June 2006
Environmental Technology
Verification Report
SRI INTERNATIONAL
JET-REMPI
(RESONANCE ENHANCED MULTI-
PHOTON IONIZATION)
Prepared by
Battelle
Batteile
fhe Business of Innovation
Under a cooperative agreement with
U.S. Environmental Protection Agency
ET1/ET1/ET1/
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THE ENVIRONMENTAL TECHNOLOGY VERIFICATION
PROGRAM
U.S. Environmental Protection Agency
Batreiie
Trtc Business o/ Innovation
ETV Joint Verification Statement
TECHNOLOGY TYPE: Dioxin Emission Monitoring System
APPLICATION: Monitoring Incinerator Emissions
TECHNOLOGY
NAME:
COMPANY:
ADDRESS:
WEB SITE:
E-MAIL:
Jet-REMPI
SRI International
333 Ravenswood Avenue PHONE: 650-859-3311
Menlo Park, CA 94025 FAX: 650-859-6196
www.sri.com
harald.oser^sri.com
The U.S. Environmental Protection Agency (EPA) has established the Environmental Technology Verification
(ETV) Program to facilitate the deployment of innovative or improved environmental technologies through
performance verification and dissemination of information. The goal of the ETV Program is to further
environmental protection by accelerating the acceptance and use of improved and cost-effective technologies.
ETV seeks to achieve this goal by providing high-quality, peer-reviewed data on technology performance to
those involved in the design, distribution, financing, permitting, purchase, and use of environmental
technologies. Information and ETV documents are available at www.epa.gov/etv.
ETV works in partnership with recognized standards and testing organizations, with stakeholder groups
(consisting of buyers, vendor organizations, and permitters), and with individual technology developers. The
program evaluates the performance of innovative technologies by developing test plans that are responsive to
the needs of stakeholders, conducting field or laboratory tests (as appropriate), collecting and analyzing data,
and preparing peer-reviewed reports. All evaluations are conducted in accordance with rigorous quality
assurance (QA) protocols to ensure that data of known and adequate quality are generated and that the results
are defensible.
The Advanced Monitoring Systems (AMS) Center, one of six technology areas under ETV, is operated by
Battelle in cooperation with EPA's National Exposure Research Laboratory. The AMS Center evaluated the
performance of the SRI Jet-REMPI (resonance enhanced multi-photon ionization) in monitoring emissions
of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). This verification
statement provides a summary of the test results.
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VERIFICATION TEST DESCRIPTION
The performance of the Jet-REMPI was evaluated in terms of relative accuracy (RA), range, data
completeness, and operational factors (ease of use, maintenance, and consumables/waste generated). RA and
range were determined by comparing Jet-REMPI results to those from reference samples collected
simultaneously using Method 23 sampling trains. Range was determined from measurements over a variety of
defined operating conditions that produced differing levels of PCDD/PCDFs. Data completeness was assessed
as the percentage of maximum data return achieved by the Jet-REMPI over the test period. Operational
factors were evaluated by means of operator observations and records of needed maintenance, vendor
activities, and expendables used.
A 2.94 thousand British thermal unit per hour, 3-Pass Wetback Scotch Marine Package Boiler (SMPB),
manufactured by Superior Boiler Works, Inc., and located at the EPA Research Triangle Park facility, was
used for the verification test. During this verification test, the SMPB was fully instrumented with continuous
emission monitors for a variety of species including oxygen, carbon monoxide, carbon dioxide, water, and
hydrogen chloride. Reference samples were collected and analyzed for PCDD/PCDFs using Method 23 with
several documented modifications.
QA oversight of verification testing was provided by Battelle and EPA. Battelle QA staff conducted a
technical systems audit, a performance evaluation audit, and a data quality audit of 10% of the test data.
This verification statement, the full report on which it is based, and the test/QA plan for this verification test
are all available atwww.epa.gov/etv/centers/centerl.html.
TECHNOLOGY DESCRIPTION
The following description of the Jet-REMPI is based on information provided by the vendor. This technology
description was not verified in this test.
Jet-REMPI is an analytical technique that is designed to selectively identify and quantify vapor-phase
constituents present at part-per-trillion levels in incinerator emissions without preconcentration or sample
collection. Ions produced by REMPI are typically detected using a time-of-flight mass spectrometer (TOP-
MS) that takes advantage of the pulsed nature and well-defined temporal character of laser ionization.
Simultaneous detection by mass and wavelength yields the extremely high chemical selectivity crucial to
identifying one trace compound in the midst of many other similar ones.
The laser system used in the verification test consists of a Nd:YAG pumped OPOTEK Vibrant OPO with
frequency doubling unit with a nominal tuning range between 250 and 340 nanometers, a 5-nanosecond pulse
width, and a repetition rate of 10 hertz. The optical line width of the system is approximately 2 centimeters
(cm)"1. The pulsed valve is an unmodified General Valve Series 9 unit, with an orifice diameter of
0.5 millimeter. The nominal opening time was 150 microseconds, with a 2.5-cm separation between the exit
of the valve and the ionization region. With the sample reservoir at atmospheric pressure, the two 250-liters-
per-second turbomolecular pumps (Varian Turbo V-250) maintain pressures in the ionization chamber and
mass spectrometer regions of 10"5 Torr, and 5 x 10"7 Torr, respectively. The mass spectrometric capabilities of
the reflectron-type TOP mass analyzer used in this verification test include an upper mass range typically up
to 500 atomic mass units and mass resolution (m/Am) greater than 500.
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VERIFICATION RESULTS
Parameter Evaluated
Relative accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/waste
generated
Method of Evaluation
Comparison to Method 23
reference samples
Comparison to Method 23
reference samples
Ratio of number of samples
successfully collected to
number of potential samples
that could have been
collected
Operator observations
Verification test staff
observations
Results
RA 78.2%
Intermethod RSD 61.5%
Intramethod RSD 8.4%
Apparent dependence of accuracy on PCDD/F
toxic equivalent (TEQ) over range of
approximately 1 to 6 nanograms TEQ/dry standard
cubic meters with better agreement at high
concentration
Apparent dependence of accuracy on sample
duration over range of 4 to 8 hours with better
agreement for longer sampling duration
100% completeness in number of samples collected
Approximately 7% downtime
Time required for installation of the Jet-REMPI
system was not verified
Significant on-site support was needed during
testing. During routine operation, a representative
of ARCADIS was on-site and constantly
monitoring instrument diagnostic and indicator
signal
Extensive training and experience with advanced
knowledge of mass spectrometry and laser
spectroscopy techniques is required for operation
of the Jet-REMPI and interpretation of the results
Repair of a faulty pulsed valve on a parallel Jet-REMPI
unit was required during the verification test. The
maintenance activities resulted in approximately
4 hours of instrument downtime.
Small amounts of compressed gas and calibration gas
standards were used during the verification test.
RSD = relative standard deviation
Original signed by Gregory A. Mack 6/6/06
Gregory A. Mack Date
Vice President
Energy, Transportation, and Environment Division
Battelle
Original signed by Lawrence W. Reiter
Lawrence W. Reiter
Director
National Exposure Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
7/26/06
Date
NOTICE: ETV verifications are based on an evaluation of technology performance under specific,
predetermined criteria and the appropriate quality assurance procedures. EPA and Battelle make no expressed or
implied warranties as to the performance of the technology and do not certify that a technology will always
operate as verified. The end user is solely responsible for complying with any and all applicable federal, state,
and local requirements. Mention of commercial product names does not imply endorsement.
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June 2006
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
SRI International
JET-REMPI
(RESONANCE ENHANCED MULTI-
PHOTON IONIZATION)
by
Ken Cowen
Tom Kelly
Amy Dindal
Zachary Willenberg
Karen Riggs
Battelle
Columbus, Ohio 43201
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Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and
Development, has financially supported the development of the technology evaluated in this
verification test. This document has been peer reviewed by the Agency. Mention of trade names
or commercial products does not constitute endorsement or recommendation by the EPA for use.
n
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Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the
nation's air, water, and land resources. Under a mandate of national environmental laws, the
Agency strives to formulate and implement actions leading to a compatible balance between
human activities and the ability of natural systems to support and nurture life. To meet this
mandate, the EPA's Office of Research and Development provides data and science support that
can be used to solve environmental problems and to build the scientific knowledge base needed
to manage our ecological resources wisely, to understand how pollutants affect our health, and to
prevent or reduce environmental risks.
The Environmental Technology Verification (ETV) Program has been established by the EPA to
verify the performance characteristics of innovative environmental technology across all media
and to report this objective information to permitters, buyers, and users of the technology, thus
substantially accelerating the entrance of new environmental technologies into the marketplace.
Verification organizations oversee and report verification activities based on testing and quality
assurance protocols developed with input from major stakeholders and customer groups
associated with the technology area. ETV consists of six verification technology centers.
Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/.
Effective verifications of monitoring technologies are needed to assess environmental quality
and to supply cost and performance data to select the most appropriate technology for that
assessment. Under a cooperative agreement, Battelle has received EPA funding to plan,
coordinate, and conduct such verification tests for "Advanced Monitoring Systems for Air,
Water, and Soil" and report the results to the community at large. Information concerning this
specific environmental technology area can be found on the Internet at
http://www.epa.gov/etv/centers/centerl.html.
in
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Acknowledgments
The authors wish to acknowledge the support of all those who helped plan and conduct the
verification test, analyze the data, and prepare this report. Many thanks to Dahman Touati of
ARCADIS and Dennis Tabor of U.S. Environmental Protection Agency (EPA) for their
contributions and to the Battelle staff who conducted the verification testing. We would also like
to thank Mr. Ernest Bouffard of the Connecticut Department of Environmental Protection,
Mr. Thomas Logan of U.S. EPA, and Mr. Todd Abel of the Chlorine Chemistry Council for their
technical review of the test/quality assurance plan and for their careful review of this verification
report. We also thank the following organizations for financial support of this verification test:
Chlorine Chemistry Council
U.S. EPA Office of Solid Waste and Emergency Response
U.S. EPA Office of Air Quality Planning and Standards
U.S. EPA Office of Research and Development.
IV
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Contents
Page
Notice ii
Foreword iii
Acknowledgments iv
List of Abbreviations vii
Chapter 1 Background 1
Chapter 2 Technology Description 2
Chapter 3 Test Design and Procedures 4
3.1 Introduction 4
3.2 Experimental Setup 5
3.2.1 Test Facility 5
3.2.2 Reference Samples 6
3.2.3 Jet-REMPI Installation and Operation 8
3.3 Test Design 8
3.3.1 Relative Accuracy 8
3.3.2 Range 9
3.3.3 Data Completeness 10
3.3.4 Operational Factors 10
Chapter 4 Quality Assurance/Quality Control 11
4.1 Audits 11
4.1.1 Performance Evaluation Audits 11
4.1.2 Technical Systems Audits 12
4.1.3 Audit of Data Quality 13
4.2 Quality Assurance/Quality Control Reporting 13
4.3 Data Review 13
Chapter 5 Statistical Methods and Reported Parameters 14
5.1 Relative Accuracy 14
5.2 Range 15
5.3 Data Completeness 15
5.4 Operational Factors 15
Chapter 6 Test Results 16
6.1 Relative Accuracy 18
6.2 Range 19
6.3 Data Completeness 20
6.4 Operational Factors 20
6.4.1 Ease of Use 22
6.4.2 Maintenance 22
6.4.3 Consumables/Waste Generation 22
Chapter 7 Performance Summary 23
Chapter 8 References 24
v
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Figures
Figure 2-1. Schematic of the Jet-REMPI Laboratory Prototype 2
Figure 3-1. Wetback Scotch Marine Package Boiler 5
Figure 3-2. Illustration of Flue Gas Duct with Sampling Locations 6
Tables
Table 3-1. Test Run Summary 9
Table 4-1. Methods and Acceptance Criteria for PE Audit Measurements 12
Table 6-1. Summary of Test Runs and Testing Conditions 16
Table 6-2. Reference Method 23 Results 17
Table 6-3. Results from the Method 23 Reference Samples 18
Table 6-4. Summary of Total PCDD/F Results from the Method 23 Samples and Jet-REMPI 19
Table 6-5. Relative Accuracy Results for the Jet-REMPI 19
Table 6-6. Summary of Percent Difference by Sampling Duration 20
Table 6-7. Activity Summary for Jet-REMPI 21
Table 7-1. Summary of Verification Test Results for Jet-REMPI 23
VI
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List of Abbreviations
AMS
APCS
CEM
cm
dscm
EMS
EPA
ETV
HW
m3
mL
ng
NIST
nm
PCDD
PCDF
PE
QA
QC
QMP
RA
REMPI
RSD
RTF
SMPB
TEQ
TOP
ISA
Advanced Monitoring Systems
air pollution control system
continuous emission monitor
centimeter
dry standard cubic meter
emission monitoring system
U.S. Environmental Protection Agency
Environmental Technology Verification
hot/wet
cubic meter
milliliter
nanogram
National Institute of Standards and Technology
nanometer
polychlorinated dibenzo-p-dioxins
polychlorinated dibenzofurans
performance evaluation
quality assurance
quality control
quality management plan
relative accuracy
resonance enhanced multiphoton ionization
relative standard deviation
Research Triangle Park
Scotch Marine Packaged Boiler
toxic equivalent
time of flight
technical systems audit
vn
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Chapter 1
Background
The U.S. Environmental Protection Agency (EPA) supports the Environmental Technology
Verification (ETV) Program to facilitate the deployment of innovative environmental
technologies through performance verification and dissemination of information. The goal of the
ETV Program is to further environmental protection by accelerating the acceptance and use of
improved and cost-effective technologies. ETV seeks to achieve this goal by providing high-
quality, peer-reviewed data on technology performance to those involved in the design,
distribution, financing, permitting, purchase, and use of environmental technologies.
ETV works in partnership with recognized testing organizations; with stakeholder groups
consisting of buyers, vendor organizations, and permitters; and with the full participation of
individual technology developers. The program evaluates the performance of innovative
technologies by developing test plans that are responsive to the needs of stakeholders,
conducting field or laboratory tests (as appropriate), collecting and analyzing data, and preparing
peer-reviewed reports. All evaluations are conducted in accordance with rigorous quality
assurance (QA) protocols to ensure that data of known and adequate quality are generated and
that the results are defensible.
The EPA's National Exposure Research Laboratory and its verification organization partner,
Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS Center
recently evaluated the performance of the SRI International Jet-REMPI (resonance enhanced
multi-photon ionization) system for monitoring emissions of polychlorinated dibenzo-p-dioxins
(PCDD) and polychlorinated dibenzofurans (PCDF).
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Chapter 2
Technology Description
The objective of the ETV AMS Center is to verify the performance characteristics of
environmental monitoring technologies for air, water, and soil. This verification report provides
results for the verification testing of the Jet-REMPI. Following is a description of the Jet-
REMPI, based on information provided by the vendor. The information provided below was not
verified in this test.
Jet-REMPI (Figure 2-1) is an analytical technique that is designed to selectively identify and
quantify vapor-phase constituents present at part-per-trillion levels in incinerator emissions
without
preconcentration
or sample
^ collection. Ions
| | produced by
| p| (i REMPIare
i _ i I typically
Ion Extraction Optics
Ion Beam Steering Plates
Ion Reflector
MicroChannel plate Detector
detected using a
time-of-flight
mass
spectrometer
(TOF-MS) that
takes advantage
of the pulsed
nature and well-
defined temporal
character of laser
ionization.
Simultaneous
Figure 2-1. Schematic of the Jet-REMPI Laboratory Prototype detection by
mass and wavelength yields the extremely high chemical selectivity crucial to identifying one
trace compound in the midst of many other similar ones.
The laser system used in the verification test consists of a Nd:YAG pumped OPOTEK
Vibrant OPO with frequency doubling unit with a nominal tuning range between 250 and 340
nanometers, a 5-nanosecond pulse width, and a repetition rate of 10 hertz. The optical line
Pulsed Gas Inlet
(out of plane)
(Supersonic Jet Expansion)
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width of the system is approximately 2 centimeters (cm) . The pulsed valve is an unmodified
General Valve Series 9 unit, with an orifice diameter of 0.5 millimeter. The nominal opening
time was 150 microseconds, with a 2.5-cm separation between the exit of the valve and the
ionization region. With the sample reservoir at atmospheric pressure, the two 250-liters-per-
second turbomolecular pumps (Varian Turbo V-250) maintain pressures in the ionization
chamber and mass spectrometer regions of 10 5 Torr, and 5 x 10 7 Torr, respectively. The
mass spectrometric capabilities of the reflectron-type TOP mass analyzer used in this
verification test include an upper mass range typically up to 500 atomic mass units and mass
resolution (m/Am) greater than 500.
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Chapter 3
Test Design and Procedures
3.1 Introduction
EPA Method 23 is the certified extractive method used for quantifying PCDD/PCDF emissions
from incinerators in the United States as well as in many other countries. This method is labor-
intensive, expensive, and requires an extended time for subsequent laboratory analysis of
collected samples. As a result, Method 23 measurements are made infrequently only for
compliance purposes and not for long- or short-term performance monitoring. Emerging
technologies are being developed to provide semi-continuous monitoring or long-term sampling
of PCDD/PCDFs and may have the potential to provide more information on PCDD/PCDF
source emissions than the relatively few samples required under federal or state regulations. For
example, in Europe, mainly in Belgium and Germany, long-term sampling of PCDD/PCDFs has
been used for compliance measurements since 2000. However, the performance of these newly
introduced technologies has not been evaluated in the United States to determine their relative
operational capabilities.
The purpose of this verification test was to generate performance data on the Jet-REMPI
emission monitoring system. The test was conducted at EPA's Research Triangle Park (RTF),
North Carolina, campus over a period of two weeks in September 2005 and was supported by
ARC AD IS under a subcontract from Battelle. The accuracy and range of the Jet-REMPI were
determined through comparisons to a modified version of Method 23 integrated sampling
method for PCDD/PCDF, l' with modifications as described in Section 3.2.2 of this report. Other
performance parameters such as data completeness and operational factors were determined from
operator observations.
This verification test was conducted according to procedures specified in the Test/QA Plan for
Verification ofDioxin Emission Monitoring Systems (EMSs), and the Quality Management
Plan (QMP)for the ETV/AMS Center. ^' As described in this report, the performance of the Jet-
REMPI was evaluated in terms of
Relative accuracy (RA),
Range,
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Data completeness, and
Operational factors (ease of use, maintenance, and consumables/waste generated).
Relative accuracy and range were determined by comparing Jet-REMPI results to those from
Method 23 reference samples collected simultaneously using Method 23 sampling trains. Range
was determined from measurements over a variety of defined operating conditions that produced
differing levels of PCDD/PCDFs. Data completeness was assessed as the percentage of
maximum data return achieved by the Jet-REMPI over the test period. Operational factors were
evaluated by means of operator observations and records of needed maintenance, vendor
activities, and expendables used.
3.2 Experimental Setup
3.2.1 Test Facility
A 2.94 thousand British thermal unit per hour, 3-Pass Wetback Scotch Marine Package Boiler
(SMPB), manufactured by Superior Boiler Works, Inc., and located at the EPA RTF facility, was
used for the verification test. This boiler (Figure 3-1) is capable of firing natural gas or a variety
of fuel oils. In this test, the oil burner was used; this burner is a low-pressure, air-atomizing
nozzle that delivered a fine spray at an angle that ensured proper mixing with the air stream. The
boiler has 33 square meters of
heating surface and generates up to
1,090 kilograms per hour of
saturated steam at pressures up to
15 pounds per square inch. Fuel
flows were measured with a liquid
volume totalizer, and stoichiometric
ratios were verified through oxygen
(Oz) and carbon dioxide (COz)
emission concentrations.
During this verification test, the
SMPB was fully instrumented with
continuous emission monitors
(CEMs) for a variety of species
including Oz, carbon monoxide
(CO), C02, water (H20), and
hydrogen chloride (HC1). Continuous emission monitoring of chemical species was performed
with two shared CEMs for the packaged boiler facility. One CEM bench included four gas
analyzers: high-range CO, low-range CO, Oz, and COz. HC1 was measured by a self-contained
bench-scale CEM system (Bodenseewerk), which uses an Altech Hot/Wet (HW) sampling
system and a Perkin-Elmer MCS-100 Infrared Multi-Component Analyzer. The MCS is capable
of measuring up to eight compounds simultaneously, using gas filter correlation and single-beam
dual-wavelength techniques. The HW probe assembly samples flue gases, while maintaining
temperatures at elevated levels. The flue gas from the unit passes through a manifold to an air
pollution control system (APCS) consisting of a natural-gas-fired secondary combustion
chamber, a fabric filter, and an acid gas scrubber to ensure proper removal of pollutants. All
Figure 3-1. Wetback Scotch Marine Package Boiler
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emission measurements are taken prior to the APCS. The SMPB facility was modified prior to
testing to accommodate all the requirements of the verification test. These modifications
included the addition of a section of duct equipped with several sampling ports at the exit of the
boiler to allow for the simultaneous installation of multiple PCDD/PCDF EMSs and operation of
duplicate Method 23 sampling trains. Figure 3-2 is a schematic illustration of the duct,
identifying the sampling locations for the reference sample trains and the Jet-REMPI. As this
figure shows, one Method 23 train sampled from a port upstream in the flue gas flow from the
Jet-REMPI's sampling port, and the other sampled downstream.
HALF-COUPLING
TYP. OF 4
\
^ 1
ri n
r
i
0 0 0
Figure 3-2. Illustration of Flue Gas Duct with Sampling Locations
A chlorinated chemical (1,2-dichlorobenzene) and a source of metal atoms (copper naphthenate)
were added to the boiler fuel to promote PCDD/PCDF formation for the EMS testing. A feed
system was designed to safely tap the chemical feed line to the fuel line just before the burner
nozzle. The feed system consisted of a 37-liter pressurized stainless steel tank, in which the
1,2-dichlorobenzene and the copper naphthenate were mixed.
The stack gas composition for each test run conducted during the verification test is presented in
Section 6.1 of this verification report.
3.2.2 Reference Samples
Reference samples were collected and analyzed for PCDD/PCDFs using Method 23, with the
following modifications established before any sample collection took place:
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Analysis was completed by high-resolution gas chromatography/low-resolution mass
spectrometry.
Mass locking was not used with low-resolution mass spectrometry.
The front and back halves of the reference samples were extracted and analyzed together
rather than separately.
The internal, surrogate, and recovery standards included several that were not required in the
standard method.
Extraction procedures called for in Method 23 were modified to allow more efficient
extraction of mono- through tri-chlorinated PCDD/PCDF (see Section 4.1.2).
ARCADIS collected the reference method samples and coordinated their analysis, which was
conducted by EPA staff at the EPA RTF facility. EPA staff ensured that the analytical
instrumentation was calibrated and the samples were analyzed according to the requirements of
the modified Method 23 and that the appropriate QA/quality control (QC) activities were
conducted according to the method. Records of all calibrations and sample analyses were
provided to Battelle and are maintained in the test files.
3.2.2.1 Reference Sample Collection
As shown in Figure 3-2, the Method 23 samples were collected at the two extreme locations of
the stack gas sampling section, to bracket the locations of the technologies being evaluated in
this verification test. The reference method sampling included pre-spiking the Method 23 XAD-2
traps with carbon-13 labeled PCDD/F pre-sampling surrogates. Both sampling trains consisted
mainly of a heated probe, heated box containing a cyclone and a filter, water-cooled condenser,
water-cooled XAD-2 cartridge, impinger train for water determination, leak-free vacuum line,
vacuum pump, and a dry gas and orifice meter with flow control valves and vacuum gauge.
Temperatures were measured and recorded in the hot box (set at 125ฐC), at the impinger train
outlet, at the XAD-2 cartridge outlet (maintained below ambient temperature), and at the inlet
and outlet of the dry gas meter. Leak checks were conducted at the beginning and end of each
sample run. Prior to sampling, all glassware, probe materials, glass wool, and aluminum foil
were cleaned following the Method 23 cleaning procedure.
3.2.2.2 Sample Recovery
Following completion of each test run, each sampling train was recovered in a clean area; and
the cleanup procedure began as soon as the probe was removed from the sample source location.
During the transportation between the test facility and the designated recovery area, both ends of
the heated probe and openings of the impinger assembly were sealed with aluminum foil or glass
caps.
The front-half and back-half trains were recovered separately but analyzed together since no
gas/solid phase PCDD/F speciation was required for this verification test. The probe and front
half of the filter housing for each sample train were rinsed with acetone followed by dichloro-
methane and collected in a single 250-milliliter (mL) amber jar. The probe and front-half filter
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housing were then rinsed with toluene and collected in a separate 250-mL amber jar. The filter
was recovered and placed in a Petri dish sealed with Teflon tape.
The back-half sample trains, which consisted of an XAD-2 cartridge, the back-half filter housing,
glass connection, and condenser, were recovered separately. The XAD-2 resin cartridge from
each train was capped at both ends and wrapped in aluminum foil during transport. As with all
sample fractions, the XAD-2 resin cartridges remained refrigerated during storage and transport.
The back-half glassware was rinsed and collected in the same way as the front-half rinses. The
solvent rinse jars for both the front- and back-half sample trains were capped with Teflon-lined
caps, sealed with Teflon tape to prevent leakage, and stored in a refrigerated space before being
sent for analysis.
3.2.3 Jet-REMPI Installation and Operation
Figure 3-2 indicates the locations of the Method 23 reference sampling ports and the location of
the Jet-REMPI sampling port. The flue gas was exhausted through an insulated duct with an
internal diameter of approximately 20 centimeters. The duct was modified prior to testing to
accommodate the installation and simultaneous operation of multiple EMS technologies in
addition to sampling ports for collecting Method 23 reference samples.
During testing, a sampling probe was used to draw sample gas from the duct into a heated
sample line approximately 10 meters in length that was used to deliver the flue gas from the duct
to the Jet-REMPI. PCDD/F surrogate compounds were continuously monitored by Jet-REMPI.
3.3 Test Design
Relative accuracy, range, data completeness, and operational factors for the Jet-REMPI were
evaluated.
3.3.1 Relative Accuracy
The RA of the Jet-REMPI was evaluated by comparing its results to simultaneous results
obtained by reference samples of the flue gas collected using Method 23. During the verification
test, a series of nine Method 23 test runs were conducted using duplicate Method 23 trains. The
Method 23 trains sampled from ports located at each end of the sampling region where the Jet-
REMPI was installed, as shown in Figure 3-2. The reference samples were recovered and
submitted for analysis by the modified version of Method 23 described in Section 3.2. The
PCDD/PCDF concentrations determined by the reference methods were compared to
corresponding results from the Jet-REMPI, averaged over the period of each Method 23 test run.
During each of the test runs, the boiler operation was maintained as constant as possible.
However, the duration of the sampling periods and the operating conditions of the boiler were
changed from run to run to provide a range of conditions under which the Jet-REMPI was
evaluated. Two sets of operating conditions were used for the test runs to generate expected high
(5-10 nanograms [ng] toxic equivalent [TEQ]/dry standard cubic meter [dscm]) and low (1-2 ng
TEQ/dscm) PCDD/PCDF concentrations. Test runs of various durations were conducted under
each set of operating conditions. Sampling periods of four hours were used to assess short-term
accuracy, whereas long-term accuracy was assessed from samples collected over 8-hour
sampling periods. Table 3-1 shows the sampling durations and boiler operating conditions for
8
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each of the nine test runs. Two Method 23 trains were used to collect each reference sample
during each test run. These trains sampled isokinetically from a single point in the gas flow, with
one of the trains sampling at each end of the sampling region.
Table 3-1. Test Run Summary
Date
9/12/05
9/13/05
9/14/05
9/15/05
9/16/05
9/17/05
9/18/05
9/19/05
9/20/05
Test Run
1
2
3
4
5
6
7
8
9
Sampling Duration
4 hours
4 hours
8 hours
8 hours
4 hours
4 hours
8 hours
8 hours
8 hours
Expected PCDD/PCDF
Concentration
Low
Low
High
High
High
High
Low
Low
High
(a) Expected concentrations based on results of baseline testing. "High" corresponds to expected total PCDD/F TEQ
of roughly 5-10 ng TEQ/dscm, and "low" corresponds to expected concentrations of roughly 1-2 ng TEQ/dscm.
Upon completion of each test run, the Method 23 trains were dismantled for sample recovery in
the field by ARCADIS staff, and all collected sample fractions were logged and stored for
transfer to the analytical laboratory. Subsequent to analysis, ARCADIS reviewed the data and
reported final PCDD/F concentrations from all trains in units of TEQ/dscm, corrected to 7% Oz.
The results from the simultaneously collected Method 23 trains were used to assess the degree of
PCDD/F loss (if any) in the duct between the two reference method sampling ports. Unless
discrepancies of greater than 30% were observed between the reference samples collected
simultaneously for total measured TEQs, the results from the reference method samples were
averaged together to produce the final reference data used for comparison to the Jet-REMPI
results. If discrepancies of greater than 30% were observed, the data were flagged and the
samples treated as independent samples for comparison to the Jet-REMPI.
3.3.2 Range
Range was assessed in terms of RA over the range of measured PCDD/PCDF concentrations and
sampling periods. The reference method samples were collected over a range of expected
PCDD/F concentrations to assess the degree of agreement of the Jet-REMPI with the reference
method. Based on results from baseline testing of the boiler conducted prior to the verification
test, the dopant injection rate and firing conditions were changed for different test runs to achieve
different expected PCDD/F concentrations (i.e., high or low concentration). Additionally, the
duration of the test runs was varied to achieve sampling periods of either 4 or 8 hours. During
each test run, the flue gas HC1 level was used as an indicator of the expected PCDD/F
-------
concentrations in the flue gas, and the dopant injection rate was varied to achieve different
expected PCDD/F levels for the test runs.
3.3.3 Data Completeness
Data completeness was assessed based on the overall data return achieved by the Jet-REMPI.
Data completeness was reported in terms of the percentage of acceptable samples collected
during the verification test and in terms of percentage of time that the Jet-REMPI system was
collecting samples compared with the Method 23 sampling trains.
3.3.4 Operational Factors
Operational factors such as maintenance needs, data output, consumables used, ease of use, and
repair requirements were evaluated based on observations recorded by Battelle and facility staff,
and in some cases by the vendor. A laboratory record book maintained at the test facility was
used to enter daily observations on these factors.
10
-------
Chapter 4
Quality Assurance/Quality Control
QA/QC procedures were performed in accordance with the QMP for the AMS Centerฎ and the
test/QA plan^ for this verification test, except as noted in Section 4.1.2.
4.1 Audits
4.1.1 Performance Evaluation Audits
A performance evaluation (PE) audit was conducted to assess the quality of the critical
measurements associated with the reference sampling and analysis methods. In the PE audit,
critical measurements were checked by comparing them with appropriate National Institute of
Standards and Technology (NIST)-traceable standards, when available. Table 4-1 shows the
critical measurements that were audited, the audit procedures and acceptance criteria for the
audit comparisons, and the audit results. An initial PE audit of the Method 23 gas flow rate did
not meet the acceptance criterion. However, the flow transfer standard used for the audit was
found to be working improperly and therefore not appropriate for comparison. The audit was
repeated using a different flow transfer standard. The results of the second audit are presented in
the table.
The PE audit of the internal standard recovery was performed by spiking one blank Method 23
train with an NIST-traceable PCDD/PCDF solution, provided by Battelle, and independent of the
internal standards used for the reference method samples. The spiked train was not used to
collect a flue gas sample, but was recovered and analyzed in the same manner as the other
Method 23 trains; and the analytical results were compared with the spike amount to assess
recovery. The target criteria for this PE audit were 40% to 130% recovery of the internal
standards for the tetra- through hexachlorinated compounds and 25% to 130% for the hepta- and
octachlorinated compounds. The actual recoveries were well within these limits, ranging from
101% to 120% for all compounds.
11
-------
Table 4-1. Methods and Acceptance Criteria for PE Audit Measurements
Critical
Measurement
Method 23 gas
sample flow rate
Method 23 stack
gas temperature
Barometric
pressure
PCDD/PCDF
internal standard
recovery
PCDD/PCDF
surrogate standard
recovery
PE Audit Method
Compare to independent flow
measurement device
Compare to independent
temperature measurement device
Compare to independent pressure
gauge
Method spike with an independent
PCDD/PCDF standard
Field spike with an independent
PCDD/PCDF standard
Acceptance Criteria
ฑ5%
ฑ2% absolute
temperature
ฑ1% absolute pressure
40% to 130%fortetra-
through hexachlorinated
compounds and
2 5% to 130%forhepta-
and octachlorinated
compounds
70% to 130% recovery
Audit Results
2.2% - 3.4%
Pass
0.0% - 0.55%
Pass
0.4%
Pass
101%- 120%
Pass
91%- 107%
Pass
The PE audit of the surrogate standard recovery was performed by spiking one blank XAD-2
cartridge with an NIST-traceable PCDD/PCDF surrogate standard solution provided by Battelle,
and independent of the surrogate standards used for the reference method samples. This spiked
cartridge was extracted and analyzed in the same manner as the other cartridges. The target
criterion for this PE audit was 70% to 130% recovery of the surrogate standards. The actual
recoveries were well within these limits, ranging from 91% to 107% for all compounds.
4.1.2 Technical Systems Audits
The Battelle Quality Manager performed a technical systems audit (TSA) on September 13 and
14, 2005, to ensure that the verification test was being performed in accordance with the AMS
lr)\ Jr)\ *-^ *
Center QMP/ ; the test/QA plan/ ; published reference methods, and any standard operating
procedures used by the test facility. In the TSA, the Battelle Quality Manager toured the test site,
observed Method 23 sampling and sample recovery, inspected documentation of reference
sample chain of custody, and reviewed laboratory record books. The Quality Manager also
checked standard certifications and Method 23 data acquisition procedures. A TSA report was
prepared, including a statement that no significant findings or corrective actions were identified.
A single deviation from the test/QA plan was documented as a result of the TSA. This deviation
involved differences between the extraction procedures used by the EPA laboratory and the
procedures in Method 23. The EPA laboratory used modified procedures that allowed for the
extraction and quantification of lower chlorinated PCDD/PCDFs (e.g., mono- through
trichlorinated PCDD/PCDFs). The modified procedures did not impact the quality of the data for
this verification test.
Additionally, the EPA AMS Center Quality Officer conducted a TSA on September 14, 2005.
There were no significant findings or correctives identified during that audit.
12
-------
4.1.3 Audit of Data Quality
At least 10% of the data acquired during the verification test were audited. Battelle's Quality
Manager, or designee, traced the data from the initial acquisition, through reduction and
statistical analysis, to final reporting, to ensure the integrity of the reported results. All
calculations performed on the data undergoing the audit were checked.
4.2 Quality Assurance/Quality Control Reporting
Each assessment and audit was documented in accordance with Section 3.3.4 of the QMP for the
ETV AMS Center. Once the assessment report was prepared, the Battelle Verification Test
Coordinator ensured that a response was provided for each adverse finding or potential problem
and implemented any necessary follow-up corrective action. The Battelle Quality Manager
ensured that follow-up corrective action was taken. The results of the TSA were sent to the EPA.
4.3 Data Review
Data generated during this test were reviewed by a Battelle technical staff member within two
weeks of generating the data. The reviewer was familiar with the technical aspects of the
verification test, but was not the person who generated the data. The person performing the
review added his/her initials and the date to a hard copy of the record being reviewed.
13
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Chapter 5
Statistical Methods and Reported Parameters
The statistical methods presented in this chapter were used to verify the RA, range, and data
completeness of the Jet-REMPI during this verification test.
5.1 Relative Accuracy
The RA of the Jet-REMPI with respect to the reference sample results was assessed as a percent
bias, using Equation (1):
(1)
RM
where:
= the absolute value of the mean of the differences between the Jet-REMPI and reference
sample results for each test run,
t0 975 = the one-tailed t-value for the 97.5% confidence level,
Sd = the standard deviation of the differences between the Jet-REMPI and reference sample
results for each test run, and
RM = the mean of the reference method results.
In addition to the RA, the intermethod relative standard deviation (RSD) was also calculated
according to Equation (2):
n
where
14
-------
j = the standard deviation of the paired Jet-REMPI and reference method results for test
run /',
Xt = the average of the paired Jet-REMPI and reference method results for test run /', and
n = the number of test runs.
The intramethod RSD was also calculated using Equation (2) where the standard deviations and
averages were calculated from the duplicate reference method results for each test run.
5.2 Range
The range of the Jet-REMPI is reported in terms of its bias relative to the reference method,
expressed both as a percent difference and absolute difference, under the variety of boiler
operating conditions and sampling durations used during the test runs.
5.3 Data Completeness
Data completeness was calculated as the percentage of the total possible data return over the
entire field period. The cause of any substantial incompleteness of data return was established
from operator observation or vendor records and noted in the discussion of data completeness
results.
5.4 Operational Factors
Operational factors were evaluated based on operator observations. No statistical comparisons of
operational factors were made.
15
-------
Chapter 6
Test Results
The results of the verification test of the Jet-REMPI are presented below for each of the
performance parameters. Test runs were designed to be either 4- or 8-hour periods at high or low
PCDD/F concentrations. Table 6-1 presents a summary of the test runs that were completed
during the verification test along with a summary of the flue gas conditions.
Table 6-1. Summary of Test Runs and Testing Conditions
Test Run
1
2
3
4
5
6
7
8
9
Date
9/12/2005
9/13/2005
9/14/2005
9/15/2005
9/16/2005
9/19/2005
9/20/2005
9/21/2005
9/22/2005
Duration
(hours)
4
4
8
8
4
4
8
8
8
Expected
PCDD/F
Cone.
Low
Low
High
High
High
High
Low
Low
High
Stack
Temp.
no
312.0
313.5
305.5
309.5
319.0
316.5
303.0
305.5
315.5
02
Cone.
(%)
4.28
4.72
4.30
5.38
5.04
5.09
4.80
3.12
3.38
CO2
Cone.
(%)
12.85
12.77
12.98
12.22
12.31
12.23
12.36
13.35
13.04
H2O Cone.
(%)
11.0
10.8
11.1
11.0
11.0
10.8
11.9
11.7
11.1
Table 6-2 lists the reference method results for each test run. The results are presented for the
Method 23 samples that were collected at the first sampling port (Port 1) and the seventh
sampling port (Port 7). The top portion of the table shows the readings for individual
PCDD/PCDF congeners. The lower portion of the table summarizes the TEQ values for each test
run according to PCDDs, PCDFs, and the total. All results have been corrected to 7% 02.
16
-------
Table 6-2. Reference Method 23 Results
Compound
2,3,7,8 -TeCDD
1,2,3,7,8 -PeCDD
1,2,3,4,7,8 -HxCDD
1,2,3,6,7,8 -HxCDD
1,2, 3,7,8,9 -HxCDD
1,2,3,4, 6,7,8 -HpCDD
1,2, 3,4, 6,7,8,9 - OCDD
2,3,7,8 -TeCDF
1,2, 3,7,8 -PeCDF
2,3,4,7,8 -PeCDF
1,2,3,4, 7,8 -HxCDF
1,2,3,6, 7,8 -HxCDF
2,3,4,6,7,8 -HxCDF
1,2, 3,7,8,9 -HxCDF
1,2, 3,4, 6,7,8 -HpCDF
1,2, 3,4, 7,8,9 -HpCDF
1,2, 3,4, 6,7,8,9 - OCDF
Total PCDD TEQ
Total PCDF TEQ
Total PCDD/F TEQ
Concentration [ng/dscm @ 7% 02]
Test Run 1
Portl
0.0
0.2
0.1
0.1
0.1
0.5
0.8
0.7
0.8
1.8
1.6
1.1
0.9
0.1
3.2
0.4
1.0
Port 7
0.0
0.2
0.1
0.1
0.1
0.5
0.8
0.6
0.8
1.8
1.6
1.2
0.9
0.1
3.5
0.5
1.3
Test Run 2
Portl
0.0
0.1
0.1
0.1
0.0
0.4
0.7
0.4
0.6
1.3
1.2
0.9
0.6
0.0
2.6
0.3
0.9
Port?
0.0
0.1
0.1
0.1
0.1
0.4
0.6
0.4
0.5
1.1
1.1
0.8
0.5
0.0
2.4
0.3
0.9
Test Run 3
Portl
0.1
0.3
0.3
0.3
0.2
1.6
3.0
2.5
3.2
6.8
6.1
4.8
3.3
0.3
12.7
2.0
6.2
Port?
0.1
0.3
0.3
0.3
0.2
1.8
3.3
2.5
3.4
7.2
6.8
5.3
3.7
0.3
13.7
2.2
6.5
Test Run 4
Portl
0.1
0.3
0.3
0.3
0.2
2.0
4.6
2.0
2.9
6.2
6.5
4.9
3.2
0.2
15.9
2.1
8.6
Port?
0.1
0.3
0.3
0.3
0.2
2.0
4.5
2.3
3.4
7.1
7.3
5.6
3.8
0.3
16.7
2.2
7.9
Test Run 5
Portl
0.1
0.3
0.3
0.3
0.2
1.8
3.2
1.8
3.0
6.5
7.2
5.4
3.6
0.3
15.5
2.1
6.7
Port?
0.0
0.2
0.2
0.3
0.2
1.4
2.6
1.6
2.4
5.2
5.7
4.2
2.7
0.2
12.2
1.6
5.3
Test Run 6
Portl
0.0
0.2
0.2
0.3
0.1
1.4
3.1
1.6
2.3
5.4
5.7
4.3
3.0
0.2
13.3
1.4
4.8
Port?
0.1
0.2
0.2
0.2
0.1
1.3
2.8
1.4
2.2
4.9
5.3
4.1
2.8
0.2
12.5
1.4
4.5
Test Run 7
Portl
0.0
0.1
0.1
0.1
0.1
0.4
0.7
0.4
0.6
1.3
1.6
1.2
0.8
0.1
3.7
0.4
1.1
Port?
0.0
0.1
0.1
0.1
0.0
0.4
0.6
0.4
0.6
1.2
1.5
1.1
0.7
0.1
3.4
0.3
1.0
Test Run 8
Portl
0.0
0.1
0.1
0.1
0.0
0.3
0.5
0.2
0.4
1.0
1.2
0.9
0.6
0.1
2.7
0.3
0.9
Port?
0.0
0.0
0.1
0.1
0.1
0.4
0.6
0.2
0.4
0.9
1.2
0.9
0.6
0.0
2.8
0.3
0.8
Test Run 9
Portl
0.0
0.1
0.2
0.2
0.1
1.0
1.8
1.6
2.1
4.6
4.5
3.4
2.3
0.2
9.6
1.4
4.3
Port?
0.0
0.1
0.2
0.2
0.1
1.1
1.8
1.5
2.0
4.4
4.6
3.4
2.3
0.2
9.7
1.5
4.1
Concentration [ng TEQ/dscm @ 7% O2]
0.22
1.41
1.63
0.23
1.39
1.62
0.17
1.03
1.19
0.14
0.88
1.01
0.42
5.39
5.81
0.46
5.76
6.22
0.42
5.13
5.55
0.44
5.82
6.26
0.42
5.41
5.84
0.35
4.28
4.63
0.31
4.43
4.74
0.29
4.08
4.37
0.11
1.13
1.24
0.10
1.07
1.17
0.10
0.83
0.93
0.07
0.81
0.87
0.23
3.71
3.94
0.25
3.60
3.85
-------
The TEQ values for each test run are also presented in Table 6-3, along with the calculated
percent difference between the results from the two Method 23 trains. With the exception of the
TEQ results for PCDD/PCDFs in Test Run 8, the results from the two trains are within 30%,
indicating no substantial biases based on the sampling port locations. Even for Test Run 8, the
large relative difference observed for the PCDDs originates from the low absolute concentrations
of PCDDs in that run. Since the PCDFs for that test run agree well for the two trains, indicating
that there was no substantial bias between the ports for that run, the average of the results was
used in all cases for evaluation of the Jet-REMPI.
Table 6-3. Results from the Method 23 Reference Samples
Test
Run
1
2
3
4
5
6
7
8
9
PCDD TEQ
Port #1
0.22
0.17
0.42
0.42
0.42
0.31
0.11
0.10
0.23
Port #7
0.23
0.14
0.46
0.44
0.35
0.29
0.10
0.07
0.25
% Diff.
-5.5%
17.7%
-7.5%
-5.3%
18.9%
6.6%
12.0%
36.4%
-10.0%
PCDF TEQ
Port #1
1.41
1.03
5.39
5.13
5.41
4.43
1.13
0.83
3.71
Port #7
1.39
0.88
5.76
5.82
4.28
4.08
1.07
0.81
3.60
% Diff.
0.3%
16.1%
-6.8%
-12.0%
23.1%
8.1%
6.1%
6.3%
2.4%
Total PCDD/F TEQ
Port #1
1.63
1.19
5.81
5.55
5.84
4.74
1.24
0.93
3.94
Port #7
1.62
1.01
6.22
6.26
4.63
4.37
1.17
0.87
3.85
% Diff.
0.6%
16.4%
-6.8%
-12.0%
23.1%
8.1%
5.8%
6.7%
2.3%
6.1 Relative Accuracy
Table 6-4 displays the results of the Jet-REMPI data in terms of the TEQ values for the total
PCDD/Fs determined by the Jet-REMPI. These results are derived from the measured
concentrations of indicator compounds that the vendor had previously correlated with PCDD/F
concentrations. As with the results from the reference method samples, the Jet-REMPI results
have been corrected to 7% Oz. The Jet-REMPI results are presented along with the averaged
result from the reference method for each test run. The percent difference between the reference
method results and the Jet-REMPI results is shown for each test run. The Jet-REMPI results were
lower than the reference method results for some test runs and higher for others. The percent
differences range from -47.8% to 296% for all the test runs. For Test Runs 6 through 9, a Perma-
pure dryer was added to the sampling line to dry the flue gas prior to analysis in an effort to
avoid clogging the pulsed valve on a parallel Jet-REMPI unit with condensed water vapor. The
parallel Jet-REMPI unit was not evaluated in this verification test but was used throughout the
test to monitor for other chemical species in the flue gas.
18
-------
Table 6-4. Summary of Total PCDD/F Results from the Method 23 Samples and Jet-REMPI
Test Run
1
2
3
4
5
6(a)
7 (a)
g(a)
g(a)
Method 23 Results
(ng TEQ/dscm)
1.62
1.10
6.01
5.90
5.23
4.55
1.20
0.90
3.89
Jet-REMPI
Results
(ng TEQ/dscm)
6.42
3.20
6.01
5.54
4.34
5.93
3.03
1.77 (5.21)(b)
2.03
Difference
(ng TEQ/dscm)
4.80
2.10
0.00
-0.36
-0.89
1.38
1.83
0.87 (4.31) (b)
1.86
Percent
Difference
296%
190%
-0.1%
-6.2%
-17.0%
30.2%
152%
96.0% (479%) (b)
-47.8%
"Test run conducted with Perma-pure dryer on sample inlet line.
Values in parentheses indicate results without Perma-pure dryer installed. This value was not included in the
calculation of RA.
Table 6-5 shows the relative accuracy results for the Jet-REMPI, expressed as a percent as
calculated by Equation (1) (Section 5.1). This calculation of RA includes the absolute differences
between the measurements for the test runs as well as the standard deviation of the differences
for all the runs. In addition, the intermethod RSD of the differences between the Jet-REMPI and
average of the Method 23 results is shown along with the intramethod RSD between the two
Method 23 trains.
Table 6-5. Relative Accuracy Results for the Jet-REMPI
Parameter
Results
RA
Intermethod RSD
Intramethod RSD
78.2%
61.5%
8.4 %
6.2 Range
The range of the Jet-REMPI is reported in terms of percent difference from the reference method
under the variety of boiler operating conditions and sampling durations used during the test runs.
The greatest absolute percent difference between the Jet-REMPI and Method 23 results was
296% and the lowest absolute percent difference was 0.1%. In general, the Jet-REMPI results
showed better agreement with the Method 23 results at high concentrations. At high PCDD/F
concentrations (i.e., > 2 ng TEQ/[cubic meter] m3), the average of the absolute percent
differences between the Jet-REMPI and the Method 23 results was 20.3%. However, at low
PCDD/F concentrations (e.g., < 2 ng TEQ/m3), the Jet-REMPI shows an average absolute
difference of 183% relative to the reference method.
19
-------
Table 6-6 summarizes the test results by sampling duration. In general, the results of Jet-REMPI
agreed more closely with the Method 23 results for the 8-hour test runs compared with the
4-hour test runs. The average absolute percent difference for 4-hour test runs was 133%, whereas
the average absolute percent difference for the 8-hour test runs was 60.4%.
Table 6-6. Summary of Percent Difference by Sampling Duration
Duration
8hr
8hr
8hr
8hr
8hr
8-Hour Average
Absolute % Difference
4hr
4hr
4hr
4hr
4-Hour Average
Absolute % Difference
Test Run
3
4
7
8
9
1
2
5
6
PCDD/F % Diff
-0.1%
-6.2%
152%
96.0%
-47.8%
60.4%
296%
190%
-17.0%
30.2%
133%
6.3 Data Completeness
Samples were successfully collected from each of the sampling test runs, and the results of the
analyses of these samples are presented in Section 6.1. As a result, the data completeness for the
Jet-REMPI was 100% for the verification test. However, as described in Section 6.4, during one
of the Method 23 test runs, the Jet-REMPI sampled the flue gas for only 4 hours of the 8-hour
duration of the test run. Thus, the Jet-REMPI collected samples during 93% of the duration of
the test runs (i.e., 4 hours downtime divided by 56 hours of test run sampling time = 7.1%
downtime).
6.4 Operational Factors
Table 6-7 summarizes the activities performed on the Jet-REMPI system during the verification
test, as well as the time required to perform those activities and the amount of downtime
experienced to complete those activities. Reported times for instrument start-up, calibration,
testing preparations, and instrument shut-down are approximations based on operator experience.
Since these operations are relatively complex and may vary depending on day-to-day variability
in instrument operation, it is difficult to quantify exactly the time required to complete the
necessary activities on a daily basis. Delays in start times of individual test runs were not
included in the estimated times although the Jet-REMPI operator continued to perform these
activities until each test run commenced.
20
-------
Table 6-7. Activity Summary for Jet-REMPI
Date
Duration
Activity
Down Time
9/12/05
Approximately
7 hours
Instrument start-up, calibration, testing
preparations.
Sample collection, desorption, and analysis.
Instrument shut-down.
9/13/05
Approximately
7 hours
Instrument start-up, calibration, testing
preparations. Sample collection, desorption, and
analysis.
Instrument shut-down.
9/14/05
Approximately
10 hours
Instrument start-up, calibration, testing
preparations.
Sample collection, desorption, and analysis.
Instrument shut-down.
NAU
9/15/05
Approximately
10 hours
Instrument start-up, calibration, testing
preparations.
Sample collection, desorption, and analysis.
Instrument shut-down.
9/15/05
Approximately
4 hours
Maintenance performed on pulsed valve on a parallel
Jet-REMPI unit.(c)
4 hours
9/16/05
Approximately
2 hours
Maintenance performed on pulsed valve on a parallel
Jet-REMPI unit prior to testing.(c)
NA
9/16/05
Approximately
4 hours
Instrument start-up, calibration, testing
preparations.
Sample collection, desorption, and analysis.
9/18/05
Approximately
6 hours
Instrument start-up, calibration, testing
preparations.
Sample collection, desorption, and analysis.
Instrument shut-down.
NAU
9/19/05
Approximately
10 hours
Instrument start-up, calibration, testing
preparations, and instrument diagnostics.
Sample collection, desorption, and analysis.
Instrument shut-down.
NAU
9/21/05
Approximately
10 hours
Instrument start-up, calibration, testing
preparations, and instrument diagnostics.
Sample collection, desorption, and analysis.
Instrument shut-down.
9/22/05
Approximately
6 hours
Instrument start-up, calibration, testing
preparations, and instrument diagnostics.
Sample collection, desorption, and analysis.
Instrument shut-down.
NAU
(!i> Operator was present during entire test run to manually record certain data and to adjust instrument settings as
needed.
NA = Not applicable. Sample installation and recovery are performed outside of sampling period.
Parallel Jet-REMPI unit was not evaluated in this verification test and was used to independently monitor for
other chemical species in the flue gas.
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6.4.1 Ease of Use
Ease of use of the Jet-REMPI was established during this verification test based on observations
of Battelle staff during the verification testing and through discussions with the operator of the
Jet-REMPI. The Jet-REMPI system was installed by representatives of ARCADIS who are on-
site contractors to EPA. Installation of the Jet-REMPI was conducted prior to testing and could
not be verified by Battelle. Operation of the Jet-REMPI during this verification test was
conducted by a single representative of ARCADIS. Operation of the Jet-REMPI requires
extensive knowledge of sophisticated laser systems and mass spectrometers, including advanced
electronic data collection and manipulation equipment. During the verification test, the operator
of the Jet-REMPI was a Ph.D. chemist/physicist with several years of experience with the Jet-
REMPI system.
6.4.2 Maintenance
For the purpose of this verification report, sample installation/recovery and system setup were
not considered maintenance activities. Outside of routine sample installation/recovery and
system set-up, the only maintenance performed on the Jet-REMPI during the verification test
involved repairing a faulty pulsed valve on a parallel Jet-REMPI unit. The parallel Jet-REMPI
unit was not evaluated in this verification test and was used to monitor for other chemical species
in the flue gas. This maintenance resulted in approximately four hours of instrument downtime
during one of the test runs.
6.4.3 Consumables/Waste Generation
During the verification test, the Jet-REMPI required the use of small amounts of compressed
nitrogen gas and calibration gas standards as consumable materials.
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Chapter 7
Performance Summary
Table 7-1 presents a summary of the results of the verification of the Jet-REMPI system during
this verification test.
Table 7-1. Summary of Verification Test Results for Jet-REMPI
Parameter Evaluated
Relative accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/waste
generated
Method of Evaluation
Comparison to Method 23
reference samples
Comparison to Method 23
reference samples
Ratio of number of
samples successfully
collected to number of
potential samples that
could have been collected
Operator observations
Verification test staff
observations
Results
RA 78.2%
Intermethod RSD 61.5%
Intramethod RSD 8.4%
Apparent dependence of accuracy on PCDD/F TEQ
over range of approximately 1 to 6 ng TEQ/dscm
with better agreement at high concentration
Apparent dependence of accuracy on sample
duration over range of 4 to 8 hours with better
agreement for longer sampling duration
100% completeness in number of samples collected
Approximately 7% downtime
Time required for installation of the Jet-REMPI
system was not verified
During routine operation, a representative of
ARCADIS was on-site and constantly monitoring
instrument diagnostic and indicator signal.
Extensive training and experience with advanced
knowledge of mass spectrometry and laser
spectroscopy techniques is required for operation of
the Jet-REMPI and interpretation of the results
Repair of a faulty pulsed valve on a parallel Jet-REMPI
unit was required during the verification test. The
maintenance activities resulted in approximately 4 hours
of instrument downtime.
Small amounts of compressed gas and calibration gas
standards were used during the verification test.
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Chapter 8
References
1. U.S. EPA Method 23Determination ofPolychlorinatedDibenzo-p-dioxins and
P oly chlorinated Dibenzofuram from Municipal Waste Combustors, U.S. Environmental
Protection Agency, February 1991. Available at: http://www.epa.gov/ttn/emc/promgate/m-
23.pdf.
2. Test/QA Plan for Verification ofDioxin Emission Monitoring Systems (EMSs), Battelle,
Columbus, Ohio, September 6, 2005.
3. Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Center,
Version 5.0, U.S. EPA Environmental Technology Verification Program, Battelle,
Columbus, Ohio, March 2004.
4. George C. Clark, Michael Chu, Dahman Touati, Barry Rayfield, Jon Stone, and
Marcus Cooke, "A Novel Low-Cost Air Sampling Device (AmbStack Sampler) and
Detection System (CALUX Bioassay) for Measuring Air Emissions of Dioxin, Furan, and
PCB on a TEQ Basis Tested With a Model Industrial Boiler," Organohalogen Compounds,
40 (1999), 79-82.
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