification test. The precision of the monitoring
systems will be determined from comparisons of paired data from duplicate monitoring systems,
and through comparisons to pooled results of the reference methods. Other performance
parameters such as data completeness, maintenance requirements, ease of use, and operational
costs will be determined from observations by the Battelle field testing staff. This test is not
intended to simulate long-term performance of these technologies at a monitoring site.
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A6.1 Technology Description
In general, the monitoring systems to be tested consist of an ambient air sampler that provides
semi-continuous measurement of the concentrations of various gaseous and particulate phase
pollutants in ambient air. The monitoring system samples ambient air at a predefined flow rate
and subsequently removes water soluble gases from the air sample using a wetted rotating
denuder (WRD) and captures the solvated gases for analysis. The aerosol passes through the
WRD and is introduced to a steam jet aerosol collector that collects the aerosol in an aqueous
solution for subsequent analysis. Both aqueous solutions are collected for 1-hour sampling
periods and analyzed for the target analytes by an on-line ion chromatography (1C) system.
Specifically, the monitoring systems provide direct measurements for the following atmospheric
components:
Particle phase: sulfate (SC>42"),
nitrate (NO3")
ammonium (NH4+)
chloride (Cl')
potassium (K+)
magnesium (Mg2+)
calcium (Ca2+)
sodium (Na+)
Gas phase: sulfur dioxide (802)
nitric acid (HNO3)
ammonia (NH3)
Concentrations of these analytes are subsequently determined from the liquid concentrations and
the sampled air volume over the collection period.
A6.2 Verification Test Description and Schedule
This verification test will involve the evaluation of duplicate semi-continuous ambient air
monitoring systems under realistic operating conditions at an existing ambient air monitoring
station. The monitoring systems will be operated continuously for 30 days, during which time a
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series of reference method samples will be collected. Each day during the test period, duplicate
integrated denuder/filter pack reference samples will be collected over successive 12-hour
periods. Thus, over the 30-day field period, a total of 120 denuder/filter pack samples will be
collected during the 60 12-hour sampling periods. The samples will be analyzed for the target
analytes by ion chromatography (1C), inductively coupled plasma atomic emission spectroscopy
(ICP-AES), and automated colorimetry (AC) and will serve as the primary reference method for
comparisons to the monitoring systems being tested. In addition, continuous gas analyzers for
SC>2 and NHs will be collocated with the monitoring systems being tested and used as secondary
reference method measurements for comparisons to the monitoring systems. Results from the
monitoring systems will be compared to the corresponding results from these gas analyzers to
assess the short term (e.g., 1-hour) accuracy of the monitoring systems.
Table 1 shows the planned schedule of testing and data analysis/reporting activities to be
conducted in this verification. The verification field test is planned to begin in September 2008
and be completed in October 2008. The period of operation of the monitoring systems at the air
monitoring site will be 30 days, with routine operation expected to begin on September 29 and
continue until October 29, 2008, or until all testing activities are completed. During testing,
duplicate denuder/filter pack reference samples will be collected twice each day, with each
sampling period covering 12 hours.
Table 1. Planned Verification Test Schedule
Date(s)
September 29-
October 29
November 15
December 1
December 15
December 31
Testing Activities
Routine operation
Reference sampling periods
Remove monitoring systems from test site
Analysis of reference samples
Complete analysis of reference samples
Data Analysis and Reporting
Prepare report template
Review and summarize field testing staff
observations
Compile data from monitoring systems
Begin draft report(s)
Perform data analysis
Continue preparation of draft report(s)
Complete draft report(s)
Complete review of draft report(s)
Revise draft report(s)
Submit final report(s) for EPA approval
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Subsequent to the verification test, a verification report will be drafted for the monitoring system
tested. This report will be reviewed by the vendor and by peer reviewers, and submitted to EPA
for final signature. In performing the verification test, Battelle will follow the technical and QA
procedures specified in this test/QA plan and will comply with the data quality requirements in
the AMS Center QMP.2
A6.3 Test Facility
The Burdens Creek Air Monitoring Site is located near EPA's campus in Research Triangle
Park, NC. This monitoring station is an operational site with ongoing ambient air monitoring
performed by EPA. The site includes six environmentally controlled double-wide trailers that
serve as shelters for the monitoring equipment and as work space for the site staff. The site also
serves as a test facility for evaluation of environmental monitoring equipment.
A7 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The objective of this verification test is to evaluate the performance of the semi-continuous
ambient air monitoring systems under realistic operating conditions. This evaluation will in part
assess the capabilities of the monitoring systems for determining the ambient concentrations of a
variety of common ambient air pollutants through comparisons to collocated reference samples
collected during the verification test period. Additionally, this evaluation will rely upon
observations to assess other performance characteristics of the monitoring systems being tested.
To ensure that these monitoring systems are suitable for use in CASTNET, EPA has established
a set of performance goals for accuracy, precision, data completeness, and instrument reliability.
The data quality objectives of this verification test must be sufficient to ensure that an
assessment of the performance of these monitoring systems can be made relative to these goals.
Below is a discussion of the EPA performance goals, the data quality objectives (DQOs) and the
criteria for measurement data that have been established to assure that the objectives of this test
are met.
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A7.1 CASTNET Performance Goals
Table 2 presents the performance goals that EPA has established for semi-continuous ambient air
monitoring systems for use in CASTNET.
Table 2. Performance Objectives for CASTNET Semi-Continuous Ambient Air Monitoring Systems
Goal
Accuracy Goal 1
Accuracy Goal 2
Accuracy Goal 3
Accuracy Goal 4
(If the instrument
does not meet
Accuracy Goal 3)
Precision Goal 1
Precision Goal 2
Completeness
Goal 1
Completeness
Goal 2
Reliability
Goal 1
Reliability
Goal 2
Reliability
Goal 3
Analytes
SO2, HNO3, NH3,
SO4 , NO3", and
NH4+
SO2, HNO3, NH3,
SO42", NO3", and
NH4+
SO2, HNO3, NH3,
SO42", NO3", and
NH4+
SO2 HNO3, NH3,
SO4 , NO3", and
NH4+
SO2 HNO3, NH3,
SO4 , NO3", and
NH4+
SO2 HNO3, NH3,
SO4 , NO3", and
NH4+
SO2, HNO3, NH3,
SO4 , NO3", and
NH4+, Na+, Ca+,
and CI"
SO2 HNO3, NH3,
SO4 , NO3", and
NH4+, Na+, Ca+,
and CI"
Instrument
measurement
mode
Power
failure
tolerance
Operator
attendance
Description
Slope (m) of linear regression by least-squares
method of mean value of reference measurements
paired with measurement of each instrument. All
data with mean reference values below 2 times the
instrument detection limit (IDL) are excluded.
Intercept (b) of linear regression by least-squares
method of mean value of reference measurements
paired with measurement of each instrument. All
data with mean reference values below 2 times the
IDL are excluded.
The median absolute relative percent differences
(MARPD) between the mean value of reference
measurements paired with measurement of each
instrument.
Perform Wilcoxon matched pairs test to determine if
the failure to achieve Accuracy Goal 3 is due to
expected measurement variation. The ratio of
observed differences in the two data sets (i.e.,
reference and instrument) to expected random
differences in the same two data sets.
MARPD between paired instrument measurements.
All data with mean instrument values below 2 times
the IDL are excluded.
Median absolute relative percent difference between
paired instrument measurements (RPDo.s) is less
than the 95th percentile of the pooled RPD of the
reference method (RPDREFo.95 ).
Percentage of test period for which valid data, as
indicated by the instrument, is available within 24
hours of collection.
Completeness of data record for comparison with
reference measurements for each test period, when
detected by reference measurements (i.e., hours of
valid measurements for each valid reference
measurement period).
Percentage of time instrument is in measurement
mode for test period
In the event of a power failure the instrument has
sufficient back-up power to perform a controlled
shutdown, restarts, and instrument returns to
measurement mode within 4 hours after power has
returned.
Average number of site visits per week required to
keep instrument operating.
Target
0.80 < m < 1.20
-10 ppb < b < 10 ppb
MARPD < 40%
p-value < 0.05
MARPD < 25%
RPDo.5 ^ RPDREFO.95
Tvalid > 80%
TReference ^ 80%
TMeasurement ^ 90%
Yes/No
N<2
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A7.3 Data Quality Objectives
The DQOs for this verification test were established based on the assessing the performance of
the monitoring systems relative to EPA's performance goals. In order to provide a suitable
benchmark for comparison, the reference samples must meet the performance goals established
for the monitoring systems being evaluated. Thus, the DQOs for this verification test include
objectives for reference method accuracy and precision, as well as data completeness for the
reference method sample collection and analysis. The DQOs are quantitatively defined in Table
3 in terms of specific data quality indicators (DQIs) and their acceptance criteria.
Table 3. DQIs and Criteria for Critical Measurements for Reference Methods.
Measurement
Filter pack flow rate
Inorganic ion analysis
(1C)
Metal ion analysis
(ICP-AES)
Ammonia analysis
(AC)
Analyte Detection
DQI
Accuracy
Precision
Accuracy
Precision
Accuracy
Precision
Accuracy
Precision
Detection
limit
Method
Comparison to NIST traceable flow transfer
standard
Comparison to NIST traceable flow transfer
standard
Analysis of standard reference material
Analysis of duplicate samples
Analysis of standard reference material
Analysis of duplicate samples
Analysis of standard reference material
Analysis of duplicate samples
Measured concentration greater than twice the
detection limit
Criteria
ฑ5%
ฑ10%
ฑ5%
MARPD < 20%
ฑ5%
MARPD < 20%
ฑ10%
MARPD < 20%
>80%
Typical reporting limits for the analytical techniques are provided in Table 4 along with the
corresponding ambient air detection limits and typical ambient concentrations of the target
analytes expected during testing.
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Table 4. Reporting Limits for Analytical Methods with Corresponding Ambient Air
Detection Limits and Approximate Ambient Concentrations Expected During
Testing.
Analyte
NO3"
SO42"
cr
Na+
K+
Mg2+
Ca2+
NH4+
Analytical
Method
1C
1C
1C
ICP-AES
ICP-AES
ICP-AES
ICP-AES
AC
Reporting Limit
0.008 mg-N/L
0.040 mg/L
0.020 mg/L
0.005 mg/L
0.005 mg/L
0.003 mg/L
0.003 mg/L
0.020 mg-N/L
Ambient Air Detection
Limit (|ig/m3)
0.03
0.1
0.07
0.02
0.02
0.01
0.01
0.07
Expected
Concentration (M,g/m3)
~~"~)
^
4
-0.5
-0.1
-0.1
-0.1
-0.1
-1.5
Additionally, the verification test relies in part on observations of the Battelle field testing staff
for assessment of the performance of the monitoring systems being tested. The requirements for
these observations are described in the discussion of documentation requirements and data
review, verification, and validation requirements for this verification test.
The quality of the reference method measurements will be assured by adherence to these DQI
criteria and the requirements of the reference methods including the calibration and QA/QC
requirements of those methods, which are discussed in detail in Sections B2-B7 of this test/QA
plan. Calibration standards and QC samples must meet National Institute of Standards and
Technology (NIST) traceability, when available. The quality of the reference method
measurements will be monitored by inclusion of blank samples and performance evaluation (PE)
samples as appropriate. Section Cl.l presents a description of the PE audit samples/
measurements to be performed and the acceptance criteria for those measurements.
The Battelle Quality Manager or his designee will perform a technical systems audit (TSA) at
least once during this verification test to augment these QA/QC requirements. This TSA will be
performed within the first week of the verification test. The EPA Quality Manager also may
conduct an independent TSA, at her discretion.
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AS SPECIAL TRAINING/CERTIFICATION
Documentation of training related to technology testing, field testing, data analysis, and reporting
is maintained for all Battelle technical staff in training files at their respective locations. The
Battelle Quality Manager may verify the presence of appropriate training records prior to the
start of testing. Battelle technical staff supporting this verification test have a minimum of a
bachelor's degree in science/engineering. The Verification Test Coordinator has a Ph.D. in
Physical Chemistry and has approximately 10 years of experience performing ETV verification
tests.
A9 DOCUMENTATION AND RECORDS
The records for this verification test may include the test/QA plan, chain-of-custody forms,
laboratory record books (LRB), data collection forms, electronic files (both raw data and
spreadsheets), and the final verification report(s). All of these records will be maintained at the
test facility or in the Verification Test Coordinator's office during the test and may be transferred
to permanent storage at Battelle's Records Management Office (RMO) at the conclusion of the
verification test. All Battelle LRBs are stored indefinitely, either by the Verification Test
Coordinator or Battelle's RMO. EPA will be notified before disposal of any files. The
documentation and results of the reference method measurements made by NCSU will be
submitted to Battelle within 10 days after completion of all sample analyses, review of the data,
and calculation of analyte concentrations in the ambient air. Section BIO further details the data
recording practices and responsibilities.
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SECTION B
MEASUREMENT AND DATA ACQUISITION
Bl EXPERIMENTAL DESIGN
This test will specifically address verification of semi-continuous ambient air monitoring
systems by evaluating the accuracy and precision of the monitoring systems, as well as data
completeness, reliability, and maintenance needs of each monitoring system. Relative accuracy
and precision will be determined for the monitoring systems by comparison of their results to
concentration measurements from the denuder/filter pack reference samples, and secondarily to
the continuous gas measurements made during testing. Precision will also be assessed through
comparison of paired results from the duplicate monitoring systems. Data completeness will be
assessed as the percentage of maximum data return that is achieved by the monitoring systems
over the test period. Reliability and maintenance needs will be evaluated by means of
observations by field testing staff, and records of needed maintenance, vendor activities, and
expendables used.
Bl.l Test Procedures
During testing, duplicate semi-continuous ambient air monitoring systems will be installed inside
an environmentally controlled shelter at the Burdens Creek Air Monitoring Site. The monitoring
systems will be operated and maintained by the vendors, and are intended to operate
continuously over the 30-day testing period. Any maintenance of the monitoring systems will be
performed by the vendor and will be documented by Battelle. Data from the monitoring systems
will be retrieved by the vendor and provided to Battelle within 24 hours of collection.
Integrated denuder/filter pack reference samples will be collected over 12-hour sampling periods
throughout the testing period. The denuder/filter pack samples will be collected from 6:00 a.m.
to 6:00 p.m. and from 6:00 p.m. to 6:00 a.m. daily. The monitoring systems will be collocated
with separate continuous gas analyzers for 862 and NHs, which will be operated and maintained
by EPA staff throughout the testing period.
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The denuder/filter pack assemblies used for this test will consist of a sodium carbonate (Na2CO3)
coated denuder and phosphorous acid (H3PO3) coated denuder in series for the collection of acid
and base gases, respectively, followed by a Teflon filter for the collection of particulate matter, a
Nylon filter for the collection of volatilized parti culate nitrate, and a H3PO3 coated denuder
"chaser" for the collection of volatilized parti culate ammonium. The denuder/filter pack samples
will be installed on the roof of the trailer housing the monitoring systems being tested and will
collect ambient air samples at a flow rate of 10 L/min through a standard "candy cane" inlet.
The denuder/filter pack samples will be retrieved and returned to the analytical laboratory for
disassembly, extraction, and analysis. After disassembly in the laboratory, the filters and
denuders will be extracted using deionized water and analyzed for target analytes. The denuder
extracts will be analyzed for SO2 (as SO42"), HONO (as NO2"), HNO3 (as NO3"), NH3 (as NH4+),
and HC1 (as Cl"). The Teflon filter extracts will be analyzed for SO42", NO3", NH4+, Cl", Ca2+,
Mg2+, Na+, and K+. The Nylon filter extracts will be analyzed for NO3", and the backup denuder
chaser extracts will be analyzed for NH4+. Analysis for SO42", NO3", and Cl" will be performed
by 1C based on the procedures described in EPA Method 300.0. Analysis for Ca2+, Mg2+, Na+,
and K+ will be performed by ICP-AES based on the procedures described in EPA Method
6010B. Analysis for NH4+ will be performed by automated colorimetry (AC) based on the
procedures described in EPA Method 350.1.
Bl.1.1 Accuracy
The accuracy of the monitoring systems will be evaluated in two ways for each of the target
analytes (SO2, HNO3, HONO, HC1, NH3, SO42', NO3', Cl', NH4+, and metal cations).
Firstly, the accuracy will be determined from a linear least squares regression analysis of the
measured concentrations of the target analytes determined from the monitoring systems and the
corresponding reference methods. For comparison to the denuder/filter pack reference samples,
average concentrations from each of the two monitoring systems will be determined separately
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for each of the 12-hour sampling periods during the testing period, by averaging the 1-hour
results over the corresponding sampling periods. For each of the duplicate monitoring systems,
these averages will then be plotted separately against the mean of the corresponding duplicate
reference method measurements. The slope and intercept of these plots will be determined from
a linear regression analysis and reported independently for each of the duplicate monitoring
systems, and for each target analyte. For the continuous gas measurements (SC>2 and NH3), 1-
hour average concentration readings from each monitoring system will be plotted against the
corresponding 1-hour average reference measurements, excluding data below twice the
instrument detection limit. Again, the slope and intercept of these plots will be determined from
a linear regression analysis and reported independently for each of the duplicate monitoring
systems.
Additionally, accuracy will be determined from the median absolute relative percent difference
(MARPD) between the mean value of the reference measurements and each monitoring system
being tested for each target analyte. The MARPD of the monitoring systems will be calculated as
the median value of the ARPD results determined using Equation 1:
C(ref),
where Ct and C(ref}i are the average target analyte concentration measured by the monitoring
systems and the mean of th
reference sampling period.
systems and the mean of the duplicate reference method concentrations, respectively, for the ith
If either of the duplicate monitoring systems fail to meet the EPA performance goal stated in
Table 2, a Wilcoxian matched pairs test will be performed to determine if the failure is the result
of expected measurement variation.
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Bl.1.2 Precision
Precision will be assessed in two ways for the monitoring systems. Firstly, precision will be
determined based on a comparison of paired measurements from the duplicate monitoring
systems being tested. For this assessment of precision, the MARPD between the paired
measurements from the duplicate monitoring systems will be calculated as the median value of
the ARPD values determined using Equation 2:
ARPD= |CO),-(C2), (2)
where C(l)t and C(2)t are the target analyte concentration measured by the first and second of the
two duplicate monitoring systems. For this calculation, measurement data below twice the
instrumental detection limit will be excluded from the analysis.
Additionally, precision will be assessed through comparisons of the MARPD to the 95th
percentile of the pooled relative percent difference of the duplicate reference method
measurements.
Bl.1.3 Data Completeness
Data completeness will be assessed in two ways, based on the overall data return achieved by
each monitoring system during the testing period. For each of the duplicate monitoring systems,
this calculation will use the total hours of apparently valid data reported by the monitoring
systems and available within 24 hours, divided by the total hours of data in the entire field
period. Also, the number of hours of valid monitoring system data will be assessed relative to
the number of hours in each reference method sampling period. The performance goals for both
of these measures of data completeness are > 80%. The causes of any substantial incompleteness
of data return will be established from operator observations or vendor records, and noted in the
discussion of data completeness results.
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Bl. 1.4 Reliability
Instrument reliability will be assessed in two ways. Firstly, reliability will be assessed in terms
of the percentage of time that the monitoring systems operate in measurement mode over the
duration of the test period. Additionally, reliability will be assessed in terms of the ability of the
instruments to perform a controlled shut-down in the case of a power failure, followed by an
automated return to measurement mode within 4 hours after power has been restored. For this
assessment, the testing staff will impose a temporary power outage at the test site and monitor
the performance of the duplicate monitoring systems during and after the power outage. These
assessments will be reported independently for the duplicate monitoring systems.
Bl. 1.5 Operational Factors
Operational factors such as maintenance needs, data output, consumables used, ease of use,
repair requirements, etc., will be evaluated based on observations recorded by Battelle and
facility staff, and explained by the vendor as needed. Battelle staff will be at the monitoring site
whenever the vendor is present and will record all activities performed on the monitoring
systems. A laboratory record book will be maintained at the test site, and will be used to enter
daily observations on these factors. Examples of information to be recorded in the record books
include the daily status of diagnostic indicators for the monitoring systems; use or replacement of
any consumables; the effort or cost associated with maintenance or repair; vendor effort (e.g.,
time on site) for repair or maintenance; the duration and causes of any down time or data
acquisition failure; and Battelle testing staff observations about ease of use of the monitoring
systems. These observations will be summarized to aid in describing monitoring system
performance in the verification report.
B1.3 Reporting
The statistical comparisons described above will be conducted separately for each target analyte
for each duplicate monitoring systems being tested, and information on the operational
parameters will be compiled and reported. A verification report will be prepared for each
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monitoring system tested, that presents the test procedures and test data, as well as the results of
the statistical evaluation of those data.
Operational aspects of the monitoring systems will be recorded by Battelle testing staff at the
time of observation during the field test, and summarized in the verification report. For example,
descriptions of the data acquisition procedures, use of vendor-supplied proprietary software,
consumables used, repairs and maintenance needed, and the nature of any problems will be
presented in the report. The verification report will briefly describe the ETV program, the AMS
Center, and the procedures used in verification testing. The results of the verification test will be
stated quantitatively, and will compare the results to the stated EPA performance goals. Each
draft verification report will be subjected to review by the vendor, EPA, and other peer
reviewers. The review comments will be addressed in a subsequent revision of the report, and
the peer review comments and responses will be tabulated to document the peer review process.
The reporting and review process will be conducted according to the requirements of the
ETV/AMS Center QMP.2
B2 SAMPLING METHOD REQUIREMENTS
Continuous gas analyzers and denuder/filter pack sampling will be performed to provide
reference method measurements. The denuder/filter pack reference samples will be collected by
NCSU as described above (Section B 1.1.1) and will serve as the primary reference method
measurement. The denuder/filter pack assemblies to be used for this verification are similar to
those used in CASTNET and will sample ambient air at a flow rate of 10 liters per minute
(L/min). The samples will be collected from the roof of the same trailer at the monitoring site
that houses the monitoring systems being tested. A standard candy cane sampling inlet will be
used to prevent liquid water from being drawn into the sample stream. A 2.5|j,m cyclone inlet
will be use to limit the size of particles in the sample stream to less than an aerodynamic
diameter of 2.5|j,m.
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Separate gas analyzers will used to measure SO2 and NH3. NH3 concentrations will be measured
with a dual-cell Nitrolux 200 photoacoustic spectrometer (Pranalytica, Inc., Santa Monica, CA).
Briefly, this method employs a modulated CC>2 laser in a line-switching configuration to excite
NH3 molecules at a wavelength of 10.784 jim (Pushkarsky et al., 2003). NH3 absorbs the IR
radiation and releases the energy to the surrounding air stream through collisional deactivation
with molecules of C>2 and N2. The resulting periodic localized heating generates a pressure wave
at the laser modulation frequency. This acoustic wave is monitored with a sensitive microphone
and the magnitude of the resulting photoacoustic signal is proportional to the number density of
NH3 molecules. Sample flow is pulled continuously through each measurement cell at a rate of
approximately 1.2 Lpm and the photoacoustic signal is integrated for 12 s. NH3 concentrations
are determined simultaneously in each detection cell. 12s data will be averaged accordingly for
comparison to the hourly data of the monitoring systems being tested and the 12-hour integrated
reference samples. The Nitrolux 200 will be configured such that Cell 1 samples from a tee at
the denuder inlet of a third monitoring system, to be operated by EPA under the same sampling
conditions (inlet physical dimensions, inlet flow rate, tubing length, tubing internal diameter,
tubing length, and sample flow rate) as for the duplicate monitoring systems being evaluated.
Cell 2 will sample from a point collocated with the inlet of the monitoring system through a
heated (50 ฐC) length of Vi" outer diameter PTFE tubing at a flow rate of 16.7 Lpm. This
configuration allows for examination of the potential effects of the monitoring system sampling
(tubing, inlet, flow rate) on NH3 response time. The photoacoustic instrument will be multipoint
calibrated (0 to 25 ppb) at the beginning and end of the demonstration period by diluting 10 ppm
NH3 (balance N2) (Scott Specialty Gases, Plumsteadville, PA) with humidified zero air.
862 concentrations will be measured using a continuous ultraviolet (UV) fluorescence analyzer.
Briefly, the method for the measurement of 862 is based on the principle that 862 molecules
absorb UV light at one wavelength and emit UV light at a different wavelength. This process is
known as fluorescence, and involves the excitation of the SC>2 molecule to a higher energy
electronic state by light absorption. Once excited, the molecule decays non-radiatively to a
lower energy electronic state from which it then decays to the original, or ground, electronic state
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by emitting a photon of light at a longer wavelength (i.e., lower energy) than the original
excitation light. The emitted light is detected and is proportional to the number density of the
SC>2 molecules. The SC>2 analyzer will sample through an independent sampling line in the
proximity of the monitoring systems being tested. The calibration of the SC>2 analyzer and the
on-going QC activities for this analyzer will be performed by EPA, and will be subject to the
calibration and QC requirements for continuous SC>2 analyzers.
Independent audits of denuder/filter pack sampling procedures will be carried out by Battelle as
part of the technical systems audit procedure (Section C1.2) and the performance evaluation
audit procedure (Section Cl.l).
B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Sample handling procedures are designed to minimize handling of the denuder/filter pack
components and limit the number of transfers of the denuder/filter packs. When not in use, the
denuders and assembled filter packs will be sealed or capped, to prevent contamination. Clean
lint-free gloves will be used when handling the denuder/filter pack components. Clean forceps
will be used when handling filters. The denuders and filter packs will be assembled in NCSU's
analytical laboratory facilities and transferred by NCSU staff to the Burden's Creek Air
Monitoring Site for sampling. Special care will be taken to avoid breathing on components of
the denuder/filter pack reference samples.
The collected 12-hour denuder/filter pack reference samples will be recovered twice weekly
from the sampling trains and transported to NCSU for disassembly, extraction, and analysis. The
sample fractions from each denuder/filter pack will include the following:
. Na2CO3 coated denuder
. HaPOs coated denuder
. Teflon filter
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Each fraction of each sample collected will be uniquely labeled and will be extracted separately
within 48 hours of receipt in the laboratory. During extraction each denuder will be capped on
one end, a measured aliquot (10 mL) of deionized water will be added to the open end of the
denuder and then it will be capped. The capped denuders will be slowly rotated to facilitate
complete extraction of the target analytes, and the extract will be poured into a clean vial and
placed in a refrigerated storage at -4ฐ C. Filter samples will be removed from the filter pack
holders and placed into separate vials with measured aliquots (5 mL) of deionized water for
extraction. The labeled vials will be capped and placed in a refrigerated storage at -4ฐ C. The
stored samples will be analyzed within 15 days of extraction.
All reference method samples will be in the custody of NCSU from sample collection through
sample recovery and analysis. Sample custody will be documented throughout sample
preparation, sample collection, sample recovery, and sample analysis, using standard chain-of-
custody forms. Each chain-of-custody form will be signed by the person relinquishing samples
once that person has verified that the chain-of-custody form is accurate. Upon receipt at the
laboratory, chain-of-custody forms will be signed by the person receiving the samples once that
person has verified that all samples identified on the chain-of-custody forms are present in the
shipping container. Any discrepancies will be noted on the form and the sample receiver will
immediately contact the NCSU technical lead to report missing, broken, or compromised
samples. Copies of all chain-of-custody forms will be delivered to the Verification Testing
Coordinator upon request, and maintained with the test records.
B4 ANALYTICAL METHOD REQUIREMENTS
Analysis of the reference method samples will be performed by 1C, ICP-AES, or AC as shown in
Table 5. The analysis will be performed based on the requirements of the methods indicated.
All QA/QC procedures specified in each method will be followed.
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Table 5. Summary of Target Analytes and Sample Analytical Methods
Fraction
Na2CO3 denuder
H3PO3 denuder
Teflon filter
Teflon filter
Nylon filter
H3PO3 denuder chaser
Analytes Analytical Technique
SO2 (as SO42-)
HONO (as NO2 )
HNO3 (as NO3 )
HC1 (as Cl")
NH3 (as NH4+)
SO42 , NO3 , NH4+, Cl
Ca2+, Mg2+, Na+, K+
NO3
NH4+
1C
AC
1C
ICP-AES
1C
AC
Method
Method 300.0
Method 3 5 0.1
Method 300.0
Method 601 OB
Method 300.0
Method 3 5 0.1
B5 QUALITY CONTROL REQUIREMENTS
As described in Section A7, reference method sampling will be carried out using denuder/filter
packs and continuous gas analyzers. A variety of quality control activities will be performed to
ensure the data quality of the reference methods. Specific quality control activities include
calibration of the gas analyzers and denuder/filter pack sampling equipment, calibration of the
analytical instrumentation, calibration checks, and analysis of duplicate samples and field blanks.
The following sections describe the quality control activities and acceptance criteria for the gas
analyzers, the denuder/filter pack sampling, and the denuder/filter pack sample analysis.
B5.1 Denuder/Filter Pack Sampling
Quality control activities for the filter pack sampling include flow rate checks (Section B7.1)
performed on the sampling trains and the collection of field blank samples. Prior to each
sampling event, each sampling train will be checked for leaks to ensure proper operation.
At least 10% of all samples collected will be field blanks. The field blanks will be collected by
installing the sampling media (i.e., denuder and filters) in the sampling train but without drawing
any air through the train. The media will then be recovered and handled like normal samples. If
contamination levels are greater than twice the instrumental detection limit the reference samples
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collected since the previously acceptable field blank sample will be flagged and the cause of the
contamination will be investigated.
B5.2 Denuder/Filter Pack Sample Analysis
The analysis of the denuder/filter pack samples will be conducted by 1C based on EPA Method
300.0, by ICP-AES based on EPA Method 6010B, and by AC based on EPA Method 350.1.
Analysis of these samples will be subject to the data quality criteria of the respective methods,
which include the analysis of blanks and calibration check standards with every batch of samples
analyzed by the different analytical methods. Table 6 summarizes the quality control
requirements of those three methods. If the sampling or analytical performance strays outside
the required tolerances, the relevant QC checks will be conducted again or the relevant QC
samples will be prepared again and reanalyzed. If performance problems persist, the reference
instrument will be recalibrated, and/or affected samples will be reanalyzed. Reference sample
results not meeting the requirements will be excluded from comparison to the continuous
monitor results.
Table 6. QC Checks for Analytical Methods
Measured
Parameter
Range
Accuracy
Accuracy
Accuracy
Precision
Detection limit
QC Check
Multipoint calibration
(daily when analysis is performed)
Multipoint calibration
(daily when analysis is performed)
Analysis of calibration check standard
(every 20th sample)
Analysis of standard reference material
sample
(every 20th sample)
Analysis of duplicate samples
(every 20th sample)
Analysis of method blank sample
(every 20th sample)
Required Performance
Concentrations must bracket range of all
sample concentrations (All methods)
r^> 0.995 (Method 300.0)
ฑ 5% of actual value (Method 300.0,
Method 601 OB)
ฑ 10% of actual value (Method 350.1)
ฑ 5% of actual value (Method 300.0,
Method 601 OB)
ฑ 10% of actual value (Method 350.1)
RPD ฑ 20% (All methods)
< 2 times the reporting limit (All methods)
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B5.3 Gas Analyzers
The continuous gas analyzers to be used for this verification test are currently in use at the
Burdens Creek site and are included in routine QC activities at the site. Quality control activities
associated with the SC>2 continuous gas analyzers include multipoint calibrations of the
analyzers, routine zero/span checks, and biweekly precision checks. A multipoint calibration of
the NH3 continuous gas analyzer will be performed before and after the verification test. No
additional QC activities will be implemented for this verification test although documentation of
the QC activities performed during testing will be provided to Battelle by EPA.
B6 INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
The equipment used for the reference method sampling and analysis will be tested, inspected,
and maintained so as to meet the data quality objectives of this verification test. System
preventive maintenance will be performed prior to the start of the verification test and of each
sampling period as needed. All major components will be checked to ensure operability and
repaired when required. Laboratory equipment maintenance is conducted as recommended by
the manufacturer on an as-needed basis. The pressure drop over the denuder/filter pack samples
will be recorded daily to ensure proper operation. If the pressure drop is found to be out of the
acceptable range corrective action will be taken as needed.
B7 INSTRUMENT CALIBRATION AND FREQUENCY
B7.1 Denuder/filter Pack Sampling Calibration
The calibration requirements for the denuder/filter pack sampling trains include a single point
flow rate calibration at the nominal flow rate using a NIST-traceable flow transfer standard (e.g.,
dry gas meter). This calibration will be performed at the beginning of the verification test with
flow checks performed no less frequently than once per week throughout the verification test.
Flows will be adjusted if measured flows are found to differ from the nominal flow rate by more
than 5% (i.e. acceptable flow range of 9.5 - 10.5 L/min).
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B7.3 Analytical Instrumentation Calibration
Prior to sample analysis, a calibration of the analytical instrumentation must be conducted
according to the respective EPA Methods. Also, calibration checks will be conducted each day
that sample analysis is performed (Section B.5.2).
B7.4 Gas Analyzer Calibration
Multipoint calibrations of the gas analyzers for the 862 and NHs measurements must be done
within six months prior to the start of the verification test. Additional calibrations should be
conducted if any of the following conditions occur:
Span check difference exceeds 15%
After any significant maintenance activities are conducted on the analyzer
Measured concentration values during direct comparison audit differ from the
certified standard values by ฑ15%.
The analyzers will be calibrated in-situ without disturbing the normal sampling inlet system to
the degree possible.
The multipoint calibration includes at least four points (three spaced over the expected range and a
zero point). The responses of the analyzers will be analyzed by linear regression to assess the
results of the calibration. The acceptance criteria for the linear regressions are: slope, 1 ฑ0.10;
intercept, zero ฑ0.010 ppm; correlation coefficient (r), > 0.995.
B8 INSPECTION/ACCEPTANCE OF SUPPLIES AND CONSUMABLES
Upon receipt of any supplies or consumables used for the denuder/filter pack reference method,
the NCSU staff will visually inspect and ensure that the materials received are those that were
ordered and that there are no visual signs of damage that could compromise the suitability of the
materials. If damaged or inappropriate goods are received they will be returned or disposed of
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and arrangements will be made to receive replacement materials. Certificates of analysis (COA)
or other documentation of analytical purity will be checked for all gases, reagents, and standards
to ensure suitability for this verification test. Unsuitable materials will be returned or disposed of
and arrangements for the receipt of replacement materials will be made.
B9 NON-DIRECT MEASUREMENTS
No non-direct measurements will be used during this verification test.
BIO DATA MANAGEMENT
Various types of data will be acquired and recorded electronically or manually by Battelle,
vendor, and NCSU staff during this verification test. All data will be recorded in permanent ink.
Corrections to records will be made by drawing a single line through the entry to be corrected
and providing a simple explanation for the correction, along with a date and the initials of the
person making the correction. Table 7 summarizes the types of data to be recorded. All
maintenance activities, repairs, calibrations, and operator observations relevant to the operation
of the monitoring systems being tested will be documented by Battelle or vendor staff in the
laboratory record book (LRB).
Results from the denuder/filter pack reference methods will be compiled by NCSU staff in
electronic format, and submitted to Battelle in the form of an analytical report at the conclusion
of reference sample analyses.
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Table 7. Summary of Data Recording Process
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Data to Be Recorded
Dates, times, and
details of test events
Monitoring system
calibration information,
maintenance, down
time, etc.
Monitoring system
readings
Continuous gas
analyzer measurement
results
Reference method
procedures,
calibrations, QA, etc.
Reference method
analysis results
Where
Recorded
ETV LRBs, field
sampling records
ETV LRBs, or
electronically
Recorded
electronically by
each monitor and
then downloaded
to computer daily
Electronically
from continuous
gas analyzers
ETV LRBs, or
data recording
forms
Electronically
from analytical
method
How Often
Recorded
Start/end of test
event
When
performed
Recorded
continuously by
each monitoring
system
Recorded
continuously by
analyzers
Throughout
sampling and
analysis
processes
Every sample
analysis
By Whom
Battelle and
NCSU
Vendor or
Battelle
Vendor for
transfer to
Battelle
EPA for
transfer to
Battelle
NCSU
NCSU
Disposition of Data
Used to
organize/check test
results; manually
incorporated in data
spreadsheets as
necessary
Incorporated in
verification report as
necessary
Converted to
spreadsheet for
statistical analysis
and comparisons
Converted to
spreadsheets for
calculation of
ambient air
concentrations, and
statistical analysis
and comparisons
Retained as
documentation of
reference method
performance
Converted to
spreadsheets for
calculation of
ambient air
concentrations, and
statistical analysis
and comparisons
Records received by or generated by any Battelle or NCSU staff during the verification test will
be reviewed by a Battelle staff member within two weeks of receipt or generation, respectively,
before the records are used to calculate, evaluate, or report verification results. If a Battelle staff
member generated the record, this review will be performed by a Battelle technical staff member
involved in the verification test, but not the staff member who originally received or generated
this verification test will be compiled and reported independently for each monitoring system.
the record. The review will be documented by the person performing the review by adding
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his/her initials and date to the hard copy of the record being reviewed. In addition, any
calculations performed by Battelle or NCSU staff will be spot-checked by Battelle technical staff
to ensure that calculations are performed correctly. Calculations to be checked include any
statistical calculations described in this test/QA plan. The data obtained from
Among the QA activities conducted by Battelle QA staff will be an audit of data quality. This
audit will consist of a review by the Battelle Quality Manager of at least 10% of the test data.
During the course of any such audit, the Battelle Quality Manager will inform the technical staff
of any findings and any immediate corrective action that should be taken. If serious data quality
problems exist, the Battelle Quality Manager will inform the AMS Center Manager who is
authorized to stop work. Once the assessment report has been prepared, the Verification Test
Coordinator will ensure that a response is provided for each adverse finding or potential
problem, and will implement any necessary follow-up corrective action. The Battelle Quality
Manager will ensure that follow-up corrective action has been taken.
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SECTION C
ASSESSMENT AND OVERSIGHT
Cl ASSESSMENTS AND RESPONSE ACTIONS
Every effort will be made in this verification test to anticipate and resolve potential problems
before the quality of performance is compromised. One of the major objectives of this test/QA
plan is to establish mechanisms necessary to ensure this. Internal quality control measures
described in this test/QA plan, which is peer reviewed by a panel of outside experts,
implemented by the technical staff and monitored by the Verification Test Coordinator, will give
information on data quality on a day-to-day basis. The responsibility for interpreting the results
of these checks and resolving any potential problems resides with the Verification Test
Coordinator. Technical staff have the responsibility to identify problems that could affect data
quality or the ability to use the data. Any problems that are identified will be reported to the
Verification Test Coordinator, who will work with the Battelle Quality Manager to resolve any
issues. Action will be taken to control the problem, identify a solution to the problem, and
minimize losses and correct data, where possible. Independent of any EPA QA activities,
Battelle will be responsible for ensuring that the following audits are conducted as part of this
verification test.
Cl.l Performance Evaluation Audit
A PE audit will be conducted within the first two weeks of testing to assess the quality of the
critical measurements associated with the reference sampling and analysis methods. Table 8
shows the critical measurements to be audited, with the audit procedures and acceptance criteria
for the audit comparisons. If the PE audit results do not meet the acceptance criteria shown, they
will be repeated. If the outlying results persist, a change in reference method instrument and a
repeat of the PE audit may be considered, and data will be flagged until the PE audit results are
acceptable. This audit will be performed once during the verification test, and will be the
responsibility of the Verification Test Coordinator or designee.
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Table 8. Methods and Acceptance Criteria for PE Audit Measurements
Critical Measurement
Denuder/filter pack sampling
flow rate
1C accuracy
ICP-AE accuracy
AC accuracy
PE Audit Method
Flow rate check with independent
NIST-traceable flow rate standard
Calibration checks with independent
NIST-traceable standards (SO42",
NCV, NH4+, CO
Calibration checks with independent
NIST-traceable standards (Ca2+,
Mg2+, Na+, K+)
Calibration check with independent
NIST-traceable standard ( NH4+)
Acceptance Criteria
ฑ 5% of nominal flow rate
ฑ 5% of actual concentration
ฑ 5% of actual concentration
ฑ 10% of actual concentration
The PE audit of the denuder/filter pack sampling flow rate will be conducted using an
independent NIST-traceable flow transfer standard. With the denuder/filter pack installed, the
flow rate through the sampling train will be measured and compared to the nominal flow rate.
The target criterion for this audit is agreement between the measured and nominal flow rate
within ฑ5%. If this criterion is not met, the cause of the problem will be investigated and
corrected if possible. Components of the sampling train will be replaced as necessary until the
flow rate criterion is met.
The PE audit of the analytical methods will be performed by supplying the analytical laboratory
with samples prepared from independent NIST-traceable standard solutions. These samples will
be analyzed and compared to the known sample concentrations. The acceptance criteria for this
audit include agreement between the measured and actual concentrations of within ฑ5% for the
1C and ICP-AE methods, and within ฑ10% for the AC method.
C1.2 Technical Systems Audits
The Battelle Quality Manager will perform a TSA at least once during this verification test. The
purpose of this audit is to ensure that the verification test is being performed in accordance with
the AMS Center QMP,2 this test/QA plan, published reference methods, and any SOPs used by
the test facility. In this audit, the Battelle Quality Manager, or designee, may review the
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reference methods used, compare actual test procedures to those specified or referenced in this
plan, and review data acquisition and handling procedures. In the TSA, the Battelle Quality
Manager will tour the test site; observe the reference method sampling and sample recovery;
inspect documentation of reference sample chain of custody; and review laboratory record
books. He will also check gas standard certifications and data acquisition procedures, and may
confer with the vendor, EPA, and NCSU testing staff. A TSA report will be prepared, including
a statement of findings and the actions taken to address any adverse findings. The EPA AMS
Center Project Officer and Quality Manager will receive a copy of Battelle's TSA report. At
EPA's discretion, EPA QA staff may also conduct an independent on-site TSA during the
verification test. The TSA findings will be communicated to technical staff at the time of the
audit and documented in a TSA report.
C1.3 Data Quality Audits
The Battelle Quality Manager, or designee, will audit at least 10% of the verification data
acquired in the verification test. The Battelle Quality Manager, or designee, will trace the data
from initial acquisition, through reduction and statistical comparisons, to final reporting. All
calculations performed on the data undergoing the audit will be checked.
C1.4 QA/QC Reporting
Each assessment and audit will be documented in accordance with Section 3.3.4 of the AMS
Center QMP.2 The results of the TSA will be submitted to EPA. Assessment reports will
include the following:
Identification of any adverse findings or potential problems
Response to adverse findings or potential problems
Recommendations for resolving problems
Confirmation that solutions have been implemented and are effective
Citation of any noteworthy practices that may be of use to others.
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C2 REPORTS TO MANAGEMENT
The Battelle Quality Manager, during the course of any assessment or audit, will identify to the
technical staff performing experimental activities any immediate corrective action that should be
taken. If serious quality problems exist, the Battelle Quality Manager will notify the AMS Center
Manager, who is authorized to stop work. Once the assessment report has been prepared, the
Verification Test Coordinator will ensure that a response is provided for each adverse finding or
potential problem and will implement any necessary follow-up corrective action. The Battelle
Quality Manager will ensure that follow-up corrective action has been taken. The test/QA plan
and final report are reviewed by EPA AMS Center quality assurance staff and the EPA AMS
Center program management staff. Upon final review and approval, both documents will then be
posted on the ETV website (www.epa.gov/etv).
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SECTION D
DATA VALIDATION AND USABILITY
Dl DATA REVIEW, VERIFICATION, AND VALIDATION REQUIREMENTS
The key data review and data verification requirements for this test are stated in Section BIO of
this test/QA plan. In general, the data review requirements specify that data generated during
this test will be reviewed by a Battelle technical staff member within two weeks of generation of
the data. The reviewer will be familiar with the technical aspects of the verification test but will
not be the person who generated the data. This process will serve both as the data review and the
data verification, and will ensure that the data have been recorded, transmitted and processed
properly. Furthermore, this process will ensure that the monitoring systems data and reference
method data were collected under appropriate testing conditions and that the reference sample
data meet the specifications of analytical methods.
The data validation requirements for this test involve an assessment of the quality of the data
relative to the DQIs and audit acceptance criteria specified for this test. The DQIs listed in
Section A7.3 will be used to validate the quality of the data. The QA audits described within
Section C of this document, including the performance evaluation audit and the audit of data
quality, are also designed to validate the quality of the data.
D2 VERIFICATION AND VALIDATION METHODS
Data verification is conducted as part of the data review as described in Section BIO of this
test/QA plan. A visual inspection of handwritten data will be conducted to ensure that all entries
were properly recorded or transcribed, and that any erroneous entries were properly noted (i.e.,
single line through the entry, with an error code and the initials of the recorder and date of entry).
Electronic data from the monitoring systems, continuous gas analyzers, and analytical equipment
used during the test will be inspected to ensure proper transfer from the datalogging system. All
calculations used to transform the data will be reviewed to ensure the accuracy and the
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appropriateness of the calculations. Calculations performed manually will be reviewed and
repeated using a handheld calculator or commercial software (e.g., Excel). Calculations
performed using standard commercial office software (e.g., Excel) will be reviewed by
inspection of the equations used for the calculations and verification of selected calculations by
handheld calculator. Calculations performed using specialized commercial software (i.e., for
analytical instrumentation) will be reviewed by inspection and, when feasible, verified by
handheld calculator, or standard commercial office software.
To ensure that the data generated from this test meet the goals of the test, a number of data
validation procedures will be performed. Sections B and C of this test/QA plan provide a
description of the validation safeguards employed for this verification test. Data validation
efforts include the completion of QC activities, and the performance of TSA and PE audits as
described in Section C. The data from this test will be evaluated relative to the measurement
DQIs described in Section A7.3, and the PE audit acceptance criteria given in Section Cl.l of
this test/QA plan. Data failing to meet these criteria will be flagged in the data set and not used
for evaluation of the monitoring systems, unless these deviations are accompanied by
descriptions of their potential impacts on the data quality.
An audit of data quality will be conducted by the Battelle Quality Manager to ensure that data
review, verification, and validation procedures were completed, and to assure the overall quality
of the data.
D3 RECONCILIATION WITH USER REQUIREMENTS
This purpose of this verification test is to evaluate the performance of semi-continuous ambient
air monitoring systems. In part, this evaluation will include comparisons of results from the
monitoring systems to the results from reference method samples generated from a well-
established EPA method for sample collection and analysis. To meet the requirements of the
user community, the reference data collected during this verification test will meet the QA
requirements of the reference methods. Additional performance data regarding operational
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characteristics of the monitoring systems will be collected by verification test personnel. To
meet the requirements of the user community, these data should include thorough documentation
of the performance of the monitoring systems during the verification test. The data review,
verification, and validation procedures described above will assure that data meeting these
requirements is accurately presented in the verification reports generated from this test, and will
assure that data not meeting these requirements will be appropriately flagged and discussed in
the verification reports.
This test/QA plan and the resulting ETV verification report(s) will be subjected to review by the
vendor, EPA, and expert peer reviewers. The reviews of this test/QA plan will assure that this
verification test and the resulting report(s) meet the needs of potential users of these monitoring
systems.
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SECTION E
REFERENCES
Allegrini, I, De Santis, F., Di Palo, V., Febo, A., C.,Possanzini, M., and Liberti, A. 1987.
"Annular Denuder Method for Sampling Reactive Gases and Aerosols in the Atmosphere."
Sci. Total Environment. Vol. 67, 1-16.
Battelle, Quality Management Plan for the ETV Advanced Monitoring Systems Center, Version
6.0, U.S. EPA Environmental Technology Verification Program, prepared by Battelle,
Columbus, Ohio, November 2005.
Harrison, R.M., Kitto, A.M.N. 1990. "Field Intercomparison of Filter Pack and Denuder
Sampling Methods for Reactive Gaseous and Paniculate Pollutants", Atmos. Environment
24A(10):2633-2640.
Pushkarsky, M.B., M.E. Webber and C.K.N. Patel. 2003. Ultra-sensitive ambient ammonia
detection using CO2-laser-based photoacoustic spectroscopy. Appl. Phys. B 77, 381-385.
Sickles, I.E., Hodson, L.L., McClenny, W.A., Paur, R.J., Ellestad, T.G. 1990. "Field Comparison
of Methods for the Measurement of Gaseous and Paniculate Contributors to Acidic Dry
Deposition." Atmos. Environ. 24A(01): 155-165.
U.S. EPA, Environmental Technology Verification Program Quality Management Plan,
EPA/600/R-03/021, U.S. Environmental Protection Agency, Cincinnati, Ohio, December
2002.
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