Batteile
The Business of Innovation
Environmental Technology
Verification Program
Advanced Monitoring
Systems Center
Test/Quality Assurance Plan
for Verification of
Isotopic Carbon Dioxide Analyzers for
Carbon Sequestration Monitoring
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TEST/QUALITY ASSURANCE PLAN
for
Verification of
Isotopic Carbon Dioxide Analyzers
for Carbon Sequestration Monitoring
Version 1.0
July 1, 2010
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/Quality Assurance Plan for Verification of
Isotopic Carbon Dioxide Analyzers
for Carbon Sequestration Monitoring
Version 1.0
July 1,2010
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 List of Acronyms and Abbreviations 4
A4 Distribution List 5
A5 Verification Test Organization 6
A6 Background 13
A7 Verification Test Description and Schedule 16
A8 Quality Objectives and Criteria for Measurement Data 21
A9 Special Training/Certification 23
A10 Documentation and Records 23
MEASUREMENT AND DATA ACQUISITION 25
Bl Experimental Design 25
B2 Sampling Method Requirements 38
B3 Sample Handling and Custody Requirements 38
B4 Analytical Method Requirements 38
B5 Quality Control Requirements 38
B6 Instrument/Equipment Testing, Inspection, and Maintenance 38
B7 Instrument Calibration and Frequency 39
B8 Inspection/Acceptance of Supplies and Consumables 39
B9 Non-Direct Measurements 40
BIO Data Management 40
ASSESSMENT AND OVERSIGHT 42
Cl Assessments and Response Actions 42
C2 Reports to Management 44
DATA VALIDATION AND USABILITY 46
Dl Data Review, Verification, and Validation Requirements 46
D2 Verification and Validation Methods 46
D3 Reconciliation with User Requirements 47
REFERENCES 48
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Section Page
Figures
Figure 1. Organizational Chart 7
Figure 2. Schematic Diagram of the ABT 19
Figures. Photograph of the ABT 20
Figure 4. Diagram of GCS site 21
Tables
Table 1. Anticipated Monitoring Needs for the GCS Sites 14
Table 2. Planned Verification Test Activities 17
Table 3. Planned Verification Test Schedule 18
Table 5. Summary of Tests and Testing Frequency 27
Table 6. Approximate CO2 Concentrations for Multi-point Challenges 29
Table 7. Approximate CC>2 Concentrations and Isotope Ratios for Bias Tests 30
Table 8. Approximate Conditions for Temperature and RH Bias Tests 31
Table 9. Summary of Data Recording Process 41
Table 10. Summary of Reports to Management 45
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A3 LIST OF ACRONYMS AND ABBREVIATIONS
%D percent difference
%R percent recovery
%RSD percent relative standard deviation
ABT ambient breeze tunnel
ADQ audit of data quality
AMS Advanced Monitoring Systems
cfm cubic feet per minute
CC>2 carbon dioxide
COA certificates of analysis
CRDS cavity ring down spectroscopy
DQIs data quality indicators
EPA U.S. Environmental Protection Agency
QMP Quality Management Plan
ETV Environmental Technology Verification
GCS geologic carbon sequestration
IRMS isotope ratio mass spectrometry
Lpm liter per minute
LRB laboratory record book
ppm parts per million by volume
PDB Pee Dee Belemnite
PE performance evaluation
PO project officer
QA quality assurance
QC quality control
QCL quantum cascade laser
QMP Quality Management Plan
RMO Records Management Office
TQAP test/quality assurance plan
TSA technical systems audit
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A4 DISTRIBUTION LIST
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Vendors
Chris Rella, Ph.D.
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, Sc.D.
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
26 W. ML King Dr.
Cincinnati, OH 45268
Battelle
Ann Louise Sumner, Ph.D.
Amy Dindal
Rodney Osborne, Ph.D.
Elizabeth Cutie
Rosanna Buhl
Battelle
505 King Ave.
Columbus, OH 43201
Peer Reviewers
Professor Sally M. Benson
Stanford University
Y2E2 Building, Mail Code 4230
473 Via Ortega, Ste. 324
Stanford, CA 94305
Chuck Dene
Electric Power Research Institute
3412 Hillview Avenue
Palo Alto, CA 94304-1395
Dominic C. DiGiulio, Ph.D.
U.S. Environmental Protection Agency
Office of Research and Development
National Risk Management Research
Laboratory Ground Water and Ecosystem
Restoration Division
919 Kerr Research Drive
Ada, Oklahoma 74820
Eben Thoma, Ph.D.
U.S. Environmental Protection Agency
(E343-02) Office of Research and
Development National Risk Management
Research Laboratory
109 TW Alexander Drive
Research Triangle Park, NC 27711
Bruce J. Kobelski
U.S. Environmental Protection
Underground Injection Control Program -
(4606M) Office of Ground Water and
Drinking Water
Ariel Rios Building
1200 Pennsylvania Avenue, N. W.
Washington, DC 20460
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A5 VERIFICATION TEST ORGANIZATION
The verification test described in this document will be conducted under 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 the U.S. Environmental Protection Agency (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 staff at a geologic carbon sequestration (GCS) site. Laboratory and
field testing will be conducted over a five-week period at three testing locations: a Battelle
laboratory in Columbus, Ohio; a Battelle testing facility in West Jefferson, Ohio; and a coal-fired
power plant where carbon dioxide (CO2) captured from the flue gas is being geologically
sequestered. The testing will involve the evaluation of commercial isotopic CO2 analyzers,
which may include cavity ring down spectroscopy (CRDS) and pulsed quantum cascade laser
(QCL) spectroscopy monitoring systems specifically for the measurement of stable carbon
isotope ratios (13C/12C) and CO2 concentration (12CO2 + 13CO2). Battelle staff at the
sequestration site will provide on-site support during the verification test.
The vendors of the CO2 analyzers 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 QA 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.
A5.1 Battelle
Dr. Ann Louise Sumner is the AMS Center Verification Test Coordinator for this test. In
this role, Dr. Sumner will have overall responsibility for ensuring that the technical, schedule,
and cost goals established for the verification test are met. Specifically, she will:
• Assemble a team of qualified technical staff to conduct the verification test.
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AMS Center
Stakeholders
Battelle
Management
Battelle AMS
Center Manager
Amy Dindal
EPA AMS Center
Project Officer
John McKernan
Battelle AMS Center
Quality Manager
Rosanna Buhl
Quality Assurance
Officer
Betsy Cutie
EPA AMS Center Quality
Manager
Michelle Henderson
Verification Test
Coordinator
Ann Louise Sumner
Vendor
Representatives
Battelle Testing
Staff
Figure 1. Organizational Chart
Hold a kick-off meeting approximately one week prior to the start of the verification
test to review the critical logistical, technical, and administrative aspects of the
verification test. Responsibility for each aspect of the verification test will be
confirmed.
Direct the team (Battelle testing staff and vendor) in performing the verification test
in accordance with this test/QA plan (TQAP).
Ensure that all quality procedures specified in the TQAP and in the AMS Center
Quality Management Plan1 (QMP) are followed.
Maintain real-time communication with the Battelle AMS Center Manager and EPA
AMS Center Project Officer and Quality Assurance Manager on any potential or
actual deviations from the TQAP.
Coordinate with Battelle Testing Staff to ensure that the planned testing will not
interfere with the carbon sequestration site operations.
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• Provide test data, including data from the first day of testing, to the Battelle AMS
Center Manager and EPA AMS Center Project Officer and Quality Assurance
Manager
• Prepare the draft and final TQAP, verification report(s), and verification statement(s).
• Conduct a technical review of all test data. Designate an appropriate Battelle
technical staff member to review data generated by the Verification Test Coordinator.
• Revise the draft TQAP, verification report(s), and verification statement(s) in
response to reviewers' comments.
• Compile data from the first day of the verification test and provide the data to EPA
for review.
• 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 TQAP, verification report(s), and statement(s).
• Establish a budget for the verification test and manage staff to ensure the budget is
not exceeded.
Ms. Amy Dindal is Battelle's manager for the AMS Center. Ms. Dindal will:
• Review the draft and final TQAP.
• 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.
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Battelle Testing Staff will conduct portions of the testing of the CO2 analyzers at each of
the three sites and will be in weekly communication with the Verification Test Coordinator, and
with technology vendors as needed. The responsibilities of the field testing staff will be to:
• Coordinate with the test site to ensure that Battelle testing staff, vendors, EPA, and
subcontractors have appropriate access to the test site.
• Coordinate with test site to ensure suitable space and electrical power to perform the
necessary testing activities at the test site.
• Coordinate the operation of the test site for the purposes of ETV testing.
• Coordinate the installation of vendors' equipment at the test sites.
• Communicate needs for safety and other training of staff working at the test site.
• Perform the verification test as described in the TQAP.
• Record qualitative observations about the maintenance and operation of the CC>2
analyzers during testing.
• Ensure that the data from the CO2 analyzers are immediately checked, and on at least
a weekly basis, compiled, recorded, and transmitted to the Verification Test
Coordinator.
• Provide input in responding to any issues raised in assessment reports and audits
related to facility operations.
• 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.
• Review draft verification reports and statements as needed.
Ms. Rosanna Buhl is Battelle's Quality Manager for the AMS Center. Ms. Buhl will:
• Review the draft and final TQAP.
• Assign a Quality Assurance Officer (QAO) for this verification test.
• Delegate to other Battelle quality staff any QAO responsibilities assigned below as
needed to meet project schedules.
• Review any audit checklists prepared by the QAO for completeness and detail.
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• Review draft and final audit reports prior to release to the VTC and/or EPA for clarity
and appropriate assessment of findings.
• Review audit responses for appropriateness.
• Review and approve TQAPs and deviations.
• Review draft and final verification report(s) and verification statement(s).
• Maintain real-time communication with the QAO on QA activities, audit results, and
concerns.
• Work with the QAO, VTC, and Battelle's AMS Center Manager to resolve data
quality concerns and disputes.
• Recommend a stop work order if audits indicate that data quality or safety is being
compromised.
Ms. Betsy Cutie is Battelle's QAO for this test. Ms. Cutie will:
• Attend the verification test kick-off meeting and lead the discussion of the QA
elements of the kick-off meeting checklist.
• Prior to the start of verification testing, verify the presence of applicable training
records, including any vendor training on test equipment.
• Conduct a technical systems audit at least once near the beginning of the verification
test.
• Conduct audits to verify data quality.
• Prepare and distribute an audit report for each audit.
• Verify that audit responses for each audit finding and observation are appropriate and
that corrective action has been implemented effectively.
• Communicate to the VTC and/or technical staff the need for immediate corrective
action if an audit identifies TQAP deviations or practices that threaten data quality.
• 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).
• Maintain real-time communication with the Battelle Quality Manager on QA
activities, audit results, and concerns, including potential schedule and budget
problems.
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• Communicate data quality concerns to the VTC and/or Battelle's AMS Center
Quality Manager; recommend the need for a stop work order if audits indicate that
data quality or safety is being compromised.
A5.2 Vendors
The responsibilities of the CO2 analyzer vendors are as follows:
• Review and provide comments on the draft TQAP.
• Approve the final TQAP prior to test initiation.
• Provide a complete CO2 analyzer 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 and maintain their technology, and to operate it in
portions of the test specified in this TQAP, or provide written consent and
instructions for Battelle staff to carry out these activities.
• 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.
A5.3 EPA
EPA's responsibilities are based on the requirements stated in the "Environmental
9 -^^ „,
Technology Verification Program Quality Management Plan" (ETV QMP). The roles of
specific EPA testing staff are as follows:
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Ms. Michelle Henderson is EPA's AMS Center QA Manager. Ms. Henderson will:
• Review the draft TQAP.
• Review the first day of data from the verification test and provide immediate
comments if concerns are identified.
• Perform at her option one external technical systems audit and/or audit of data quality
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 or safety is being compromised.
• Prepare and distribute an assessment report summarizing results of the external audit.
• Review the draft verification report(s) and statement(s).
Dr. John McKernan is EPA's Project Officer for the AMS Center. Dr. McKernan will:
• Review the draft TQAP.
• Approve the final TQAP.
• Review and approve deviations to the approved final TQAP.
• Appoint a delegate to review and approve deviations to the approved final TQAP in
his absence, so that testing progress will not be delayed. Review the first day of data
from the verification test and provide immediate comments if concerns are identified.
• 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.
A5.5. Verification Test Stakeholders
This TQAP and the verification report(s) and verification statement(s) based on testing
described in this document will be reviewed by experts in the fields related to carbon
sequestration and/or analytical instrumentation. The following experts have been providing
input to this TQAP and have agreed to provide a peer review:
• Sally M. Benson, Stanford University, Global Climate and Energy Project Director
• Chuck Dene, Electric Power Research Institute
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• Dominic C. DiGiulio, US EPA
• Bruce J. Kobelski, US EPA
• Eben Thoma, US EPA
The responsibilities of verification test stakeholders include:
• Participate in technical panel discussions (when available) to provide input to the test
design.
• Review and provide input to the TQAP
• Review and provide input to the verification report(s)/verification statement(s).
In addition, the TQAP in general was reviewed with the broader AMS Center
Stakeholder Committee as a presentation during regular stakeholder teleconferences, including
the November 5, 2009 meeting, and input from the committee was solicited.
A6 BACKGROUND
A6.1 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 technology categories recommended for testing are isotopic CC>2 analyzers.
In particular, the use of isotopic CC>2 analyzers for the monitoring of carbon sequestration sites
for possible leakage was identified as an area of interest for technology verification.
Research on carbon storage in geologic reservoirs such as saline formations, coal seams,
and depleted oil and gas fields, has gained momentum in recent years as interest in mitigation of
greenhouse gases, such as CC>2, has increased and a number of pilot-studies have recently been
brought online. Capture and geologic sequestration of CO2 involves capturing emissions at a
power plant or other large source, separating the emissions to isolate CO2, and compressing the
gas. The compressed CC>2 is injected into a deep underground rock formation. Potential sites are
carefully evaluated for adequacy of containment layers, seismic stability, and other factors. As
pilot- and full-scale geologic sequestration programs continue to be implemented, so do the
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needs to monitor leakage. GCS sites are expected to have several types of monitoring needs, as
presented in Table 1.
Table 1. Anticipated Monitoring Needs for the GCS Sites
Location
High risk areas
(transmissions
lines, wells,
etc.)
Sensitive
ecosystems/
population
centers near
sequestration
site
Sequestration
field
Hazard
Subsurface
emissions
Above
surface
equipment
leaks
Intrusion from
nearby well
or geologic
feature
Quantify total
emissions
Monitoring Needs
• May result in high CO2 in
adjacent area (depending on
magnitude of leak)
• CO2 source easily identified
• Portable single-point analyzer
for conducting surveys
• Remote survey tool
• Sensitive ambient monitoring
• Ability to identify or
characterize CO2 source
• Survey tools
• Open path systems
• Flux chambers
Practical Considerations
• Ability to detect subsurface
leak above ground
• High sensitivity analyzers
provide early detection
• Ability to pinpoint leak location
• Variability in ambient CO2
concentrations
• Ability to detect leaks in
ambient air
• Variability in ambient CO2
concentrations
• High sensitivity analyzers
provide early detection
• Ability to quantify emissions
over large geographic area
• Trace mapped emissions to
source
Stable isotope analysis can be used in environmental forensics, for example to aid in
IT I /^ IT -in
determining the source of carbon dioxide. Deviations in the ratio of C to C ( C/ C) in
atmospheric CC>2 relative to that in ambient air can be used to identify input from other carbon
sources, such as fossil fuel combustion, since atmospheric, carbonate, and plant-derived carbon
differ in their 13C/12C relative to the Pee Dee Belemnite (PDB) standard. The relative difference
in stable carbon isotope from the PDB standard, referred to as 513C, is calculated as shown in
Equation A-l and expressed in per mil (%o), or part per thousand.
613C
Sample
13
C/1ZC
Sample
13
C/12C
PDB
- 1 ) X1000
(A-l)
Since the PDB standard was highly enriched in 13C, most naturally occurring carbon
sources have a negative 513C value. For example, ambient air CO2 has a global average 513C
close to -8 per mil (i.e., parts per thousand) (cf, ref 3) and the global mean value from a 1991
inventory of fossil fuel types was -28.5 per mil.4'5 Stable isotope measurements are traditionally
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conducted on discrete samples, such as air collected in canisters, in the laboratory using isotope
ratio mass spectrometry (IRMS), but recent advances in spectroscopic monitoring technology
have made it possible to conduct in situ measurements of stable isotope ratios with high
frequency and precision. 6'7
The use of isotopic CO2 analyzers for ambient air monitoring in areas near GCS sites, for
example, could be used to identify intrusion of non-ambient CC>2 and provide information about
its source. Large-scale leaks in high risk areas where the source is well-understood can be
detected by conventional CC>2 analyzers. Fast-response, portable analyzers, including infrared
"cameras," could be useful as a survey tool to quickly assess larger geographic areas for large-
scale leaks. The high sensitivity and fast response of isotopic CO2 analyzers have the potential
to detect smaller leaks and identify larger subsurface leaks before exceeding the detection limits
of less sensitive techniques. Spectroscopic isotopic CC>2 analyzers have been proposed as a
potentially viable technology for monitoring GCS sites, nearby communities, and sensitive
ecosystems for CO2 leaks, where analyzers would need to have sufficient accuracy and precision
to detect background ambient air concentrations (-350 ppm) and 513C values (—8 per mil) and
capture daily/seasonal variability.
A.6.2 Technology Description
One technique for isotopic CC>2 detection is cavity ring down spectroscopy (CRDS), in
which sensitivity to target analytes is enhanced through the use of multi-pass optical cells that
vastly increase the effective pathlength of the absorbing radiation over typical absorption
techniques.8'9 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
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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
IT I r\
absorbing gas, in this case, both the C and C isotopes of CC>2 in the cavity.
A7 VERIFICATION TEST DESCRIPTION AND SCHEDULE
The purpose of this verification test is to generate performance data on isotopic CO2
analyzers with a particular focus on applications relevant to GCS monitoring applications,
specifically for the sequestration of CC>2 from a coal-fired power plant. The data generated from
this verification test are intended to provide organizations and users interested in GCS
monitoring with information on the potential use of these analyzers for that application and on
their performance under such conditions.
A7.1 Verification Test Description
Battelle testing staff will conduct the test over a period of approximately 5 weeks, which
will involve three distinct activities, or phases, as summarized in Table 2. In Phase 1, the
analytical performance of the CC>2 analyzers will be evaluated under controlled laboratory
conditions with respect to CC>2 isotopic composition and CC>2 concentration. Gas standards of
known isotopic composition and concentration will be used to generate test samples over a range
of CC>2 concentrations and a minimum of two isotopic compositions. During Phase 2, the CC>2
analyzers will be installed in a chamber in which CC>2 leaks will be simulated in ambient air
under controlled conditions and the minimum detectable leak rate will be determined for 13C-
depleted CC>2. Phase 3 will include mobile surveys of the GCS site transmission lines and
infrastructure and continuous monitoring at the GCS site. If feasible within test site operating
requirements, captured CC>2 will intentionally be released to simulate an above-ground leak in a
high-risk area. The CC>2 analyzers will be evaluated on the following performance parameters:
• Accuracy and bias
• Linearity
• Precision
• Response time
• Minimum detectable leak rate
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Table 2. Planned Verification Test Activities
Phase
1
2
3
Location
Battelle Laboratories
Columbus, OH
ABT
Battelle
West Jefferson, OH
GCS site
WV
Testing Activities
Installation
Analyzer operation training
Gas standard challenges
Controlled leak simulations
Mobile surveys
Intentional CO2 release
Continuous ambient monitoring
Remove CO2 analyzers from test site
Data completeness
Operational factors.
When possible, parameters will be assessed with respect to CC>2 concentration and
isotopic composition. Accuracy and bias will be assessed for the CC>2 analyzers being verified
by determining the degree of agreement with known concentrations and isotopic ratios of CC>2
from compressed gas standards. Precision will be assessed in terms of the repeatability of the
CC>2 concentration and isotopic ratio measurements under stable test conditions using CC>2
compressed gas standards. Linearity and response time will also be assessed using commercial
compressed gas standards of CC>2. Minimum detectable leak rate will be assessed by simulating
CC>2 leaks under controlled and ambient conditions. Data completeness will be determined from
a review of the valid data collected during the verification testing period and evaluated separately
for mobile/survey data collection efforts. Operational performance parameters such as
maintenance requirements, ease of use, and field portability will be determined from
observations by the Battelle testing staff. Information on costs will be provided by the
technology vendor. This test is not intended to simulate long-term performance of these
technologies at a monitoring site, but rather assess the feasibility of their use for various GCS
o
monitoring scenarios, such as those suggested by the GEO-SEQ Project Team, who recommend
that monitoring plans be tailored to address the specific conditions and risks for a given site.
Subsequent to the verification test, Battelle will draft a separate verification report for
each analyzer tested. The reports will be reviewed by the respective technology vendor and by
peer reviewers, revised, and submitted to EPA for final approval. In performing the verification
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test, Battelle will follow the technical and QA procedures specified in this TQAP and will
comply with the data quality requirements in the AMS Center QMP.1
A7.2 Proposed Testing Schedule
Table 3 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 2010 and be
completed in July 2010. Each phase of the test is expected to span approximately one to three
weeks.
Table 3. Planned Verification Test Schedule
Phase
1
2
3
Approximate
Date(s),
July 6 -16
July 19-22
July 27 -30
August 13
August 27
September
10
Location
Battelle
Columbus, OH
ABT
Battelle
West
Jefferson, OH
GCS site
WV
Testing Activities
Installation
Analyzer operation
training
Gas standard challenges
Controlled leak
simulations
Mobile surveys
Intentional CO2 release
Continuous ambient
monitoring
Remove CO2 analyzers
from test site
Data Analysis and Reporting
Begin preparation of report
template
Review and summarize testing
staff observations
Compile data from CO2
analyzer(s)
Review and summarize testing
staff observations
Compile data from CO2 analyzer
Begin data analysis
Review and summarize testing
staff observations
Compile data from CO2 analyzer
Perform data analysis
Begin draft report(s)
Complete draft report(s)
Complete peer review of draft
report(s)
Revise draft report(s)
Submit final report for EPA
approval
A7.3 Battelle Laboratory Testing Facilities
Phase 1 testing will be conducted in Battelle laboratories in Columbus, Ohio. Battelle
staff will conduct testing in laboratories that are fully equipped for the production and delivery of
CC>2 in test atmospheres of controlled temperature and humidity.
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A7.4 Ambient Breeze Tunnel
The Ambient Breeze Tunnel (ABT) facility is located at the Battelle West Jefferson
campus. It will be used to generate and deliver CC>2 leaks in ambient air for the purpose of
characterizing the minimum detectable leak rate of the CC>2 analyzers. The ABT has physical
dimensions of approximately 150 x 20 x 20 feet (L x W x H), while the entire facility area
measures approximately 190 x 60 feet. Included in the facility are test trailers that can be used to
conduct tests, analyze test data, and provide storage. The area is secured by a gated fence to
offer a protected location for test equipment and related materials. The site provides a secure
location to set up and conduct tests or perform maintenance, while allowing operators access to
all the amenities of the facility (storage, power, air compressor, internet access, etc.).
As shown in Figure 2, the ABT itself is divided into five major sections. Although it will
be used for this test to release CO2 as a controlled leak, the facility was designed to generate
aerosol. The aerosol generation section is the segment of the test system where the challenge
aerosol is generated, but in this case where the CC>2 gas will be released. The baffles in the
mixing section of the ABT enhance mixing of the CC>2 gas with the ambient air by creating
mixing inducing vortices. Whereas the inlet baffle upstream of the aerosol generation section
creates relatively large mixing vortices, the "checkerboard" baffle plane generates smaller
mixing vortices. The result is a series of mixing vortices starting out relatively large at the ABT
inlet and growing increasingly smaller through the length of the ABT mixing section. In the
Exhaust
- Blower Filter
LLDoors
Reference Samphn
and Test Section
Mixing
Baffles
Test Control Center
Aerosol
Generation Center Generation
Figure 2. Schematic Diagram of the ABT
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transition section, the flow velocity across the cross section is fairly consistent, and the air
continues to mix with the intentionally generated material due to turbulence. The sampling
section is the portion of the ABT where sampling instrumentation, including the systems being
tested and those instruments used to characterize the challenge, are located. The exhaust section
of the ABT contains the large blower that pulls air through the test system at volumetric flow
rates of up to about 120,000 cubic feet per minute (cfm). The blower is contained within a
wooden structure called the blower house, which is essentially a large room with a cement floor,
wooden ceiling and walls, and two large "filter doors" designed to hold a total of 56 filters (28
filters per door) with standard nominal dimensions of 2 x 2 feet. During testing, the amount of
CC>2 released is expected to increase the CO2 concentration in the ABT by only a small amount
(i.e., 1 ppm). A photograph of the ABT is shown in Figure 3.
Figure 3. Photograph of the ABT
A7.5 GCS Test Site
Field testing will be conducted at a coal-fired power plant in West Virginia, where CO2
from the flue gas is being captured, separated, compressed, and stored in a geologic formation
over 7,000 feet below the surface. Figure 4 shows a diagram of the GCS site (not to scale).
When operational, approximately 100,000 metric tons per year (tonnes/year) (-274 tonnes/day)
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of captured and compressed CO2 will be provided for injection into the two deep wells. The
injection wells, monitoring wells, above-ground transmission pipeline, and other site features are
accessible by vehicle for conducting mobile surveys and as sites for continuous monitoring.
Battelle staff will position a shed near the main injection well to provide shelter for the CC>2
analyzers; power is available at the injection well site.
CO2 Compression
and Injection
Depth
(ft bgs)
Injection
Well
1,000-
2,000 —
3,000-
4,000-
5,000 —
6,000 —
7,000 —
8,000 —
9.000—
10,000 —
CO2 Pipeline
Slipstream Capture
CC>2 Capture
and Separation
Confining
^Layers
Storage
Reservoir
v Liquid
Supercritical
CO2
NOT TO SCALE
Figure 4. Diagram of GCS Site
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AS QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA
The objective of this verification test is to evaluate the performance of the CO2 analyzers
under potential scenarios relevant to GCS monitoring. This evaluation will in part assess the
capabilities of the CC>2 analyzers for determining the CC>2 concentration and isotope ratio in the
ambient air and to detect leaks of CC>2 gas with isotope ratios different from ambient air.
Additionally, this verification test will include instrument challenges using CC>2 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 CC>2
analyzers being tested including data completeness, ease of use, and maintenance requirements.
DQIs indicate the minimum quality of data required to meet the objectives of the
verification test and are different than the QA/QC requirements. To ensure that this verification
test provides suitable data for a robust evaluation of performance, a data quality indicator (DQI)
has been established for leak flow rate accuracy in Phase 2. The DQI was established to ensure
that data used to support the quantitative performance evaluations of the CO2 analyzers are of
sufficient quality. The DQI for these supporting measurements is quantitatively defined in Table
4 along with the acceptance criteria. Quantitative performance parameters for vendor technology
performance are discussed in Section B.
Table 4. DQI and Criteria for Critical Supporting Measurements
Phase
2
DQI
Leak flow rate
accuracy
Method of
Assessment
Comparison to
independent flow
transfer standard
Frequency
Each
simulated leak
test
Acceptance
Criteria
±10%
Corrective
Action
Investigate
discrepancy.
Inspect meter and
replace meter box
as needed.
During Phase 2, the accuracy of the leak flow rate will be verified using an independent
flow transfer standard. If greater than 10% relative percent difference is found, Battelle will
investigate the discrepancy and replace the flow transfer standard as needed. Additionally, the
verification test relies in part on observations of the Battelle field testing staff for assessment of
the performance of the CC>2 analyzers 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.
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The Battelle QAO will perform a technical systems audit (TSA) of laboratory and field-
based testing activities to augment these QA/QC requirements. A TSA of Phase 1 laboratory-
based testing activities will be performed within the first week of the verification test. A TSA of
field testing activities will be performed within the first week of the Phase 3 GCS field testing.
The EPA Quality Manager also may conduct an independent TSA, at her discretion.
A9 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 has a
minimum of a bachelor's degree in science/engineering.
Portions of the verification test described in this TQAP will be performed at a GCS site.
All participants in this verification test (i.e., Battelle, EPA, and vendor staff) will adhere to the
health and safety requirements of the GCS site and in Battelle facilities. For example, personal
CC>2 monitors will be used in locations where high CC>2 levels may be encountered. Vendor staff
will operate only their CC>2 analyzers during parts of the verification test. They are not
responsible for, nor permitted to, operate the test site equipment or perform any other verification
activities identified in this TQAP.
Battelle testing staff will give a site-specific safety briefing to all staff visiting the test site
or Battelle laboratories/facilities. This briefing will include a description of emergency operating
procedures (i.e., in case of fire, tornado, laboratory accident), identification, location, and
operation of safety equipment (e.g., fire alarms, fire extinguishers, eye washes, exits), and host
site PPE requirements and site-specific procedures.
A10 DOCUMENTATION AND RECORDS
The documents and records for this verification test include the TQAP, certificates of
analysis (COA), 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
documents and records will be maintained in the Verification Test Coordinator's office during
the test and will be transferred to permanent storage at Battelle's Records Management Office
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(RMO) at the conclusion of the verification test. Documents and records generated at the ABT
and GCS test site will be stored in a secure location until they can be transferred to the
Verification Test Coordinator (within one week of generation). Electronic documents and
records will also be uploaded to a SharePoint site designated for this test and will be provided to
EPA upon request. 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. 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 TQAP will specifically address verification of
isotopic CO2 analyzers for GCS monitoring applications by evaluating the following
performance factors:
• Accuracy and bias
• Linearity
• Precision
• Response time
• Minimum detectable leak rate
• Data completeness
• Operational factors.
The verification test will be conducted over a period of approximately 5 weeks. A
window of approximately one week prior to testing will be available for installing the CO2
analyzers at the facility, and conducting a trial run of the CO2 analyzers before the verification
test begins. The installation and training period is scheduled to begin in late June, 2010. The
19 1 ^
analyzers undergoing verification will report total CO2 concentrations ( CO2 + CO2) and
isotopic composition (513C) for all testing activities. The verification testing will involve a
combination of controlled gas challenges in an indoor laboratory environment and a sheltered
ambient breeze tunnel, survey measurements for above-ground leak detection, and continuous
ambient monitoring, conducted in three distinct phases:
• Phase 1 - Battelle will evaluate the analytical performance of the CO2 analyzers
under controlled laboratory conditions. The CO2 analyzers will be challenged with
gas standards of known isotopic composition and concentration to generate test
samples over a range of CO2 concentrations and isotopic compositions. Bias with
respect to ambient temperature and relative humidity (RH) will also be assessed.
• Phase 2 -Battelle will evaluate the minimum detectable CO2 leak rate for 13C-
depleted CO2. Battelle will install the CO2 analyzers in the ABT where CO2 leaks
1 9
will be simulated in ambient air under controlled conditions by releasing pure CO2.
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• Phase 3 - Battelle will evaluate the ability of the CC>2 analyzers to survey GCS site
transmission lines and infrastructure for leaks and be used for continuous monitoring
at the GCS site. If feasible within test site operating requirements, captured CO2 will
intentionally be released to simulate a high risk area, above ground leak.
The CC>2 analyzer readings during Phase 1 will be compared to the delivered
concentrations and isotopic ratios as calculated based on dilution ratios and concentration and
isotopic ratio of the certified gas standards used for testing. For Phases 2 and 3, the CO2
analyzers will be evaluated based on a determination of the minimum detectable CC>2 leak, where
the leak source gas is pure (99.95%) 12CC>2. The leak rate at a range of 513C values between
ambient air (approximately -8 per mil) and those expected for fossil fuel combustion
(approximately -30 per mil) will be calculated based on the results of the minimum detectable
1 9
leak determination from Phase 1 and the actual concentration of CC>2 in the gas standard. If an
intentional release of captured CC>2 is conducted, the time elapsed before the leak is detected by
the CO2 analyzers will be reported.
Table 5 presents a summary of the tests to be performed. The time durations specified in
the following sections were set assuming the CO2 analyzers are operated with 1-minute time
resolution. If higher time resolution settings are used, the test durations may be shortened
provided that a minimum of five CC>2 analyzer measurements could be reported during a given
test condition. The Verification Test Coordinator will determine what time resolution will be
used during the verification test to balance practical considerations against the requirements
described in this TQAP, with input from the technology vendor.
Throughout the verification test, each CC>2 analyzer undergoing testing will be operated by the
vendor's own staffer by Battelle staff trained by the vendor. However, the intent of the testing
is for the CC>2 analyzers to operate in a manner simulating use by GCS site operators to monitor
and/or survey a facility on a continuous basis or to monitor ambient air nearby a GCS site with
little user intervention. 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 CO2
analyzer in normal unattended operation. Repair or maintenance procedures may be carried out
at any time, but testing may not be interrupted, and data completeness will be reduced if such
activities prevent collection of CC>2 analyzer data required for verification.
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Table 5. Summary of Tests and Testing Frequency
Phase
1
1
1
1
2
3
Performance
Parameter
Accuracy and
Bias
Linearity
Precision
Response
Time
Minimum
Detectable
Leak Rate
Leak
Response
Rate
Objective
Determine degree
of quantitative
agreement with
compressed gas
standard
Determine linearity
of response over a
range of CO2
concentrations
Determine
repeatability of
successive
measurements at
fixed CO2 levels
Determine 95%
rise and fall time
Determine the
minimum
detectable CO2
leak rate under
controlled and
ambient conditions
Determine the
amount of time
between an
intentional release
of captured CO2
and detection of
the leak by the
CO2 analyzers
Comparison
Based On
Challenges with
CO2 gas
standards of
known 513C at 3
RH levels and 3
temperatures
Dynamic spiking
with gas standards
Repetitive
measurements
under constant
facility conditions
measured
Recording
successive
readings at start
and end of
sampling CO2 gas
standard
Repetitive
measurements of
a low-level 12CO2
leak
Recording the
elapsed time
between start of
release and
positive detection
Testing
Frequency
-3 runs at each of
12 nominal
concentrations
(one 513C value)
-1 run at each of
15 combinations
ofRH,
temperature, and
CO2 concentration
(one 513C value)
-3 runs at each of
9 combinations of
CO2 concentration
and 513C)
-3 runs at each of
12 nominal
concentrations
(one 513C value)
-3 runs at each of
9 combinations of
CO2 concentration
and 513C)
-3 runs at each of
12 nominal
concentrations
(one 513C value)
Once during each
day of dynamic
spiking testing
Once
Once (optional)
Number of
Data
Points
78
36
36
3
1
1
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Bl.l Test Procedures
The CC>2 analyzers undergoing verification will be installed at an appropriately sheltered
location at each test site and/or on a mobile platform for conducting surveys. For gas standard
challenges, the inlet port for the CC>2 analyzers will be connected to a manifold to which gas
standards will be delivered and that is equipped with an ambient pressure vent. Excess CO2 and
instrument exhaust will be vented to a hood or outside inhabited areas. A broad range of
concentrations will be tested at a single 513C to establish basic concentration-based performance
of the CC>2 analyzers; however, fewer concentrations will be tested for bias tests involving
different 513C values due to schedule and resource limitations.
B1.1.1 CO2 Concentration Accuracy, Bias, Precision, and Linearity
During Phase 1, each of the CC>2 analyzers will be challenged with a series of compressed
CO2 gas standards diluted in CCVfree zero air to achieve measurements in the range of expected
ambient air concentrations (i.e., 350 ppm) and also at higher concentrations (up to 5000 ppm
CC>2) to simulate concentrations that could be observed in high hazard areas. Three non-
consecutive measurements will be recorded at each of twelve different nominal concentration
levels at one 513C value. Each concentration will be supplied to the analyzers for at least twenty
minutes. A calibrated programmable dilution system may be used to automatically supply the
diluted gas standards to the CC>2 analyzers. Table 6 shows the approximate CC>2 concentration
values to be supplied to the analyzers being tested, and the order in which the concentrations will
be supplied. As Table 6 indicates, the CO2 concentrations will first be supplied to the analyzers
in increasing order, then in random order, and finally in decreasing order. Dilutions will be
prepared from a certified compressed mixture of 11% CC>2 in air (Air Liquide Acublend Master
Class, 11.0% ±1%). These tests will be conducted at room temperature without added humidity.
The room temperature will be recorded daily using a calibrated thermometer.
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Table 6. Approximate CO2 Concentrations for Multi-point Challenges
Nominal CO2
Concentration (ppm)
0
100
200
300
400
500
750
1600
2450
3300
4150
5000
Measurement Number
1
2
3
4
5
6
7
8
9
10
11
12
16
22
18
14
23
20
15
17
21
19
24
13
36
35
34
33
32
31
30
29
28
27
26
25
Bl.1.2 Isotopic Ratio Bias
During Phase 1, the analyzer response to the series of CC>2 gas standards will be used to
evaluate accuracy, bias, precision, and linearity with respect to CO2 concentration. Section B1.2
presents the statistical procedures that will be used. Accuracy will be calculated at each
concentration and for each replicate relative to the nominal CC>2 concentration. Bias will be
calculated for each series of multi-point CC>2 challenges. The analyzer precision will be
demonstrated by the reproducibility of the analyzer response at each nominal CO2 concentration
after a stable reading is achieved. Linearity will be assessed by establishing a multi-point
calibration curve from the analyzer response.
Analyzer bias with respect to the 513C value will be assessed by challenging the analyzers
with dilutions from three CC>2 isotope mixtures [SMU Stable Isotope Laboratory, through Oztech
Trading Corporation, -3.61; -10.41; and -40.80 per mil (0.01 standard deviation)], each at three
CC>2 concentrations (see Table 7). Bias will be calculated for each 513C value. Each CC>2
concentration/513C pair will be delivered to the analyzers three times for a total of 27 data points.
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Table 7. Approximate CO2 Concentrations and Isotope Ratios for Bias Tests
Approximate
-3.61 d
-10.41
-40.8
61JC(permil)
:001(a)
±0.01
±0.01
Nominal CO2 Concentrations
(ppm)
350
500
1000
350
500
1000
350
500
1000
(a) Uncertainties are standard deviations reported on COAs for each gas standard.
El. 1.3 Temperature and RH Bias
Assessments of bias due to the ambient and sample temperature and RH will be assessed
during Phase 1 by installing the analyzers in a temperature and RH-controlled chamber and
delivering dilutions of a CC>2 gas standard to the chamber at three concentrations under varying
temperature and RH conditions. The CC>2 gas dilutions will pass through a coil placed within the
chamber so the sample temperature will match ambient temperatures. Battelle staff will adjust
the RH of the CO2 gas dilutions by humidifying all or a portion of the gas stream using water
bubblers or similar apparatus. The RH of the sample will be verified using an independent
calibrated sensor. The specific target conditions are listed in Table 8. If possible, a high
RH/high temperature (i.e., >90% RH and >30°C) condition will also be included. The analyzers
will be subjected to each condition once for a minimum of twenty minutes. One 513C value will
be used for these tests. Bias will be calculated as described in Section B1.2.
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Table 8. Approximate Conditions for Temperature and RH Bias Tests
Approximate RH
(%)
0±10%
50 ±10%
90 ±10%
Approximate
Temperature (°C)
20±2°C
4±2°C
20 ± 2°C
32 ± 2°C
20 ± 2°C
32 ± 2°C (optional)
Nominal CO2
Concentration (ppm)
350
500
1000
350
500
1000
350
500
1000
350
500
1000
350
500
1000
350
500
1000
Bl.1.4 Response Time
The data collected for the multi-point CO2 challenges (Section B 1.1.2) during Phase 1
will also be used to determine the analyzer response time. The 95% rise time and 95% fall times
will be calculated for the consecutive concentration steps (Table 6, measurements 1-12 and
25-36). Calculations for response time are described in Section Bl.2.6.
Bl.1.4 Minimum Detectable Leak Rate
The minimum leak rate that can be detected above ambient variability and the precision
of the CC>2 analyzers will be determined under controlled conditions during Phase 2. The
analyzers will be installed in the Reference Sampling and Test Section of the ABT. A leak will
be considered to be successfully identified if an increase or decrease in the measured 513C,
greater than 2 times the variability in ambient 513C, is measured by the CC>2 analyzer for at least
three consecutive measurement points. The ambient air 513C variability will be determined from
one hour of ambient air CC>2 analyzer data measured on the day of testing. Injection of pure
(99.95%) 12CC>2 into the ambient air diluent being drawn into the ABT will be used to simulate a
low-level leak of 13C-depleted CC>2. This approach assumes that a low-level leak would be well-
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mixed in the ambient air diluent before reaching the CC>2 analyzers undergoing verification,
which is expected for a flow rate of approximately 30,000 cfm (approximately 5 miles per hour
velocity). The equivalent leak rate as a function of source 513C will be back-calculated for
several relevant 513C values, including the expected value for the GCS field site. This
calculation will assume that the magnitude of the measured changes in 513C values from ambient
levels will be the same for the pure (99.95%) 12CC>2 and for the calculated leak levels for 13C-
depleted CC>2. This assumption allows the calculation of CC>2 release rate necessary to achieve
the overall 513C change for a given 513C source value, knowing the ambient 513C value and the
19
flow rate of air through the ABT. It should be noted that the use of a pure C source for leakage
(i.e., -1000 per mil) maximizes instrument sensitivity to 513C, although not to total CC>2
concentration; thus, conditions during an actual leak would be different with respect to both 513C
and total CC>2 concentration. Although it would be preferable to simulate leaks using a mixture
of 13CC>2 and 12CC>2 at a ratio that would be realistic for fossil fuel combustion, a substantial
quantity of CC>2 source gas would be needed to meet the low-level leak conditions described
above and falls outside the limitations of this verification test.
The initial 12CC>2 leak rate will be set at a nominally detectable level that is twice the
standard deviation (s) in 513C measured by the analyzer for a period of at least one hour on the
day of testing or the vendor's reported 513C precision, whichever is greater. Leaks at that rate
will be introduced three times for approximately 20 minutes with at least 15 minutes of ambient
air flow between simulated leaks. If all three leaks are successfully detected, the leak rate will be
reduced at the discretion of the testing staff. At each leak rate, the CO2 analyzer will report at
least 4 data points during each of three trials, for a minimum of 12 data points. Once a leak rate
that is not identified for each of the three trials has been reached, the rate will be increased to a
level where all three replicates are successfully identified. This leak rate is the minimum
detectable limit for the technology under the test conditions. If time permits, this process may be
repeated during the Phase 2 test period. A conventional CO2 analyzer will be used to monitor the
CC>2 concentration in the ambient air diluent to assist in identifying changes in air mass or nearby
CC>2 sources that could impact the CC>2 concentration or 513C. Keeling plots may also be used to
evaluate the CO2 analyzer's ability to detect CO2 leaks. Specifically, uncertainty in the intercept
of the Keeling plot will be determined.
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Bl. 1.5 Ambient Air Monitoring
In the evenings and when the CC>2 analyzers are not undergoing testing during Phase 3,
they will be installed in a shelter near the GCS wellhead and set up to monitor ambient air. The
purpose of this activity is to evaluate data completeness and operational factors during
deployment for ambient monitoring. The ambient air measurements (CC>2 concentration and
513C) and meteorological conditions will be reported with summary statistics (average and
standard deviation). While the analyzers are installed at the wellhead, a planned release of
captured CC>2 will be conducted if feasible within plant operations. The leak rate response time,
the time between initiation of the release and when the leak is detected by the CO2 analyzers as
described in Section Bl.1.4, will be determined.
Bl.1.6 Mobile Surveys
During Phase 3, the CC>2 analyzers will be transported to road-accessible features of the
GCS, such as transmission lines, monitoring wells, and abandoned wells. The purpose of these
tests is to evaluate the ease of use and operational factors of the analyzers during use in a mobile
survey mode. Analyzers will be installed on a mobile platform, such as a pick-up truck, and set
up to sample continuously as the analyzers are moved to and between target features. In addition
to the above-ground transmission lines, a minimum of three groundwater monitoring wells and 6
soil gas monitoring wells will be surveyed. Features will be selected at the discretion of testing
staff based on access, atmospheric/meteorological conditions, and potential of specific features
to leak captured or sequestered CC>2. The feature locations will be documented in a manner that
will not identify the GCS site location, but provide descriptive information about the type of
feature and its role in carbon capture or sequestration. Ambient air CC>2 concentrations and 513C
values will be recorded as the feature is approached, while in the immediate vicinity of the
feature, and as the analyzer is moved away from the feature. Approximate survey location and
speed data will be collected using a common GPS devices (e.g., GPS equipped cellular
telephone); GPS coordinates will not be reported. Since meteorology can influence the level of
detection, meteorological conditions near each feature will be recorded and reported. During
testing, the vehicle speed will be recorded and maintained as constant as possible and care will
be taken to ensure that exhaust from the vehicle transporting the analyzers does not contribute to
the measured CC>2 signal. A sampling line will be used to supply the analyzers with ambient air.
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To the extent possible, the vehicle will be driven such that the exhaust is downwind of the
sampling line. Measurements recorded during the mobile surveys, particularly while the vehicle
is idling, will be closely investigated to assess if there is any potential interference from the
vehicle exhaust. If evidence of interference is suspected, the suspect data will be flagged and
reported accompanied by an explanation.
Bl.l. 7 Data Completeness
No additional test procedures will be carried out specifically to address data
completeness. This parameter will be assessed based on the overall data return achieved by each
analyzer.
Bl. 1.8 Operational Factors
Operational factors such as maintenance needs, calibration frequency, data output,
consumables used, ease of use, repair requirements, and sample throughput will be evaluated
based on operator observations. Battelle testing staff will document observations in a laboratory
record book (LRB) or data sheets. Examples of information to be recorded include the daily
status of diagnostic indicators for the technology, 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 technology down time or data acquisition failure,
operator observations about technology startup, ease of use, clarity of the vendor's instruction
manual, user-friendliness of any needed software, overall convenience of the technologies and
accessories/consumables, or the number of samples that could be processed per hour or per day.
Battelle will summarize these observations to aid in describing the technology performance in
the verification report on each technology.
B1.2 Statistical Evaluation
The statistical methods and calculations used for evaluation of the quantitative
performance parameters are described in the following sections.
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B 1.2.1 Accuracy
Accuracy of the CC>2 analyzers with respect to the individual CC>2 gas standards will be
assessed as the percent recovery (%R), using Equation B-l:
r /Y - XM
%R =14- X 100
L \ X }\ (B-l)
where Y is the average measured CO2 analyzer value and X is the nominal CC>2 gas standard
concentration. The average, minimum, and maximum %R values will be reported for each series
of multi-level CO2 challenges. The accuracy of the analytical standards, as certified by the
manufacturer, will also be reported. Similarly, the accuracy of the CC>2 analyzers with respect to
isotope ratio will be determined where Y is the average measured CC>2 analyzer 513C value and X
is the nominal 513C value.
B 1.2.2 Bias
Bias of the CC>2 analyzers is defined as a systematic error in measurement that results in
measured error that is consistently positive or negative compared to the true value. The bias will
be calculated as the average percent difference (%D) of the CO2 analyzer compared to the
nominal CC>2 gas standard value (with respect to concentration and isotope ratio) and will be
calculated for each series of multi-point CC>2 challenges and isotope ratio bias tests, using
EquationB-2:
(B-2)
where A: is the number of valid comparisons, and Y and X are the same as stated in B 1.2.1. For
temperature and RH bias, the basis of comparison for isotope ratio will be the ratio measured by
the CC>2 analyzer at room temperature without added water vapor (dry conditions).
Bl.2.3 Precision
The precision of the CC>2 analyzers will be evaluated from the triplicate responses to each
CC>2 gas standard supplied during the multi-point challenges (outlined in Table 6). The precision
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will be defined as the percent relative standard deviation (%RSD) of the triplicate measurements
and calculated for each CC>2 concentration and isotope ratio listed in Table 6, using
Equation B-3:
%RSD; = — X 100
Tt
Y' (B-3)
where Yi is the average analyzer response at CC>2 concentration or isotope ratio /', and s the
standard deviation of the analyzer responses at that concentration. The overall average %RSD
will also be calculated for each series of multi-point CO2 challenges (with respect to CO2
concentration) and for each gas standard (with respect to CC>2 513C) and will include the %RSD
for all CC>2 concentrations tested for each gas source.
Bl.2.4 Linearity
Linearity with respect to concentration and isotopic ratio will be assessed by a linear
regression analysis of the gas challenge data using the calculated CC>2 concentrations or 513C as
the independent variable and the CO2 analyzer results as the dependent variable. The results of
the gas challenge tests will be plotted and linearity will be expressed in terms of slope, intercept,
r\
and coefficient of determination (R ).
B1.2.5 Minimum Detectable Leak Rate
The minimum detectable leak rate that represents the minimum level successfully
identified by each of three trials will be determined experimentally; all trial results will be
reported. The equivalent leak rate at several 513C values of interest, such as -30 per mil, will be
calculated based on the flow rate of-30 per mil CO2 that would be needed to give the same
change in measured 513C with respect to ambient air (-8 per mil). For example, a leak rate of 0.9
Lpm of 99.95% 12CC>2 would result in a 513C of-11.0 per mil under expected conditions at the
ABT. The equivalent final 513C could be achieved with a leak rate of 46.9 Lpm for a -30 per mil
CC>2 source. (Note that the change in total CO2 concentration would not be equivalent for the
two CC>2 sources.) In addition, the isotopic ratios measured by the CO2 analyzers will be plotted
versus the inverse of the CC>2 concentration (i.e., in Keeling plots) and the uncertainty in the
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intercept determined. The intercept will represent the isotopic ratio of the leak source. When the
Keeling plot intercept for a given leak rate is equal to the known value of the leak, within the
uncertainty of the intercept, the leak rate would be considered to be "detectable." Keeling plots
will also be developed for intentional releases at the GCS site, if conducted.
Bl.2.6 Response Time
Response time will be assessed in terms of both the rise and fall times (with respect to
CO2 concentration) of each CO2 analyzer when sampling CC>2 gas standards. Rise time (i.e., 0%
- 95% response time) will be determined by recording all CC>2 analyzer readings as the gas
supplied to the analyzers is switched between increasing concentration CC>2 standards. 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 CC>2 analyzer readings as the
CC>2 concentration in the gas supplied is reduced in concentration. For CC>2 analyzers which
provide periodic rather than continuous readings, determination of rise and fall times may
involve interpolation between readings. Rise and fall times will each be determined once during
multi-point gas challenges. Rise and fall times will be reported in units of seconds.
B1.2.7 Data Completeness
Data completeness will be assessed based on the overall data return achieved by each
CC>2 analyzer during the testing period. For each of the CC>2 analyzers, this calculation will use
the total number of apparently valid data points reported by the analyzers divided by the total
number of data points potentially 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.
B1.3 Reporting
The statistical comparisons described above will be conducted separately for each CC>2
analyzer being tested, and information on the operational performance will be compiled and
reported. A verification report will be prepared for each CO2 analyzer 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 CC>2 analyzer 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 samples will not be collected during this test.
B3 SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Reference samples will not be collected during this test.
B4 ANALYTICAL METHOD REQUIREMENTS
No analytical methods are needed for this test.
B5 QUALITY CONTROL REQUIREMENTS
Reference measurements will not be collected as part of this verification test.
B6 INSTRUMENT/ EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
When Battelle staff operate and maintain the CO2 analyzers undergoing testing, those
activities will be performed as directed by the vendor. Otherwise, operation and maintenance of
the analyzers will be the responsibility of the analyzer vendors.
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B7 INSTRUMENT CALIBRATION AND FREQUENCY
The calibration of instrumentation used in this verification test, such as dilution systems
and flow controllers, will be verified immediately prior to use in this verification test. A
minimum of three flow rates for each flow controller or flow reader will be verified with an
independent factory-calibrated flow meter. Calibration of the meteorological station will have
been performed within 1 year of the verification test.
The CO2 analyzers undergoing testing will be calibrated initially by the respective
analyzer vendors at the time of installation, at the vendor's discretion. Calibration gases will not
be provided for vendors' use; instrument calibration gases must be independent of those used for
testing activities. In the event that recalibration is deemed necessary, that recalibration will be
carried out by the analyzer vendor, or by Battelle staff under the direction of the vendor. All
calibrations performed will be documented by Battelle staff in the LRB dedicated to the
respective analyzer.
B8 INSPECTION/ACCEPTANCE OF SUPPLIES AND CONSUMABLES
Upon receipt of any supplies or consumables used for the gas challenges, Battelle 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 air used for diluting CC>2 standards for delivery to the CC>2 analyzers will be
commercial ultra-high purity (UHP, i.e., minimum 99.999% purity). Compressed gas standards
containing CC>2 will be obtained for use in the laboratory-based gas standard challenges, for
example 11% CO2 in air, and obtained from Air Liquide America Specialty Gases LLC
IT I r\
(formerly Scott Specialty Gases). Certified mixtures of CCV CC>2 will be obtained for the
19
isotope bias testing from Oztech Trading Corporation. Pure CC>2 (99.95%) will be obtained for
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leak rate determination testing from Cambridge Isotopes. 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.
BIO DATA MANAGEMENT
Various types of data will be acquired and recorded electronically or manually by
Battelle and vendor staff during this verification test. All manually-recorded 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 9 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 LRB. 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 or subcontractor staff during the
verification test will be reviewed by a Battelle staff member within five days 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 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 TQAP.
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Table 9. Summary of Data Recording Process
Data to Be Recorded
Dates, times, and
details of test events
CO2 analyzer
calibration information,
maintenance, down
time, etc.
CO2 analyzer readings
Supplemental CO2
concentration and
meteorological
parameter
measurement 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
and
meteorological
station
How Often
Recorded
Start/end of
test event
When
performed
Recorded
continuously by
each
monitoring
system
Recorded
continuously by
analyzers
By Whom
Battelle staff
Vendor and
Battelle staff
Vendor staff
for transfer to
Battelle
Battelle staff
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
statistical analysis
and comparisons
Battelle will provide technology test data and associated reference data (including
records; data sheets; notebook records) from the first day of testing within one day of receipt to
EPA for simultaneous review. The goal of this data delivery schedule is prompt identification
and resolution of any data collection or recording issues. These data will labeled as preliminary
and will not have had a QA review before their release.
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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
TQAP is to establish mechanisms necessary to ensure this. Internal quality control measures
described in this TQAP, 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, who will
contact the Battelle AMS Center Manager, Battelle AMS Center Quality Manager, EPA AMS
Center Project Officer, and EPA AMS Center Quality Manager if any deviations from the TQAP
are observed. The Verification Test Coordinator will describe the deviation in a teleconference
or by email, and once a path forward is determined and agreed upon with EPA, the deviation
form will be completed. Technical staff has 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 by the Verification Test Coordinator and Battelle testing staff to
identify and appropriately address the issue, 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
Since no reference measurements will be conducted, no performance evaluation (PE)
IT I r\
audits are planned for this verification test. The certified CO2/ CO2 gas mixtures to be used in
this verification test have COAs and a calibrated dilution system will be used to ensure that test
reference gas concentrations are accurate.
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C1.2 Technical Systems Audits
The Battelle QAO will perform a TSA during performance of laboratory and field-testing
activities. The purpose of these audits is to ensure that the verification test is being performed in
accordance with the AMS Center QMP1 and this TQAP. In this TSA, the Battelle QAO may
compare actual test procedures to those specified or referenced in this plan, and review data
acquisition and handling procedures. The Battelle QAO will prepare a project-specific checklist
based on the TQAP requirements to guide the TSA, which will include a review of the test
location and general testing conditions; observe the testing activities; and review laboratory
record books. She will also check gas standard certifications and data acquisition procedures,
and may confer with the vendor staff. The Battelle QAO will prepare an initial TSA report and
will submit the report to the EPA Quality Manager (with no corrective actions documented) and
Verification Test Coordinator within 10 business days after completion of the audit. A copy of
each final TSA report (with corrective actions documented) will be provided to the EPA AMS
Center Project Officer and Quality Manager within 20 business days after completion of the
audit. 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 QAO, or designee, will audit at least 10% of the sample results data acquired
in the verification test and 100% of the calibration and QC data versus the TQAP requirements.
Four ADQs will be conducted for this project: The first batch of data will be audited within
10 business days of receipt and assessed using a project-specific checklist. Additional ADQs
will be audited within 10 business days of receipt of all Phase 1, 2, and 3 data. During these
audits, the Battelle QAO, or designee, will trace the data from initial acquisition (as received
from the vendor's technology), through reduction and statistical comparisons, to final reporting.
All calculations performed on the data undergoing the ADQ 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. All QC data and all
calculations performed on the data undergoing the audit will be checked by the Battelle QAO.
Results of each ADQ will be documented using the checklist and reported to the Verification
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Test Coordinator and EPA within 10 business days after completion of the audit. A final ADQ
that assesses overall data quality, including accuracy and completeness of the technical report,
will be prepared as a narrative and distributed to the Verification Test Coordinator and EPA
within 10 business days of completion of the 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 all audits will be submitted to EPA within 10 business days
as noted above. 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. (If the QA audit identifies a technical
issue, the Verification Test Coordinator or Battelle AMS Center Manager will be
consulted to determine the appropriate corrective action.
• 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
C2 REPORTS TO MANAGEMENT
During the field and laboratory evaluation, any TQAP deviations will be reported
immediately to EPA. The Battelle Quality Manager and/or Verification Test Coordinator, 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. A summary of the required
assessments and audits, including a listing of responsibilities and reporting timeframes, is
included in Table 10. If serious quality problems exist, the Battelle Quality Manager will notify
the AMS Center Manager, who is authorized to stop work. Once the assessment reports have
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 TQAP and final report are reviewed by the EPA AMS Center Quality Manager and
the EPA AMS Center Project Officer. Upon final review and approval, both documents will
then be posted on the ETV website (www.epa.gov/etv).
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Table 10. Summary of Assessment Reports1
Assessment
Each ISA
(Initial)
Each ISA
(Final)
ADQ (Initial)
ADQ (Phases 1 ,
2, and 3)
ADQ
(Final)
Prepared By
Battelle
Battelle
Battelle
Battelle
Battelle
Report Submission
Timeframe
10 business days after ISA is
complete
ISA response is due to QAO
within 10 business days of
receipt from QAO
ISA responses will be verified
by the QAO and provided
within 20 business days
ADQ will be completed within
10 business days after receipt
of first data set
ADQ will be completed within
10 business days after all data
for a phase is submitted
10 business days after
completion of the verification
report review
Submitted To
EPA ETV AMS Center
EPA ETV AMS Center
EPA ETV AMS Center
EPA ETV AMS Center
EPA ETV AMS Center
Any QA checklists prepared to guide audits will be provided with the audit report.
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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 TQAP. 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 were collected
under appropriate testing.
The data validation requirements for this test involve an assessment of the quality of the
data relative to the DQI for this test referenced in Table 4. Any deficiencies in these data will be
flagged and excluded from any statistical comparisons to the CO2 analyzers 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 TQAP. 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, such as "wn" for wrong number, and the initials
of the recorder and date of entry). Electronic data from the CO2 analyzers, 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
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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 TQAP 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 a TSA audit as described
in Section C. The data from this test will be evaluated relative to the measurement DQIs
described in Section A7 of this TQAP. Data failing to meet these criteria will be flagged in the
data set and not used for evaluation of the CO2 analyzers, 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 isotopic CO2
analyzers for use in GCS monitoring. In part, this evaluation will include demonstrations of the
monitoring ability of CO2 analyzers to detect various kinds of leaks from GCS sites. To meet
the requirements of the user community, input on the tests described in this TQAP has been
provided by external experts. Additional performance data regarding operational characteristics
of the CO2 analyzers 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 TQAP and the resulting ETV verification report(s) will be subjected to review by
the vendor, EPA, and expert peer reviewers. The reviews of this TQAP 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 EPA/600/R-03/021, U.S. Environmental Protection Agency,
Cincinnati, Ohio, January 2008.
3. Trolier, M., J. W. C. White, P. P. Tans, K. A. Masarie, and P. A. Gemery, Monitoring the
isotopic composition of atmospheric CO2: Measurements from the NOAA Global Air
Sampling Network, J. Geophys. Res., 707(D20), 25, 897-25, 916. (1996)
4. Andres, R. J., G. Marland, T. Boden, and S. Bischof, Carbon dioxide emissions from fossil
fuel consumption and cement manufacture, 1751-1991, and an estimate of their isotopic
composition and latitudinal distribution, in 1993. Global Change Institute, edited by T.
Wigley and D. Schimel, Cambridge Univ. Press, New York, 1996.
5. Andres, R. J., G. Marland, I. Fung, and E. Matthews (1996), A 1° x 1° distribution of carbon
dioxide emissions from fossil fuel consumption and cement manufacture, 1950-1990, Global
Biogeochem. Cycles, 10, 419-429.[AGU1 http://cdiac.ornl.gov/ftp/db 1013/db 1013 .txt
6. Esler, M.B., Griffith, D.W.T., Wilson, S.R., and Steele, L.P. Precision Trace Gas Analysis by
FT-IR Spectroscopy. 2. The 13C/12C Isotope Ratio of CO2. Anal. Chem., 2000, 72 (1), pp
216-221.
7. Becker, J. F.; Sauke, T. B.; Loewnstein, M. Stable Isotope Ratio Measurements Using
Tunable Diode Laser Spectroscopy. Opt. 1992, 31, 1921-1927.
8. Busch KW, Busch MA, Cavity Ringdown Spectroscopy: An Ultratrace Absorption
Measurement Technique. ACS Symposium Series 720, Oxford (1997).
9. Atkinson, D. B., "Solving chemical problems of environmental importance using cavity ring-
down Spectroscopy," The Analyst 128, 117-125 (2003).
10. GEO-SEQ Best Practices Manual Geologic Carbon Dioxide Sequestration: Site Evaluation to
Implementation, Ernest Orlando Lawrence Berkeley National Laboratory, September, 2004.
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