Bairene
The Business of Innovation
Environmental Technology
Verification Program
Advanced Monitoring
Systems Center
Test/QA Plan for Verification
of Cavity Ring-down Spectroscopy
Systems for Ammonia Monitoring
in Stack Gas
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TEST/QA PLAN
for
Verification of
Cavity Ring-down Spectroscopy Systems
For Ammonia Monitoring in Stack Gas
Version 1.0
June 24, 2009
Prepared by
Battelle
505 King Avenue
Columbus, OH 43201-2693
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SECTION A
PROJECT MANAGEMENT
Al VENDOR APPROVAL PAGE
ETV Advanced Monitoring Systems Center
Test/QA Plan for Verification of
Cavity Ring-down Spectroscopy Systems
For Ammonia Monitoring in Stack Gas
Version 1.0
June 24, 2009
APPROVAL:
Name
Company
Date
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A2 TABLE OF CONTENTS
Section Page
PROJECT MANAGEMENT 1
Al Vendor Approval Page 1
A2 Table of Contents 2
A3 Distribution List 3
A4 Verification Test Organization 4
A5 Background 10
A6 Verification Test Description and Schedule 12
A7 Quality Objectives and Criteria for Measurement Data 15
A8 Special Training/Certification 17
A9 Documentation and Records 18
MEASUREMENT AND DATA ACQUISITION 19
Bl Experimental Design 19
B2 Sampling Method Requirements 28
B3 Sample Handling and Custody Requirements 28
B4 Analytical Method Requirements 29
B5 Quality Control Requirements 29
B6 Instrument/ Equipment Testing, Inspection, and Maintenance 31
B7 Instrument Calibration and Frequency 32
B8 Inspection/Acceptance of Supplies and Consumables 33
B9 Non-Direct Measurements 33
BIO Data Management 33
ASSESSMENT AND OVERSIGHT 37
Cl Assessments and Response Actions 37
C2 Reports to Management 40
DATA VALIDATION AND USABILITY 41
Dl Data Review, Verification, and Validation Requirements 41
D2 Verification and Validation Methods 41
D3 Reconciliation with User Requirements 42
REFERENCES 44
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A3 DISTRIBUTION LI ST
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Vendors
Eric Crosson
Picarro Inc.
480 Oakmead Parkway
Sunnyvale, CA 94085
EPA
Michelle Henderson
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
26 W. ML King Dr.
Cincinnati, OH 45268
John McKernan
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
26 W. ML King Dr.
Cincinnati, OH 45268
Rabon Johnson
I&C Center
714 Swan Pond Road
Harriman, TN 37748
Peer Reviewers
Dennis Mikel
USEPA
OAQPS Mail Code: C304-06
Research Triangle Park, NC 27711
Will Ollison
American Petroleum Institute
1220 L St., NW
Washington DC 20005
Battelle
Kenneth Cowen
Amy Dindal
Bradley Goodwin
Thomas Kelly
Zachary Willenberg
Battelle
505 King Ave.
Columbus, OH 43201
Collaborators/Subcontractors
Chuck Dene
Electric Power Research Institute
3412 Hillview Avenue
Palo Alto, CA 94304-1395
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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 the EPA,
with the support of the Instrumentation and Control (I&C) Center located at the Tennessee
Valley Authority's (TV A) Kingston Fossil Plant. The performance of this test is being funded in
part by the Electric Power Research Institute. A 90-day period of field testing will be conducted
at the plant and will involve the evaluation of commercial cavity ring-down spectroscopy
(CRDS) monitoring systems specifically for the measurement of ammonia in stack gas. I&C
Center staff will provide on-site support during the verification test. A commercial stack-testing
company will provide ammonia reference method sampling under subcontract to Battelle.
The vendors of the CRDS systems being tested will install, operate, and repair or maintain one 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.
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, vendor, I&C Center staff, and subcontractor) in performing
the verification test in accordance with this test/QA plan.
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Battelle
Manaaement
Battelle AMS Center
Quality Manager
Zachary Willenberg
r
Stack Sampling
Crew
Battelle AMS
Center Manaaer
Amy Dindal
Verification
Testing Leader
Thomas Kelly
Verification Test
Coordinator
Kenneth Cowen
Battelle Testing
Staff
EPA AMS Center
Proiect Officer
John McKernan
EPA AMS Center
Quality Manager
Michelle Henderson
I&C Center
Staff
Figure 1. Organizational Chart
> Ensure that all quality procedures specified in the test/QA plan and in the AMS
Center Quality Management Plan1 (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.
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> 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.
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 discover adverse findings that
will compromise data quality or test results.
Battelle Field Testing Staff will oversee portions of the testing of the CRDS systems.
Specifically, Battelle staff will be on-site during the first and last week of the verification test,
and will be in weekly communication with the I&C Center staff during the other portions of the
verification testing, and with technology vendors as needed. The responsibilities of the field
testing staff will be to:
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> Perform the verification test as described in the test/QA plan.
> Communicate with the I&C Center testing staff on the planning, performance, and
reporting of the reference sampling and analysis.
> Record qualitative observations about the maintenance and operation of the CRDS
systems during testing.
> Perform on-site analysis of aliquots of the collected reference samples to provide
preliminary indications of flue gas ammonia concentrations.
> Assure that the data from the CRDS 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
SectionB 1.2.
> 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 documenting adherence to the test/QA plan.
A4.2 Vendors
The responsibilities of the CRDS system vendors are as follows:
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> Review and provide comments on the draft test/QA plan.
> Approve the final test/QA plan prior to test initiation.
> Provide a complete monitoring system for evaluation during the verification test.
> Provide all other equipment/supplies/reagents/consumables needed to operate their
monitoring system for the duration of the verification test.
> Supply a representative to install, operate, and maintain their technologies during the
verification test.
> Provide the data from the monitoring system to the Battelle field testing staff within
one 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"2 (ETV QMP). The roles of specific EPA
testing staff are as follows:
Ms. Michelle Henderson is EPA's AMS Center Quality Manager. Ms. Henderson 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.
> Prepare and distribute an assessment report summarizing results of the external audit.
> Review the draft verification report(s) and statement(s).
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Dr. John McKernan is EPA's Project Officer for the AMS Center. Dr. McKernan will:
> Review the draft test/QA plan.
> Approve the final test/QA plan.
> Review and approve deviations to the approved final test/QA plan.
> Appoint a delegate to review and approve deviations to the approved final test/QA
plan in his absence, so that testing progress will not be delayed.
> 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 I&C Center
I&C Center personnel are responsible for providing on-site support during testing, and will:
> Ensure that Battelle testing staff, vendors, and subcontractors have appropriate access
to the test site.
> Ensure suitable space and electrical power to perform the necessary testing activities
at the test site.
> Coordinate the operation of the host facility for the purposes of ETV testing.
> Coordinate the installation of vendors' equipment at the host facility.
> Communicate needs for safety and other training of staff working at the host facility.
> Provide on-site staff to assist during testing.
> Provide calibrated facility monitoring equipment.
> Provide data on facility operations during testing, for the verification reports.
> Provide input in responding to any issues raised in assessment reports and audits
related to facility operations.
> Review draft verification reports and statements.
Mr. Rabon Johnson is the I&C Center Technical Lead for this verification test. Mr. Johnson will:
> Review the draft test/QA plan.
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> Be the primary I&C contact for Battelle' s Verification Test Coordinator.
> Ensure that designated I&C staff are available for the verification test.
> Coordinate distribution of the test/QA plan to I&C staff.
> Ensure that I&C Center staff conduct test procedures according to the test/QA plan.
> Review and approve all data and records related to I&C operation.
A4.5. Reference Method Stack Sampling Subcontractors
Reference method sampling for ammonia will be conducted by one or more subcontractors to
Battelle. Analysis of the collected samples will be conducted by Battelle or one or more
subcontractors to Battelle. Such subcontractors may include organizations responsible for
operation of the host facility. The responsibilities of such subcontractors are:
> Assemble trained technical staff to conduct reference method sampling for the
verification test.
> Perform the reference method sampling in adherence to the quality requirements in
this test/QA plan and the requirements of the EPA Conditional Test Method - (CTM-
027) Procedure for Collection and Analysis of Ammonia in Stationary Sources.3
> Oversee and conduct laboratory analysis of the reference method samples as
appropriate.
> Report reference method analytical and quality assurance results to Battelle in an
agreed-upon format.
> Support Dr. Cowen in responding to any issues raised in assessment reports and
audits related to reference method sampling and analysis.
A5 BACKGROUND
A5.1 Technology Need
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
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technology categories recommended for testing are CRDS systems. In particular, the use of
CRDS systems for the measurement of ammonia in flue gas at a coal fired power plant was
identified as an area of interest for technology verification.
Selective catalytic reduction (SCR) technologies are commonly used on coal-fired power plants
to reduce nitrogen oxides (NOX) emissions through a chemical reaction with ammonia (NH3).
These technologies require the introduction of large quantities of NHs to reduce the NOX
emissions in a stoichiometric fashion. However, frequently a small amount of excess NHa is
introduced which subsequently is emitted in the flue gas. This excess ammonia, called slip, is
frequently difficult to measure because of its relatively low concentration. CRDS systems have
been proposed as a potentially viable means of monitoring ammonia slip because of the highly
sensitive nature of the CRDS technique.
A.5.2 Technology Description
CRDS systems are spectrometers that enhance sensitivity to target analytes through the use of
multi-pass optical cells that vastly increase the effective pathlength of the absorbing radiation
over typical absorption techniques.4'5 In CRDS, the beam from a laser enters a cavity defined by
two or more highly reflective mirrors. As the light in the cavity reflects back and forth between
the mirrors, a small portion of the light exits the cavity since the mirrors are not completely
reflective. The amount of light exiting the cavity is directly proportional to the intensity in the
cavity. Thus, by monitoring the intensity of light exiting the cavity, the intensity of the light in
the chamber can be deduced.
In the absence of an absorbing species in the cavity, once the laser is turned off the light intensity
inside the cavity will steadily leak out and decay (or "ring-down") to zero in an exponential
fashion. If a gas species that absorbs the laser light is introduced into the cavity, a portion of the
light will be absorbed and the ring-down time will shorten compared to that in a cavity without
any additional absorption due to a targeted gas species. Measurement of the respective ring-
down times thus allows for an accurate determination of the concentration of the absorbing gas
in the cavity.
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A6 VERIFICATION TEST DESCRIPTION AND SCHEDULE
The purpose of this verification test is to generate performance data on CRDS monitoring
technologies with a particular focus on monitoring of ammonia under normal operating
conditions in a full-scale coal-fired power plant utilizing an SCR NOx control technology. The
data generated from this verification test are intended to provide organizations and users
interested in installing and operating these systems with information on their potential reliability.
A6.1 Verification Test Description
The test will be conducted over a period of approximately 90 days and will involve the
continuous operation of CRDS monitoring systems at an operational coal-fired power plant.
During testing, the CRDS systems will continuously monitor ammonia slip concentration in the
flue gas downstream of the SCR. If feasible within plant operating requirements, the host
facility will intentionally introduce upset conditions to change the ammonia slip at various times
during the verification test.
The CRDS systems will be evaluated on the following performance parameters:
> Accuracy
> Comparability
> Precision
> Linearity
> Zero/Calibration drift
> Response time
> Data completeness
> Operational factors.
Accuracy will be assessed for the CRDS systems being verified by determining the degree of
agreement with known concentrations of ammonia compressed gas standards. During the first
and last full weeks of testing, duplicate reference method samples will be collected to assess the
comparability of the CRDS measurements with the standard reference method results. Precision
will be assessed in terms of the repeatability of the ammonia measurements under stable test
conditions using ammonia compressed gas standards. Calibration drift, zero drift, linearity, and
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response time will also be assessed using commercial compressed gas standards of ammonia and
zero air. Data completeness will be determined from a review of the valid data collected during
the verification testing period. Operational performance parameters such as maintenance
requirements, ease of use, and costs will be determined from observations by the Battelle field
testing staff and from on-site I&C Center staff. This test is not intended to simulate long-term
performance of these technologies at a monitoring site.
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, revised, and submitted
to EPA for final approval. 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.1
A6.2 Proposed Testing Schedule
Table 1 shows the planned schedule of testing and data analysis/reporting activities to be
conducted in this verification. The verification process is planned to begin in June 2009 and be
completed in November 2009. The period of operation of the monitoring systems at the
Kingston Fossil Plant will be approximately 90 days, with routine operation expected to begin on
June 29 and continue until September 17, 2009, or until all testing activities are completed.
During testing, duplicate reference samples will be collected thrice each day during two separate
five day periods. One of these five day periods will occur within the first three weeks of the
verification test (i.e., June 29-July 17,) and the second will occur within the last three weeks of
the verification test (i.e., August 31-September 17). The actual reference method sampling
periods will be determined based on the availability of the stack testing crew. Additionally,
dynamic spiking test runs will be conducted within the first three weeks and the last three weeks
of the verification test period to challenge the CRDS systems with ammonia compressed gas
standards in a repeatable fashion to assess system accuracy and precision. Also, zero and
calibration drift measurements will be made by means of ammonia standard challenges
conducted weekly throughout the verification test.
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Table 1. Planned Verification Test Schedule
Date(s)
June 25-26
June 29- September 17
June 29-July 17
June 29-July 17
June 29-September 17
August 31- September 17
September 14-17
September 18
October 16
November 13
November 30
Testing Activities
Installation/shakedown
Verification testing period
Dynamic spiking test runs
Reference sampling period
Weekly zero/calibration checks
Reference sampling period
Dynamic spiking test runs
Remove CRDS systems from test site
Data Analysis and Reporting
Prepare report template
Review and summarize field testing staff
observations
Compile data from CRDS systems
Compile reference method results
Begin draft report(s)
Perform data analysis
Complete draft report(s)
Complete peer review of draft report(s)
Revise draft report(s)
Submit final report(s) for EPA approval
A6.3 Test Facility
TVA's Kingston Fossil Plant is a 1.7 gigawatt (GW) coal fired power plant located on Watts Bar
Reservoir on the Tennessee River near Kingston, Tennessee. The plant has nine generating
units: units 1-4, rated at 175 megawatt (MW) each, and units 5-9, rated at 200 MW each. Each
of the nine power generating units operates in steady state and is equipped with a cold-side SCR
system to reduce nitrogen oxide emissions. Figure 2 shows a schematic illustration of a typical
SCR installation at a coal fired power plant. The CRDS systems will be installed on a section of
duct work downstream of the SCR and upstream of the air preheater (APH) and electrostatic
precipitator (ESP), which are separated by approximately 75 meters at the Kingston Fossil Plant.
Collocated sampling ports will be used for reference method sampling. In general, there are
multiple ports within several feet of the probe providing sample to the CRDS systems. Traverse
sampling will be conducted once to assess stratification in the duct. However, the probe used for
providing sample gas to the CRDS systems is fixed and will not vary. Reference method
sampling will be performed at the same depth in the duct as the CRDS sampling. A schematic of
the actual set up will be included in the verification report.
The I&C Center is a 4,500 ft facility adjacent to the Kingston Fossil Plant in Harriman, TN.
I&C Center staff will provide on-site support during the verification test.
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Boilrl
Economizer
Bypass
To Disposal
Figure 2. Schematic illustration of typical SCR installation at a coal fired power plant.
(Source http://www.netl.doe.gov/technologies/coalpower/cctc/index.html).
A7 QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The objective of this verification test is to evaluate the performance of the CRDS systems under
realistic operating conditions at an operational coal fired power plant. This evaluation will in
part assess the capabilities of the CRDS systems for determining the ammonia concentration in
the flue gas through comparisons to collocated reference samples collected during the
verification test period. Additionally, this verification test will include instrument challenges
using ammonia gas standards to assess performance under controlled and repeatable test
conditions. The verification test will also rely upon operator observations to assess other
performance characteristics of the CRDS systems being tested including data completeness, ease
of use, and maintenance requirements.
To ensure that this verification test provides suitable data for a robust evaluation of performance,
a variety of data quality objectives (DQOs) have been established for this test. The DQOs
indicate the minimum quality of data required to meet the objectives of the verification test and
are different than the QA/QC requirements of the reference method. The DQOs for this
verification test were established to assess the performance of the CRDS systems relative to
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reference measurements and challenges with compressed gas standards. In order to provide a
suitable benchmark for comparison, the reference measurements and standard gas challenges
must meet the DQOs. The DQOs for this verification test include specific objectives for
reference method measurements, dynamic spiking challenges, zero/calibration drift
measurements, and data completeness. The DQOs are quantitatively defined in Table 2 in terms
of specific data quality indicators (DQIs) and their acceptance criteria.
Table 2. DQIs and Criteria for Critical Measurements for Reference Methods.
DQI
Reference method
sampling flow rate
accuracy
Reference method
precision
Dilution accuracy
Reference method
representativeness
Reference method
data completeness
Dynamic spiking data
completeness
Zero/calibration check
data completeness
Dynamic spiking gas
standard flow rate
accuracy
Method of Assessment
Comparison to independent
flow transfer standard
Comparison of duplicate
reference method samples
In-probe introduction of
challenge gas with CEM
measurement
Duct traverse
measurements
Calculation of percent valid
data
Calculation of percent valid
data
Calculation of percent valid
data
Comparison to independent
flow transfer standard
Frequency
At least once for
each reference
method meter
box
Each reference
method sampling
period
At least once
during testing
At least once
during testing
After data
validation
After data
validation
After data
validation
Each dynamic
spiking run
Acceptance
Criteria
±10% of target
flow rate
±35%
agreement
±10% of
calculated
concentration
±35%
> 80% valid
paired samples
> 90% valid
results
> 90% valid
results
±10%
Corrective Action
Inspect meter box and
repeat comparison;
replace meter box as
needed.
Investigate discrepancy
if possible. Reanalyze
samples. Discard if not
resolved.
Investigate discrepancy
if possible. Repeat
measurement and
recalibrate.
Investigate discrepancy
if possible. Repeat if
possible.
Conduct additional
reference method
sampling if possible
Conduct additional
dynamic spiking testing
if possible
Conduct additional
zero/cal. check testing if
possible
Investigate discrepancy.
Inspect meter and
replace meter box as
needed.
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)
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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.
Additionally, the verification test relies in part on observations of the Battelle field testing staff
for assessment of the performance of the CRDS 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 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.
A8 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 described in this test/QA plan will be performed at the I&C center facility.
All participants in this verification test (i.e., Battelle, EPA, subcontractor, and vendor staff) will
adhere to the health and safety requirements of the facility. Vendor staff will operate only their
CRDS systems during parts of the verification test. They are not responsible for, nor permitted
to, operate the combustion source, or perform any other verification activities identified in this
test/QA plan.
All visiting staff at the host facility will be given a site-specific safety briefing prior to the
installation and operation of the CRDS systems. This briefing will include a description of
emergency operating procedures (i.e., in case of fire, tornado, laboratory accident) and
identification, location, and operation of safety equipment (e.g., fire alarms, fire extinguishers,
eye washes, exits).
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A9 DOCUMENTATION AND RECORDS
The records for this verification test 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 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. For each week of ammonia reference method sampling,
the documentation and results of the reference method measurements made by the subcontractor
staff will be submitted to Battelle within 10 days after completion of each week of reference
method sampling. Section BIO further details the data recording practices and responsibilities.
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SECTION B
MEASUREMENT AND DATA ACQUISITION
Bl EXPERIMENTAL DESIGN
The verification test described in this test/QA plan will specifically address verification of CRDS
systems for ammonia monitoring in flue gas by evaluating the following performance factors:
> Accuracy
> Comparability
> Precision
> Linearity
> Zero/Calibration drift
> Response time
> Data completeness
> Operational factors.
The verification test will be conducted over a period of approximately 90 days. A window of
approximately one week prior to testing will be available for installing the CRDS systems at the
facility, and conducting a shakedown run of the CRDS systems before the verification test
begins. The installation/shakedown period is scheduled to begin June 18, 2009. The 90 days of
testing will follow immediately after the setup/shakedown period.
The verification testing will involve continuous monitoring of ammonia in the flue gas by the
CRDS systems over the entire 90 day test period, with reference method sampling conducted on
each day during two separate five day periods. One of these five day periods will occur within
the first three weeks of the verification test (i.e., June 22-July 12,) and the second will occur
within the last three weeks of the verification test (i.e., August 31-September 17). The actual
reference method sampling periods will be determined based on the availability of the stack
testing crew. On each day of reference method sampling, duplicate reference method samples
will be collected over each of three different sampling periods for a total of 30 pairs of duplicate
reference samples in this test. The reference method sampling will be performed based on the
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methods described in EPA CTM-027 for time integrated sampling and analysis of ammonia from
stationary sources with the following modifications:
. Sampling will not be conducted isokinetically since only gaseous ammonia is measured
by the CRDS systems.
. Sampling will not be conducted with a nozzle since isokinetic sampling is not necessary.
Since sampling will not be peformed isokinetcially, the sampling flow rate and duration
will be determined in a manner that is sufficient to allow the collection of a sample
volume that results in an aqueous NH4+ concentration that falls between 10-50% of the
calibration range of the ion chromatography (1C) analysis method (e.g., between 1-5
Hg/mL solution), assuming an ammonia concentration of 2 ppm in the flue gas.
. Samples collected during the verification will be split into two aliquots with one aliquot
submitted for analysis by 1C based on the procedures in CTM-0273, and the other
analyzed immediately in the field by an ion selective electrode (ISE) based on the
procedures in South Coast Air Quality Management District, Method 207.1:
Determination of Ammonia Emissions from Stationary Sources.6
The average CRDS readings during these periods will be compared with the ammonia
concentrations determined from the reference method samples. During each day of reference
method sampling and at least once per week during the other periods of testing, a zero and span
check will be conducted on the CRDS systems by challenging each with zero air and an
ammonia gas standard of known concentration at approximately 80% of full scale for the CRDS
system. Thus, a total of 21 zero/span checks will be used to assess drift of the CRDS systems
during the test period. These data will also be used to assess response time of the CRDS systems.
During the first three and last three weeks of testing, each of the CRDS systems will be
challenged independently with a series of runs involving dynamic spiking of compressed
ammonia gas standards into the CRDS intake gas flow, with 12 test runs at each of three
different nominal concentrations and 36 test runs at the background concentration. The results of
these runs will be used to assess accuracy and precision of the CRDS systems as well as the
linearity in instrument response of the CRDS systems.
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Table 3 presents a summary of the tests to be performed.
Table 3. Summary of Tests and Testing Frequency
Performance
Parameter
Accuracy
Comparability
Linearity
Precision
Cal/Zero Drift
Response Time
Objective
Determine degree of
quantitative
agreement with
compressed gas
standard
Determine degree of
quantitative
agreement with
reference method
Determine linearity of
response over a
range of NH3
concentrations
Determine
repeatability of
successive
measurements at
fixed NH3 levels
Determine stability of
zero gas and span
gas response over
successive days
Determine rise and
fall time
Comparison
Based On
Dynamic spiking with
NH3 gas standards
Reference method
results
Dynamic spiking with
gas standards
Repetitive
measurements under
constant facility
conditions measured
Zero gas and NH3
gas standard
Recording
successive readings
at start and end of
sampling NH3gas
standard
Testing
Frequency
12 runs at each of
three nominal
concentrations during
the first and last
week of testing
Three runs per day
during two separate
5-day periods (10
days total)
12 runs at each of
three nominal
concentrations during
both the first and last
full weeks of testing
Each reference
method sampling
run, and each
dynamic spiking run
Each day during
reference sampling
and once per week
during other testing
periods
Once during each
day of dynamic
spiking testing
Number of
Data Points
72
30 duplicate
pairs
72 above
background
and 72
background
102
21
2
Throughout the verification test, each CRDS system undergoing testing will be operated by the
CRDS vendor's own staffer by on-site I&C Center staff trained by the vendor. However, the
intent of the testing is for the CRDS systems to operate continuously in a manner simulating
operation at a combustion facility. As a result, once the verification test has begun, no
adjustment or recalibration will be performed, other than what would be conducted automatically
by the CRDS systems in normal unattended operation. Repair or maintenance procedures may
be carried out at any time, but testing will not be interrupted, and data completeness will be
reduced if such activities prevent collection of CRDS system data required for verification.
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Bl.l Test Procedures
The CRDS systems undergoing verification will be installed on a section of duct work
downstream of the SCR and upstream of the APH and ESP. The ports for the reference method
sampling will be located on the same duct with the CRDS systems and as close as possible to the
sampling locations of the CRDS systems. The sampling ports will be assigned so that no CRDS
system is affected by the operation of any other CRDS system or by the reference method
sampling. The CRDS systems will be installed with a means of spiking compressed gas into the
sampling probe upstream of the in-line filter.
At either the beginning or the end of each test day during the weeks when reference method
testing is conducted, the CRDS systems undergoing testing will be supplied (one at a time) with
zero gas and then with a commercial compressed gas standard containing ammonia. The order in
which the CRDS systems are challenged in this way will be varied from day to day.
Bl. 1. 1 Reference Method Sampling
During verification testing, reference sampling will be conducted simultaneously with two trains
collocated with the CRDS systems being tested. Thus each of the three reference sampling
periods during a test day will provide two reference ammonia samples for comparison to the
CRDS data. Reference method sampling will be conducted based on the procedures in CTM-
027, with the modifications described above. The sampling duration for each run is expected to
be typically between 30 and 60 minutes, although actual times will be based on the actual
sampling flow rate and observed flue gas NHs levels.
Unique sample identification numbers will be implemented so that final data used for
verification can be traced back through the analytical process to the original sample. Field blank
samples will also be recovered from one blank sampling train on each of three days during each
week that reference method samples are collected. Before sample recovery, that blank train will
be transported to the sampling location. Care will be taken that the blank train is selected at
random from the prepared trains, so that different trains are used as the blank on different days.
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Results of the individual reference method measurements will be normalized to 7% 02. It is
expected from previous results that the precision of duplicate reference method results will be
within about 35 percent relative percent difference (RPD), determined as
RPD= Rl~R2 xlOO
(Rl+R2)/2
where RI and R2 are the reference method results for the duplicate trains.
It is expected that day-to-day reproducibility of ammonia levels in the facility will also be within
that range. Thus, during normal operation it is expected that the ammonia levels will be
consistent to ± 35% throughout each week of testing. As a result, the entire set of reference
method results, not merely those from a single test day, will be considered in screening for
reference data quality. The reference method results will be reviewed before verification
comparisons are made, to identify individual outliers from the full set of reference method
results. That is, the reference method results will be screened for two factors:
> Precision of results from co-located sampling trains
> Consistency of results with previous and later results at the respective sampling
location
The ammonia concentration values and the associated RPD values for each test run will plotted
as a function of test number to graphically illustrate any trends in ammonia concentrations and
identify potential outliers in the RPD values. Reference method pairs that exhibit an RPD that
exceeds 35% will be flagged, and effort will be made to find an assignable cause for the
divergent result. Reference method results which are flagged as outliers will be reported, but
will not be used for verification unless appropriately documented. The intent of this approach is
to provide a valid set of reference data for verification purposes, while also illustrating the degree
of variability of the reference methods.
Bl.1.2 Dynamic Spiking
During the first three weeks and last three weeks of testing, each of the CRDS systems will be
challenged with a series of dynamic spiking runs. The dynamic spiking will be conducted by
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injecting ammonia gas into the probe tip upstream of the parti culate filter such that the ammonia
spike passes through as much of the sampling system as possible. The ammonia gas standard
will be mixed with the flue gas at a ratio of <1 part spike gas to 9 parts flue gas. The flow rate of
the compressed gas and the dilution ratio of the spike gas will be used to calculate the expected
increase in ammonia concentration introduced during the spiking. An Environics Model 6100
dilution system will be used to deliver the appropriate spike gas concentration to CRDS system.
During these runs the ammonia concentrations will be increased by approximately 2, 5, and 8
ppmv above the native flue gas concentration. At each spike concentration, a series of CRDS
challenge runs will be conducted including 12 spiked and 12 unspiked sample measurements.
These measurements will be performed by sampling pairs of spiked samples, followed by
sampling pairs of unspiked samples. Prior to measurement, each CRDS will be readied by
purging the gas cell with at least 10 volumes of flue gas spiked with zero air. After this purging
is completed, a standard ammonia gas mixture will be introduced, at a measured flow rate, to the
sampling probe. The CRDS readings of the spiked sample will be recorded after at least 10
volumes of gas have passed through the CRDS gas cell. A second such spiked sample will be
measured after at least five volumes of gas have passed through the CRDS gas cell after the
measurement of the first spiked sample. After the second spiked sample is measured, a pair of
unspiked samples will be measured following the same procedure as the spiked samples with the
exception that zero air will be substituted for the ammonia spike gas. The procedures for the
collection of the spiked and unspiked samples will be conducted a total of six times at each of the
spike concentrations to obtain 12 spiked and 12 unspiked samples at each concentration. The
procedures will be once each during the first three weeks and last three weeks of the verification
test (June 29 - July 17 and August 31- September 17).
Bl.1.3 Zero/Calibration Checks
During each day of reference method sampling and at least once during each other week of
verification testing the CRDS systems being evaluated will be independently supplied with zero
air and a compressed gas standard to assess zero and calibration drift of the systems. The same
compressed gas standard will be used in all such checks, to assess drift in CRDS response.
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B1.2 Statistical Evaluation
Prior to any statistical evaluations, all results from the reference method sampling and the CRDS
systems being evaluated will be normalized to 7% O2 using the results from the facility CEMs
operating during the verification test.
Bl.2.1 Accuracy
The relative accuracy (RA) of the CRDS systems will be assessed from the dynamic spiking
results using Equation 1 :
RA =
where Prefers to the difference between the calculated ammonia concentration from the dynamic
spiking and the average of the CRDS measurements recorded during the respective spiking
periods, and x corresponds to the calculated spike concentration. Sd denotes the sample standard
deviation of the differences, while tan_i is the t value for the 100(1 -a)th percentile of the
distribution with n-1 degrees of freedom. The relative accuracy will be determined for an a
value of 0.025 (i.e., 97.5 percent confidence level, one-tailed). The RA calculated in this way
d
can be interpreted as an upper confidence bound for the relative bias of the analyzer, i.e., —,
x
where the superscript bar indicates the average value of the differences or of the reference
values. Relative accuracy will be calculated separately at each of the spiking levels, and
separately for each CRDS system undergoing verification.
Bl.2.2 Comparability
Comparability between the CRDS results and the Method 207.1 reference method results will be
assessed using Equation 1, but with d representing the difference between the average of paired
reference method results and the average of the CRDS results from the period during which the
paired reference method samples were collected, and x corresponding to the average of the
paired reference method results. Comparability will be calculated using all reference method
sample results (assuming all reference method samples can be treated as independent results),
and separately for each CRDS system undergoing verification.
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Bl.2.3 Precision
Precision will be calculated in terms of the percent relative standard deviation (RSD) of the
CRDS measurements made during the dynamic spiking test runs and reference method sampling
periods. During each such run, all the readings from each CRDS system undergoing testing will
be recorded, and the mean will be calculated. The precision will be calculated as the standard
deviation of the mean values divided by the mean. Precision will be calculated for each dynamic
spiking target concentration level. Precision in dynamic spiking response will be reorted
separately from precision in flue gas monitoring.
Bl. 2.4 Linearity
Linearity will be assessed by a linear regression analysis of the dynamic spiking data using the
calculated ammonia concentrations as the independent variable and the CRDS results as the
dependent variable. The "known" ammonia concentrations will be subject to uncertainty from
variable flue gas ammonia background concentrations. The results of the dynamic spiking test
will be plotted and linearity will be expressed in terms of slope, intercept, and coefficient of
determination (r2).
Bl.2.5 Zero/Calibration Drift
Calibration and zero drift will be reported in terms of the mean, relative standard deviation, and
range (maximum and minimum) of the readings obtained from the CRDS in the routine weekly
sampling of the same ammonia standard gas, and of zero gas. These results, along with the range
of the data, will indicate the week-to-week variation in zero and standard readings.
Bl.2.6 Response Time
Response time will be assessed in terms of both the rise and fall times of each CRDS when
sampling the ammonia gas standard. Rise time (i.e., 0% - 95% response time) will be
determined by recording all CRDS readings as the gas supplied to the CRDS is switched from
zero gas to the ammonia standard. Once a stable response has been achieved with the gas
standard, the fall time (i.e., the 100% to 5% response time) will be determined in a similar way,
by recording all CRDS readings as the gas supplied is switched from the ammonia standard back
to zero gas. For CRDS systems which provide periodic rather than continuous readings,
determination of rise and fall times may involve interpolation between readings.
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Rise and fall times will each be determined once during dynamic spiking testing performed in
each of the first and last weeks of testing for each CRDS. Rise and fall times will be reported in
units of seconds.
Bl.2.7 Data Completeness
Data completeness will be assessed based on the overall data return achieved by each CRDS
system during the testing period. For each of the CRDS systems, this calculation will use the
total number of apparently valid data points reported by the monitoring systems divided by the
total number of data points potential available in the entire field period. The causes of any
incompleteness of data return will be established from operator observations or vendor records,
and noted in the discussion of data completeness results.
El. 2.8 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 I&C
Center staff, and explained by the vendor as needed. Battelle or I&C Center staff will be at the
Kingston plant 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 CRDS 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 observations about ease of use of the CRDS systems. These
observations will be summarized to aid in describing CRDS system performance in the
verification report.
B1.3 Reporting
The statistical comparisons described above will be conducted separately for each CRDS system
being tested, and information on the operational performance will be compiled and reported. A
verification report will be prepared for each CRDS system tested, that presents the test
procedures and test data, as well as the results of the statistical evaluation of those data.
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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
regarding CRDS system performance will be stated quantitatively. Each draft verification report
will be subjected to review by the vendor, EPA, and other peer reviewers. The resulting 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 and submitted to
EPA. The reporting and review process will be conducted according to the requirements of the
ETV/AMS Center QMP.1
B2 SAMPLING METHOD REQUIREMENTS
Reference method sampling will be conducted based on the procedures described in EPA CTM-
027,3 with the exception of the modifications described in Section Bl of this test/QA plan. This
method uses an EPA Method 177 sampling train that consists of a borosilicate or quartz probe
liner, borosilicate or quartz nozzle, Pitot tube, differential pressure gauge, in-stack filter holder
and filter, ice-cooled Greenberg-Smith impingers for sample collection, and metering system.
For this verification test, isokinetic sampling will not be conducted, so no nozzle is necessary.
The sampling will be conducted at a selected sampling rate until an appropriate volume has been
collected that is sufficient to provide samples with NH4+ concentrations in solution of between 1-
5 |j,g/mL, based on an assumed flue gas concentration of 2 ppmv NH?. The sampling rate and or
sampling time may be adjusted if on-site analysis of previous reference method samples
indicates adjustments should be made.
B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Samples will be recovered from the reference method trains within two hours of sample
collection according to the procedures described in Section 4.1 of CTM-027. Each of the
reference samples will be split into two aliquots, with one aliquot preserved as described in
Section 4.1 of CTM-027 and the other aliquot analyzed on-site by the SCAQMD Method 207.1
using an ISE. The analyses performed by ISE are meant to serve as an on-site indication of the
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reference method sampling results and are not anticipated to be used for verification purposes.
The on-site analysis will be conducted within two hours of sample recovery by Battelle, using
available on-site facilities. The front and back impingers will be analyzed separately on-site by
ISE. Samples will be warmed as needed to within ±2°C of the temperature of the standards used
for calibration of the ISE. Although filter samples will be collected, they will not be analyzed
for this verification test.
The aliquots to be analyzed by 1C according to CTM-027 will be stored and transported to the
analytical laboratory under refrigerated conditions at 4 °C ±2 °C until analysis. Prior to analysis,
the samples will be allowed to warm slowly to room temperature, and will be analyzed within 4
hours of removal from the refrigerated conditions.
B4 ANALYTICAL METHOD REQUIREMENTS
The samples analyzed on-site will be analyzed using a calibrated ISE as described in the
SCAQMD Method 207.1. The ISE will be calibrated using at least four NH4+ standard solutions
bracketing the concentration range of interest (e.g., 0.1-10 |j,g/mL). The samples and the
standard solutions will be analyzed at the same temperature, preferably about 25°C ± 2°C.
The samples analyzed by 1C will be analyzed according to the procedures described in CTM-
027. Calibration of the 1C will be performed according to the procedures in Section 4.2 of CTM-
027 and include six standard solutions that bracket the concentration range of interest (e.g., 0.1-
10 ng/mL).
B5 QUALITY CONTROL REQUIREMENTS
Table 4 summarizes the QC requirements of the reference method sampling and analysis,
including frequency of the QC activities, the acceptance criteria, and corrective actions. QC
requirements for the ISE analysis have also been included although it is not expected that the ISE
analysis will be used for any statistical comparisons to the CRDS systems being tested.
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Table 4. Quality Control Requirements for Reference Method Sampling and Analysis
QC Activity
Field blank train
Pre-test leak check
Post-test leak check
Meter box calibration
ISE calibration
ISE blank solution
check
Duplicate sample
analysis
Calibration
verification solution
check
Matrix spike check
Temperature stability
check
1C calibration
1C blank solution
check
1C duplicate sample
analysis
Calibration
verification solution
check
Frequency
1 per day of
reference method
sampling
Each sampling run
Each sampling run
Each sampling run
Each day of analysis
Beginning of each
batch
Each sample
After every fifth
duplicate sample
and at the end of
sample batch
Once per batch
Each standard
solution and sample
Each day of analysis
Beginning of each
batch
After every tenth
sample
After every tenth
sample
Acceptance Criterion
< 1 0% of expected
ammonia concentration
< 4% of average flow rate
< 4% of average flow rate
< 5% difference in DGM
calibration factor
-54 > Slope > -60
r2 > 0.997
<10% of expected
ammonia concentration
Relative percent
difference (RPD) < 5%
Relative percent accuracy
(RPA)<10%
None established
±2°C
Slope = 1 .0 ± 1 0%
r^o.gg
<10% of expected
ammonia concentration
Relative percent
difference (RPD) < 5%
Relative percent accuracy
(RPA)< 10%
Corrective Action
Clean sampling train
components; obtain new
solvents/solutions
Check sampling train, reseed
connections, and replace
components, as necessary.
Inspect sampling train, Flag
data
Check sampling train, reseed
connections, and replace
components as necessary.
Recalibrate
Check the electrode, prepare
fresh standards, troubleshoot
the instrument, or perform
routine instrument
maintenance
Recalibrate ISE, prepare new
calibration standards, as
needed
Recalibrate ISE, prepare new
samples as needed
Recalibrate ISE, prepare new
calibration standards, as
needed
Although there are no criteria
for acceptability of percent
recovery, the data are useful
for identifying possible errors
in the analysis
Recalibrate, reanalyze
samples
Recalibrate 1C, prepare new
calibration standards, as
needed
Recalibrate 1C, prepare new
calibration standards, as
needed
Recalibrate 1C, prepare new
samples as needed
Recalibrate 1C, prepare new
calibration standards, as
needed
During each week of reference method sampling, a total of five sampling trains (one per day)
will be used as field blank samples. These trains will be prepared and transported to the
sampling location but will not be used to collect a sample of flue gas. The blank trains will then
be disassembled and the field blank solutions will be analyzed on-site by ISE to ensure that the
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background concentration due to on-site handling and exposure is < 10% of the expected
ammonia content of the samples. If background ammonia levels are greater than 10% of the
expected sample ammonia concentrations, the cause of the contamination will be investigated
and rectified, if possible.
Laboratory blank solutions will be prepared from 0.04 N H2SO4 for ISE analysis, and analyzed
prior to analysis of the reference samples. A laboratory blank solution will also be analyzed after
every 10th reference method sample to ensure no drift in the ISE calibration. If the blank levels
are greater than 10% of the expected sample concentrations, the cause of the contamination will
be investigated and rectified, and all analyses performed after the most recent acceptable blank
will be invalidated and analysis of those samples will be repeated (if possible).
Laboratory spike solutions will be prepared in 0.04 N H2SO4 with concentrations approximately
equal to ammonia concentrations expected from the collection of a sample of flue gas containing
2 ppmv ammonia. These solutions will be prepared for ISE and 1C analysis using a NIST
traceable ammonia solutions different than those used for the calibration of the ISE and 1C. The
solutions will be analyzed prior to analysis of the reference samples. A laboratory spike solution
will also be analyzed after every 10th reference method sample to ensure no drift in the ISE or 1C
instrumentation. If the measured concentrations are not within ±10% of the spike concentration,
the cause of the discrepancy will be investigated and rectified if possible. If such a discrepancy
is observed, all analyses performed after the most recent acceptable spike will be invalidated and
analysis of those samples will be repeated (if possible).
B6 INSTRUMENT/ EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
The glassware, filters, and associated equipment for performance of the reference method
sampling will be supplied by the subcontractor and will meet the requirements of the CTM-027
for ammonia measurement. Multiple trains will be supplied so that six trains (i.e., three
sampling runs with two trains each) may be sampled in a single day, in addition to at least five
blank trains and five spiked trains per week. Preparation, sampling, sample recovery, and
cleaning of used trains will be the responsibility of the stack sampling subcontractor in this
verification test.
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B7 INSTRUMENT CALIBRATION AND FREQUENCY
B7.1 Sampling Meter Box
The sampling metering instrumentation used for the reference sample collection will be
calibrated based on the requirements of EPA Method 5,8 and references therein. These
requirements include those for the dry gas meter, temperature, and pressure sensors, but will
exclude those of the nozzle calibrations which are not required since sampling will not be
performed isokinetically.
Additionally, Class 1 glassware will be used for preparation of calibration and audit solutions.
The balance used to measure impinger solution masses will be calibrated using NIST-traceable
weights that bracket the expected range of masses to be measured. Agreement between
measured and actual weights will be within the greater of 1% or 0.5 g.
B7.2 Ion Selective Electrode
The ISE will be calibrated according to the manufacturer's recommendations using at least three
different solutions, prepared from NIST traceable ammonium standards that bracket the NH4+
concentration range of interest (e.g., 0.1-10 |j,g/mL). Immediately after calibration, at least four
standard solutions will be reanalyzed using the ISE. If the ISE reading does not agree within
10% of the standard concentrations the calibration will be repeated. The calibration will be
conducted on-site daily during each week of reference sampling.
B7.3 Ion Chromatograph
The 1C used for analysis of the reference method samples will be calibrated according to
manufacturer's recommendations using at least six different solutions, prepared from NIST
traceable ammonium standards, that bracket the NH4+ concentration range of interest (e.g., 0.1-
10 |j,g/mL). Immediately after calibration, at least three standard solutions will be reanalyzed
using the 1C. If the 1C readings do not agree within 10% of the standard concentrations the
calibration will be repeated. The calibration will be conducted daily during each day of analysis.
B7.4 Facility CEMs
This verification will make use of monitoring equipment already integrated into the Kingston
facility. This equipment includes monitors for major flue gas constituents (62, CCh) and for
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chemical contaminants (CO, NOX, SO2), as well as sensors for temperature and pressure installed
at the facility. These devices are considered part of the host facility for purposes of this test, and
will be operated and calibrated by the host facility during this verification according to normal
facility procedures. All calibration results must be documented for inclusion in the verification
test data files and verification report.
B8 INSPECTION/ACCEPTANCE OF SUPPLIES AND CONSUMABLES
Upon receipt of any supplies or consumables used for the dynamic spiking testing and for the
reference method sampling and analysis, Battelle or subcontractor 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 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.
The high purity gases used for zeroing of the CRDS systems will be commercial ultra-high
purity (UHP, i.e., minimum 99.999% purity) air or nitrogen. Compressed gas standards
containing ammonia will be obtained for use in the calibration checks and the dynamic spiking
activities of the CRDS systems. These will consist of ammonia in a nitrogen matrix, at levels
appropriate to achieve increases above background concentrations of approximately 2, 5, and 8
ppmv during dynamic spiking, and for use in the calibration checks performed during testing.
Multiple cylinders of uniform concentration will be obtained, if required to meet the gas
consumption rates during the test. All cylinders will include a COA specifying analytical purity
and the cylinder calibration expiration date.
B9 NON-DIRECT MEASUREMENTS
No non-direct measurements will be used during this verification test.
B10 DATA MANAGEMENT
Various types of data will be acquired and recorded electronically or manually by Battelle,
vendor, and I&C Center staff during this verification test. All data will be recorded in permanent
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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 5 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). Measurements taken during the collection of the reference
method samples will be compiled by subcontractor staff in hard copy or electronic format, and
submitted to Battelle in the form of an analytical report at the conclusion of reference sampling
periods. Figure 3 shows an example field data sheet that will be used by the stack sampling
crew. Report formats will include all necessary data to allow traceability from the raw data to
final results.
Records received by or generated by any Battelle, subcontractor, or I&C Center 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 the record. The review will be documented by the person
performing the review by adding his/her initials and date to the hard copy of the record being
reviewed. In addition, any calculations performed by Battelle, subcontractor, or I&C Center
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.
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Table 5. Summary of Data Recording Process
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Data to Be Recorded
Dates, times, and
details of test events
CRDS system
calibration information,
maintenance, down
time, etc.
CRDS system readings
Host facility CEM
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
ETV LRBs, or
data recording
forms or
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, I&C
Staff, and
subcontractor
staff
Vendor,
Battelle, I&C
Center staff
Vendor or I&C
Center staff
for transfer to
Battelle
I&C Center for
transfer to
Battelle
Subcontractor
or Battelle
Subcontractor
or Battelle
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 flue
gas concentrations,
and statistical
analysis and
comparisons
Retained as
documentation of
reference method
performance
Converted to
spreadsheets for
calculation of flue
gas concentrations,
and statistical
analysis and
comparisons
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.
Changes to requirements in the approved test/QA plan will be documented on the appropriate
form in the AMS QMP and be brought to the attention of the EPA AMS Center Project Officer
(PO) and EPA AMS Center QA Manager. If approval by the EPA PO or his designee is not
received within 24 hours of notification testing will be halted until a suitable resolution has been
achieved.
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 dynamic spiking procedures and the reference
sampling and analysis methods. Table 6 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
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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.
The PE audit of the dynamic spiking flow rate will be conducted using an independent NIST-
traceable flow transfer standard (e.g., Bios, Model DC-2, or comparable). The target criterion
for this audit is agreement between the measured and nominal flow rate within ±10%. 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.
Table 6. Methods and Acceptance Criteria for PE Audit Measurements
Critical Measurement
Dynamic spiking flow rate
Stack Temperature
Barometric Pressure
Flue Gas Differential Pressure
Mass (H20)
Ammonia (overall measurement)
Ammonia (ISE analysis)
Ammonia (1C analysis)
PE Audit Method
Compare to independent flow transfer
standard
Compare to independent temperature
measurement
Compare to independent pressure
measurement
Compare to independent pressure
measurement
Check balance with calibrated weights
Spike reference method trains
Blind audit sample
Blind audit sample
Acceptance Criteria
±10% actual flow rate
±2% absolute temperature
±0.5 inch of H2O
±0.5 inch of H2O
±1% or 0.5 g, whichever is
larger
± 20% bias in spike
recovery
± 10% of standard
concentration
± 10% of standard
concentration
The PE audit will include spiking reference method sampling trains with known amounts of
ammonia, and conducting sample analysis on the train without sampling the combustion gas. A
NIST-traceable ammonium standard solution will be used for that purpose. During each week of
sampling, five blank trains will be prepared spiked with a known amount of an ammonia
standard solution, such that the ammonium concentration in the sample solution is within 10-
50% of the calibration range of the 1C (e.g., 1-5 |j,g/mL). The spiked trains will be transported to
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the sampling location but will not be used to collect a sample of flue gas. The trains will then be
disassembled and the spiked samples will be analyzed both on-site by ISE and in the laboratory
by 1C, and the percent recovery will be calculated. Agreement of ammonia determined in
sample analysis with that spiked into the sample train is expected to be within 20 percent. If the
recovery of the field spikes is not >80% and <120%, no additional reference sampling will be
conducted until the cause of the discrepancy is investigated and rectified if possible. Because
reference sample analysis is performed on site by ISE, PE audit results for the overall ammonia
measurement will be available during the test, and will be used to improve reference method
procedures, if necessary.
The PE audit of the analytical methods will be performed by supplying audit samples prepared
from independent NIST-traceable standard solutions. These audit samples will be analyzed and
compared to the known sample concentrations. The acceptance criterion for this audit is for
agreement between the measured and actual concentrations within ±10%.
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,1 this test/QA plan, published reference methods, and any SOPs used by
the test facility. In this TSA, the Battelle Quality Manager, or designee, may review the
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, I&C Center, and subcontractor 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.
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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 (as received from the ISE, I&C, and vendors), through reduction and
statistical comparisons, to final reporting. All calculations performed on the data undergoing the
audit will be checked. Data must undergo a 100% validation and verification by technical staff
(i.e. Verification Test Coordinator, or designee) before it will be assessed as part of the data
quality audit.
C1.4 QA/QC Reporting
Each assessment and audit will be documented in accordance with Section 3.3.4 of the AMS
Center QMP.1 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.
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 QA 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, reference method QC requirements, and audit acceptance criteria specified
for this test in Tables 2, 4, and 6, respectively. The results of the reference method QC activities
and the PE audit results will be compared with the appropriate acceptance criteria in Tables 4
and 6, respectively, to ensure that the reference method measurements were properly performed.
Furthermore, the results of the reference method measurements and dynamic spiking
measurements will be compared with the appropriate DQIs listed in Table 2 to validate the
quality of the data. Any deficiencies in these data will be flagged and excluded from any
statistical comparisons to the CRDS systems being tested, unless these deviations are
accompanied by descriptions of their potential impacts on the data quality.
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).
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Electronic data from the CRDS 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
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 ISA 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, 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 CRDS systems. In part,
this evaluation will include comparisons of results from the monitoring systems to the results
from reference method samples generated from the SCAQMD Method 207.1. To meet the
requirements of the user community, the reference data collected during this verification test will
meet the QA requirements of the reference method. Additional performance data regarding
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operational characteristics of the monitoring systems will be collected by verification test
personnel. To meet the requirements of the user community, these data will 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 are 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 help to improve
the design of the verification test and the resulting report(s) such that they better meet the needs
of potential users of these monitoring systems.
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SECTION E
REFERENCES
1. Battelle, Quality Management Plan for the ETV Advanced Monitoring Systems Center,
Version 7.0, U.S. EPA Environmental Technology Verification Program, prepared by
Battelle, Columbus, Ohio, November 2008.
2. U.S. EPA, Environmental Technology Verification Program Quality Management Plan, EPA
Report No: 600/R-08/009, U.S. Environmental Protection Agency, Cincinnati, Ohio, January 2008.
3. U. S. EPA, Conditional Test Method (CTM-027) Procedure for Collection and Analysis of
Ammonia in Stationary Sources, August 1997. Available at:
http://www.epa.gov/ttn/emc/ctm.html
4. Busch KW, Busch MA, Cavity Ring-down Spectroscopy: An Ultratrace Absorption
Measurement Technique. ACS Symposium Series 720, Oxford (1997).
5. Atkinson, D. B., "Solving chemical problems of environmental importance using cavity ring-
down Spectroscopy," The Analyst 128, 117-125 (2003).
6. SCAQMD, Method 207.1: Determination of Ammonia Emissions from Stationary Sources,
South Coast Air Quality Management District, Source Test Engineering/Laboratory Services,
April 2006.
7. U.S. EPA, Method 17 - Determination of Parti culate Matter Emissions from Stationary
Sources, Available at: http://www.epa.gov/ttn/emc/promgate.html
8. U.S. EPA, Method 5 - Determination of Particulate Matter Emissions from Stationary
Sources, Available at: http://www.epa.gov/ttn/emc/promgate.html
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