June 2006
Environmental Technology
Verification Report
bm becker messtechnik gmbh
AMESA
(ADSORPTION METHOD FOR
SAMPLING DIOXINS AND FURANS)
Prepared by
Battelle
Batreiie
7/K 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
v>EPA Baffeiie
U.S. Environmental Protection Agency ^e Business of Innovation
ETV Joint Verification Statement
TECHNOLOGY TYPE: Dioxin Emission Monitoring System
APPLICATION: Monitoring Incinerator Emissions
TECHNOLOGY
NAME: Adsorption Method for Sampling Dioxins and Furans
COMPANY: bm becker messtechnik gmbh
ADDRESS: Kolner Strasse 6 PHONE: +49 6196 936 160
D-65760 Eschborn, Germany FAX: +49 6196 936 165
WEB SITE: www.becker-messtechnik.de/
E-MAIL: info@becker-messtechnik.de
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 bm becker messtechnik gmbh AMESA (Adsorption Method for Sampling Dioxins and
Furans) in monitoring emissions of poly chlorinated dibenzo-p-dioxins (PCDD) and poly chlorinated
dibenzofurans (PCDF). This verification statement provides a summary of the test results.
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VERIFICATION TEST DESCRIPTION
The performance of the AMESA 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 AMESA 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 AMESA 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 dioxide, 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 AMESA is based on information provided by the vendor. This technology
description was not verified in this test.
The AMESA long-term sampling apparatus is based on the isokinetic sampling of flue gas and the adsorption of
PCDD, PCDF, and other persistent organic pollutants on an exchangeable adsorption-resin-filled cartridge. The
AMESA system consists of a titanium sampling probe with probe shaft and heat exchanger, a cartridge unit as a
collection point, and a control cabinet. The titanium probe is used for both the isokinetic sampling and cooling of
the hot flue gas to less than 50°C. The cooled flue gas, together with any accumulated condensate, is fed into the
cartridge filled with adsorption resin (XAD-2) via an upstream quartz wool filter. Flue gas conditions are
monitored using sensors in the probe and are used by the control unit to adjust sampling rates to maintain
isokineticity. The PCDD/Fs can be collected over a period of up to one month and then analyzed in a laboratory.
All data required for the subsequent determination of the mass concentration are gathered automatically and
stored on a static random access memory card.
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VERIFICATION RESULTS
Parameter
Accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/waste
generated
Method of Evaluation
Comparison to Method 23
reference samples
Percent difference 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
Results
RA
Intermethod RSD
Intramethod RSD
PCDDs
48.2%
37.4%
10.0%
PCDFs
49.0%
20.9%
8.4%
PCDD/Fs
48.2%
21.9%
8.4%
No dependence of accuracy on PCDD/F toxic equivalent
(TEQ) over range of approximately 1 to 6 nanograms
TEQ per dry standard cubic meter
No dependence of accuracy on sample duration over
range of 4 to 16 hours
100% completeness
in number of samples collected
Installation of the AMES A system was completed by a
representative of becker messtechnik within 48 hours
Effectively operated after 2 hours of training in basic
operation
Installation of sampling media and removal of sampling
media completed in approximately 15 minutes each(a)
Approximately 3% down time
No maintenance was required.
XAD-2 and glass wool were used in the sampling cartridges
for sample collection. Methylene chloride, acetone, and
toluene were used to rinse the probe liner and sampling
tube.(a)
Installation and removal of sampling media were not typical of normal installation. The small duct diameter on the
boiler required a special installation and included routine removal and rinsing of the probe liner and sampling line,
which is not typically performed after each sampling period.
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
bm becker messtechnik gmbh
AMESA (Adsorption Method for
Sampling Dioxins and Furans)
by
Ken Co wen
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 and collaborated in the extramural program described
here. 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.
11
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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 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/center 1 .html.
111
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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 USEPA, 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 AMESA Installation and Operation 8
3.3 Test Design 9
3.3.1 Relative Accuracy 9
3.3.2 Range 10
3.3.3 Data Completeness 11
3.3.4 Operational Factors 11
Chapter 4 Quality Assurance/Quality Control 12
4.1 Audits 12
4.1.1 Performance Evaluation Audits 12
4.1.2 Technical Systems Audits 13
4.1.3 Audit of Data Quality 14
4.2 Quality Assurance/Quality Control Reporting 14
4.3 Data Review 14
Chapter 5 Statistical Methods and Reported Parameters 15
5.1 Relative Accuracy 15
5.2 Range 16
5.3 Data Completeness 16
5.4 Operational Factors 16
Chapter 6 Test Results 17
6.1 Relative Accuracy 19
6.2 Range 21
6.3 Data Completeness 22
6.4 Operational Factors 22
6.4.1 Ease of Use 23
6.4.2 Maintenance 24
6.4.3 Consumables/Waste Generation 24
Chapter 7 Performance Summary 25
Chapters References 26
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Figures
Figure 2-1. Photograph of AMESA 2
Figure 3-1. Wetback Scotch Marine Package Boiler 5
Figure 3-2. Illustration of Flue Gas Dust with Sampling Locations 6
Figure 3-3. Installation of AMESA Sampling Probe 8
Figure 3-4. AMESA Control Unit 9
Tables
Table 3-1. Test Run Summary 10
Table 4-1. Methods and Acceptance Criteria for PE Audit Measurements 13
Table 6-1. Summary of Test Runs and Testing Conditions 17
Table 6-2. Reference Modified Method 23 Results 18
Table 6-3. Results from the Modified Method 23 Reference Samples 19
Table 6-4. AMESA Results 20
Table 6-5. Summary of Results from the Modified Method 23 Samples and AMESA 21
Table 6-6. Relative Accuracy Results for the AMESA 21
Table 6-7. Summary of Percent Difference Values by Sampling Duration 22
Table 6-8. Activity Summary for AMESA 23
Table 7-1. Summary of Verification Test Results for AMES A 25
VI
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List of Abbreviations
AMESA
AMS
APCS
CEM
dscm
EMS
EPA
ETV
HW
LCD
NIST
PCDD
PCDF
PE
QA
QC
QMP
RA
RSD
RTF
SRAM
SMPB
TEQ
TSA
Adsorption Method for Sampling Dioxins and Furans
Advanced Monitoring Systems
air pollution control system
continuous emission monitor
dry standard cubic meter
emission monitoring system
U.S. Environmental Protection Agency
Environmental Technology Verification
hot/wet
liquid crystal display
National Institute of Standards and Technology
polychlorinated dibenzo-p-dioxins
polychlorinated dibenzofurans
performance evaluation
quality assurance
quality control
quality management plan
relative accuracy
relative standard deviation
Research Triangle Park
static random access memory
Scotch Marine Packaged Boiler
toxic equivalent
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 bm becker messtechnik gmbh AMES A (Adsorption
Method for Sampling Dioxins and Furans) in 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 AMES A. Following is a description of the AMES A,
based on information provided by the vendor. The information provided below was not verified
in this test.
The AMES A (Figure 2-1) long-term sampling apparatus is based on the isokinetic sampling of
flue gas and the adsorption of PCDD, PCDF, and other persistent organic pollutants on an
exchangeable adsorption-resin-filled cartridge. The AMES A system consists primarily of three
system components:
Titanium sampling probe with probe shaft and heat exchanger
Cartridge unit as a collection point
Control cabinet.
The titanium probe is used for both the isokinetic sampling and cooling of the hot flue gas to less
than 50°C. The cooled flue gas, together with any accumulated condensate, is fed into the
cartridge filled with adsorption resin
(XAD-2) via an upstream quartz wool
filter.
Flue gas conditions are monitored using
sensors in the probe and are used by the
control unit to adjust sampling rates to
maintain isokineticity.
The PCDD/Fs can be collected over a
period of up to one month and then sent
to a laboratory for analysis. The time
required for sample analysis will vary
depending on the method employed and
the laboratory response time. For this
verification test, AMESA cartridge
samples were analyzed in the same
Figure 2-1. Photograph of AMESA
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laboratory and by the same method as the reference samples collected during the test, and the
rinsate samples were analyzed by an independent laboratory. All data required for the
subsequent determination of the mass concentration are gathered automatically and stored on a
static random access memory (SRAM) card.
The control cabinet consists of a
Measuring gas cooler;
Condensate collection container;
Condensate pump;
Filter with a Condensate detector;
Mass flow measuring device;
Gas meter with a counting device and a temperature and pressure reading point; and
Frequency converter and a rotary vane pump.
The control unit includes both menu-driven software and a process computer. The system is
operated via five keys and a liquid crystal display (LCD) screen. This screen is also used to set
parameters and retrieve important operational data. All data relevant for measurements is stored
in the form of parameters which can be released only by means of a key switch. The computer
monitors the function of all aggregates and registers all data required for the subsequent
evaluation of the samples taken. At regular intervals, data are stored on an electronic data carrier
(SRAM card). The SRAM card is later evaluated, together with the analysis results, to ascertain
the mass concentration.
In addition to this ETV verification test, other evaluations of the AMESA system have been
completed. The AMESA system was approved by the German Technical Inspection Authority
(TUV) in 1997, has received the MCerts certification in October 2005, and participated in a
performance test for the Taiwanese EPA in 2001. During these tests many validation
measurements against the respective standard methods (EN 1948, method 23 etc.) were done.
The AMESA has also been deployed in approximately 100 applications. Results from these
other tests and applications are available from the vendor.
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Chapter 3
Test Design and Procedures
3.1 Introduction
EPA Method 23(1) 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 AMES A 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
ARCADIS under a subcontract from Battelle. The accuracy and range of the AMES A were
determined through comparisons to a modified version of Method 23 for the integrated sampling
of PCDD/PCDFs(1), 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
AMESA 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).
RA and range were determined by comparing AMESA 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 AMESA 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 are verified through dioxide
(O2) and carbon dioxide (CO2)
emission concentrations.
During this verification test, the
SMPB was fully instrumented with
continuous emission monitors
(CEMs) for a variety of species
including O2, carbon monoxide
(CO), CO2, water (H2O), and
Figure 3-1. Wetback Scotch Marine Package Boiler
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, O2, and CO2. 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
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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 AMESA. As this
figure shows, one Method 23 train sampled from a port upstream in the flue gas flow from the
AMES A's sampling port, and the other sampled downstream.
AMESA
HALF-COUPLING
TYP. OF 4
Method 23 trains
ri n i
r
n
o o o
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. (4) A feed
system was designed to safely tap the 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.
Values for the stack gas composition from the SMPB for each test run conducted during the
verification test are 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 and surrogate 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/PCDFs.
ARCADIS collected the reference method samples and coordinated their analysis, which was
conducted by EPA staff at the EPA RTF facility. To minimize potential bias caused by
interlaboratory analysis differences, the AMESA samples were also analyzed by EPA staff. 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. Additionally,
rinsate samples from the probe liners and sampling lines from the AMESA were collected and
analyzed by an independent contract laboratory. The results of those analyses were combined
with the results of the AMESA samples analyzed at the EPA laboratory to generate the final
results presented in this report.
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 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 125°C), at the impinger train outlet, at the XAD-2
cartridge outlet (maintained to be 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.
7
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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 the rinsate was collected in a single 250-milliliter (mL) amber jar. The probe and
front-half filter housing were then rinsed with toluene and the rinsate was 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 train, 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 the rinsate was 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 AMESA Installation and Operation
Figure 3-3 shows the installation of the AMESA sampling unit on the duct. Since the diameter of
the exhaust duct was considerably smaller than normal full-scale applications, the installation of
the AMESA probe was modified from the normal configuration. The modified installation
required a section of unheated Teflon tubing (approximately 1 meter in length) to deliver the
sample gas from the exit of the probe to the sampling media. Because of the potential for loss of
PCDD/F in this unheated line,
the rinsate samples noted in
Section 3.2.2 were collected and
analyzed. It should be noted that
the connection between the rigid
Teflon and the metal probe liner
is known to be a potential source
for leaking, especially when
nothing additional (such as a
tapping clip or sealing tape) is
used to secure the tubing to the
metal. A leak test was performed
according to the EPA method
prior to and after each test run
but did not include the Teflon
tubing part of the train. A
continuous leak check of the
. i i T A 11 * AA/TTHOA o i« T» i. sampling train was not
Figure 3-3. Installation of AMESA Sampling Probe / B, T , . ,
performed. Leaks in the
sampling train could potentially result in sample volumes that are biased high and consequently
reported analyte concentrations biased low relative to actual flue gas concentrations. Although
no attempt was made in this verification test to determine if there were leaks of this type, in the
standard AMESA installation the connections are made using a sealed thread and a small
clamped flange, which assures good sealing and minimizes leaks in the sampling train.
8
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Figure 3-4. AMESA Control Unit
3.3.1 Relative Accuracy
Immediately prior to each test ran, a sampling
cartridge was installed in the AMESA sampling
unit and an empty data card was installed in the
control unit. During the verification test, the
AMESA system was manually started and
stopped for each test ran, although the AMESA
allows for automated operation. After completion
of each test run, the sampling cartridge, probe
liner, and tubing leading from the probe to the
sampling unit were removed. The probe liner and
tubing were rinsed with methylene chloride and
then with toluene. The rinsate and sampling
cartridges were stored in a freezer until transport
to their respective laboratories for analysis.
Figure 3-4 shows the control unit of the AMESA
system which was located approximately
10 meters from the sampling unit.
3.3 Test Design
RA, range, data completeness, and operational
factors for the AMESA were evaluated.
The RA of the AMESA 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 AMESA was
installed, as shown in Figure 32. 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 AMESA, 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 ran to
provide a range of conditions under which the AMESA was evaluated. Two sets of operating
conditions were used for the test runs to generate expected high (i.e., 5-10 ng TEQ/dscm) and
low (i.e., 1-2 nanograms [ng] toxic equivalent [TEQ]/dry standard cubic meter [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 composite samples collected over two 8-hour
sampling periods on successive days (i.e., totaling 16 hours per sample). Table 3-1 shows the
sampling durations and boiler operating conditions for each of the nine test runs. Two Method 23
trains were used to collect each reference sample during each test ran. 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.
-------
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% Oi.
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 AMESA results.
If discrepancies of greater than 30% were observed, the data were flagged and the samples
treated as independent samples for comparison to the AMESA.
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
9/1 8/05 & 9/19/05
9/20/05
Test Run
1
2
3,4
5
6
7,8
9
Sampling Duration
4 hours
4 hours
16 hours (2x8 hours)
4 hours
4 hours
16 hours (2x8 hours)
8 hours
Expected PCDD/PCDF
Concentration^
Low
Low
High
High
High
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.
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 AMESA 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 a range of sampling periods from 4 to 16 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.
10
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3.3.3 Data Completeness
Data completeness was assessed based on the overall data return achieved by the AMESA. It
was reported as the percentage of acceptable samples collected during the verification test out of
the total number of test runs and as the percentage of time that the AMESA system was
collecting samples relative to the total duration of test runs.
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.
11
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Chapter 4
Quality Assurance/Quality Control
QA/QC procedures were performed in accordance with the QMP for the AMS Center(3) and the
test/QA plan(2) for this verification test.
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.
12
-------
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
±5%
±2% absolute
temperature
±1% absolute pressure
40% to 130% for tetra-
through hexachlorinated
compounds; and
25% 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
Center QMP,(3) the test/QA plan,(2) 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.
13
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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.(3) 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.
14
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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 AMESA during this verification test.
5.1 Relative Accuracy
The RA of the AMESA with respect to the reference sample results was assessed as a percent
bias, using Equation (1):
d
*ln I
xlOO
RM
where
\d = the absolute value of the mean of the differences between the AMESA and reference
sample results for each test run,
t0915 = the one-tailed t-value for the 97.5% confidence level,
Sd = the standard deviation of the differences between the AMESA 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):
(2)
where
15
-------
i = the standard deviation of the paired AMESA and reference method results for test ran z,
Xi = the average of the paired AMESA and reference method results for test run z, 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 ran.
5.2 Range
The range of the AMESA 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.
16
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Chapter 6
Test Results
The results of the verification test of the AMES A 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 (a)
9/15/2005(a)
9/16/2005
9/19/2005
9/20/2005 (a)
9/2 1/2005 (a)
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.
(°F)
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
4.8
3.12
3.38
C02
Cone.
(%)
12.85
12.77
12.98
12.22
12.31
12.23
12.36
13.35
13.04
H2O Cone.
(%)
8
8
8
10
8
8
8
8
8
The samples for Test Runs 3 and 4 and 7 and 8 were collected on a single cartridge for the AMESA and
analyzed as a single 16-hour test run.
Table 6-2 lists the reference method results for each test run. The results are presented for the
modified 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 toxic equivalent (TEQ)
values for each test run according to PCDDs, PCDFs, and the total. All results were corrected to
7% O2.
17
-------
Table 6-2. Reference Modified 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% O2]
Test Run 1
Port 1
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?
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
Concentrationa[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
oo
' TEQ values calculated using the WHO 98 TEF values.
-------
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 because of 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, so the average
of the results was used in all cases for evaluation of the AMESA.
Table 6-3. Results from the Modified 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
Portttl
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 analytical results of the AMESA samples for individual PCDD and PCDF
congeners, as well as the TEQ values for PCDDs, PCDFs and the totals determined for the
AMESA samples. Note that a single composite sample was collected for Test Runs 3 and 4, as
well as for Test Runs 7 and 8. As with the reference method samples, these results have been
corrected to 7% Oi. In Table 6-5, the AMESA results are presented along with the averaged
result from the reference method for each test run. In this table, the reference method results for
Test Runs 3 and 4, and for Test Runs 7 and 8 were combined to represent a single sample
totaling 16 hours. The percent difference between the reference method results and the AMESA
results is shown for each test run. For all but one of the test runs, the AMESA results were lower
than the reference method results. The percent differences range from 5.0% to -31.0% for all the
test runs. Although the AMESA was located closer to Port 7 than to Port 1, the average of the
reference method results from the two ports was used for the comparison to the AMESA.
It should be noted that the AMESA is typically used to collect long-term samples (i.e., several
week duration) versus short term sampling. Therefore, this verification test does not mimic a
typical real-world application of the AMESA.
It should also be noted that since the installation of the AMESA was not a standard installation
because of modifications needed to accommodate the AMESA on the small duct diameter,
19
-------
several potential factors which were not evaluated in this test may have contributed to bias of the
AMESA relative to the reference method results. Because of the non-standard installation, it is
possible that leaks occurred in the sampling train, which can result in a negative bias in analyte
concentration. Also, since the nozzle could not be rinsed between runs, carry-over from run to
run may have occurred.
Table 6-4. AMESA 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
Concentration [ng/dscm @ 7% O2]
Test
Runl
0.01
0.06
0.07
0.08
0.05
0.72
1.96
0.44
0.61
1.35
1.23
1.01
0.94
0.00
3.45
0.47
1.90
Test
Run 2
0.01
0.04
0.04
0.05
0.03
0.23
0.40
0.35
0.46
1.02
0.86
0.72
0.49
0.00
1.65
0.17
0.56
Test
Run
3-4
0.07
0.23
0.24
0.28
0.18
1.36
2.68
1.58
2.00
4.67
4.02
3.28
2.97
0.03
9.57
1.38
4.56
Test
Run 5
0.02
0.15
0.26
0.30
0.18
1.23
2.03
1.33
1.89
4.21
3.96
3.11
2.67
0.11
8.76
1.25
3.79
Test
Run 6
0.02
0.13
0.14
0.17
0.11
0.97
1.84
1.19
1.61
3.59
3.41
2.82
2.53
0.00
7.52
1.02
2.98
Test
Run
7-8
0.01
0.05
0.07
0.08
0.05
0.61
1.23
0.34
0.52
1.16
1.34
1.09
0.99
0.04
3.41
0.49
1.68
Test
Run 9
0.01
0.08
0.14
0.17
0.10
0.72
1.15
1.17
1.38
3.25
2.78
2.23
1.94
0.04
5.74
0.84
2.29
Concentration3 [ng TEQ/dscm @ 7% O2]
Total PCDD TEQ
Total PCDF TEQ
Total PCDD/F TEQ
0.09
1.11
1.20
0.07
0.79
0.86
0.38
3.73
4.11
0.25
3.42
3.67
0.20
2.96
3.16
0.08
1.03
1.11
0.14
2.58
2.71
' TEQ values calculated using the WHO 98 TEF values.
20
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Table 6-5. Summary of Results from the Modified Method 23 Samples and AMESA
Test Run
1
2
3 and 4(a)
5
6
7 and 8(a)
9
Average Method
23 Results (ng
TEQ/dscm)
1.62
1.10
5.96
5.23
4.55
1.05
3.89
AMESA
Results (ng
TEQ/dscm)
1.20
0.86
4.11
3.67
3.16
1.11
2.71
Absolute
Difference
(ng TEQ/dscm)
-0.42
-0.24
-1.85
-1.56
-1.39
0.05
-1.18
Percent
Difference
-26.0
-22.1
-31.0
-29.8
-30.6
5.0
-30.3
(a)
The samples for Test Runs 3 and 4 and for Test Runs 7 and 8 were collected on a single cartridge for the
AMESA and analyzed as a single 16-hour test run.
Table 6-6 shows the relative accuracy results for the AMESA, expressed as a percent as
calculated by Equation (1) (Section 5.1). The RA result for combined PCDD/F measurements is
48.2%. Separately, RA calculations are 49.0% for the PCDDs and 48.2% for the PCDFs,
respectively. 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. As a result, the RA percentage results reported in Table 6-6 are greater than the percent
differences shown in Table 6-5. In addition, the intermethod RSD of the differences between the
AMESA and average of the Method 23 results is shown, along with the intramethod RSD
between the two Method 23 trains.
Table 6-6. Relative Accuracy Results for the AMESA
Parameter
RA (%)
Intermethod RSD Intramethod RSD
PCDD TEQ (n = 7)
PCDF TEQ (n = 7)
PCDD/F TEQ (n = 7)
48.2
49.0
48.2
37.4
20.9
21.9
10.0
8.4
8.4
6.2 Range
The range of the AMESA 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.
Overall, no clear pattern exists in terms of the percent difference as a function of total TEQ
concentration. The greatest percent difference between the AMESA and Method 23 results was
-31.0% and the lowest percent difference was 5.0%. The magnitude of the differences ranged
from 0.05 ng TEQ/dscm to 1.85 ng TEQ/dscm.
21
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Table 6-7 summarizes the test runs by sampling duration. The average absolute percent
difference for 4-hour test runs was 27.1%, and the average absolute percent difference for the 8-
and 16-hour test runs was 22.1%. Thus, there was no strong apparent dependence of AMESA
accuracy relative to Method 23 on the length of the sampling run during this test.
Table 6-7. Summary of Percent Difference Values by Sampling Duration
Duration
16 hr
16 hr
8hr
> 4 hr Average
Absolute % Diff
4hr
4hr
4hr
4hr
4 hr Average Absolute
% Diff
Test Run
3 and 4
7 and 8
9
1
2
5
6
% Difference
-31.0
5.0
-30.3
22.1
-26.0
-22.1
-29.8
-30.6
27.1
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
AMESA was 100% for the verification test. However, as described in Section 6.4, during some
of the Method 23 test runs, the AMESA did not sample the flue gas for the entire sampling
period. However, overall the AMESA sampled the flue gas for approximately 97% of the total of
the sampling periods (i.e., 113 minutes downtime divided by 3360 minutes test run sampling
time = 3.4% downtime).
6.4 Operational Factors
Table 6-8 summarizes the activities performed on the AMESA system during the verification
test, as well as the time required to perform those activities and the amount of down time
experienced to complete those activities.
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Table 6-8. Activity Summary for AMESA
Date
9/12/05
9/12/05
9/12/05
9/13/05
9/13/05
9/14/05
9/15/05
9/16/05
9/16/05
9/16/05
9/19/05
9/19/05
9/19/05
9/20/05
9/21/05
9/22/05
9/22/05
Duration
20 minutes
15 minutes
15 minutes
15 minutes
15 minutes
15 minutes
15 minutes
15 minutes
50 minutes
15 minutes
20 minutes
48 minutes
15 minutes
15 minutes
15 minutes
15 minutes
15 minutes
Activity
Sample installation, instrument setup
Signal from O2 CEM was not received. Operator
programmed a constant Oi concentration and
started sampling
Sample recovery, data retrieval
Sample installation, instrument setup
Sample recovery, data retrieval
Sample installation, instrument setup
Sample recovery, data retrieval
Sample installation, instrument setup
Leak check failed, cartridge had a chip in the
thread, replaced cartridge with a new one
Sample recovery, data retrieval
Sample installation, instrument setup
Break occurred, discovered pitot flue gas sensor
tubes not connected, operator error
Sample recovery, data retrieval
Sample installation, instrument setup
Sample recovery, data retrieval
Sample installation, instrument setup
Sample recovery, data retrieval
Down Time
NA(a)
15 minutes
NA(a)
NA(a)
NA(a)
NA(a)
NA(a)
NA(a)
50 minutes
NA(a)
NA(a)
48 minutes
NA(a)
NA(a)
NA(a)
NA(a)
NA(a)
(a)
NA = Not applicable. Sample installation and recovery were performed outside of sampling period.
6.4.1 Ease of Use
The AMESA system was installed by a single representative of becker messtechnik and was
completely ready for testing within 2 days after the start of installation. Operation of the AMESA
system during the verification test was conducted by representatives of Battelle. During the first
week of testing, the representative of Battelle who operated the AMESA system was an
experienced scientist with a Ph.D. in physical chemistry and approximately 15 years of
experience in operating advanced scientific equipment. During the second week of testing, the
representative of Battelle who operated the AMESA system was also an experienced scientist
with a bachelor's degree in chemistry and approximately five years of experience in operating
advanced scientific equipment. Both representatives of Battelle were trained by a representative
of becker messtechnik for a period of approximately 2 hours. During training, the representatives
of Battelle were provided with a detailed overview of the basic operation of the AMESA
including demonstration of several important software menus used for instrument setup and
operation. Training also included a demonstration of sample installation and recovery. The
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representatives of Battelle were also asked to demonstrate several hands-on activities involving
sample installation/recovery, as well as system setup, to illustrate adequate training to the
vendor.
Installation and retrieval of the sampling media required approximately 10 to 15 minutes for each
process. However, these times were longer than would be required under normal operation since
a clean probe liner and clean Teflon tubing were installed prior to each test run and removed
after each test run for rinsing. During normal operation, only the sampling cartridge is
installed/retrieved on a routine basis, each process requiring less than two minutes.
6.4.2 Maintenance
For the purpose of this verification report, sample installation/recovery and system setup were
not considered to be maintenance activities. Outside of routine sample installation/recovery and
system set-up, no maintenance was performed on the AMESA during the verification test.
6.4.3 Consumables/Waste Generation
During the verification test, the AMESA required the use of several standard consumable
materials. The consumables that were used included XAD-2 resin (approximately 75 grams per
sample collected) and glass wool that were used in the sampling cartridge for sample collection,
as well as methylene chloride, acetone, and toluene (approximately 5 mL each) for rinsing of the
sampling probe and Teflon sampling line. Note that this rinsing was needed because of the
sampling configuration used in the test and would not be needed in a typical installation.
Additional consumables included solvents and PCDD/F standards used in the extraction and
analysis of the collected samples.
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Chapter 7
Performance Summary
Table 7-1 is a summary of the results of the AMES A verification test.
Table 7-1. Summary of Verification Test Results for AMESA
Parameter Evaluated
Relative accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/waste
generated
Method of Evaluation
Comparison to Method 23
reference samples
Percent difference
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
Not applicable
Observation
Results
PCDDs PCDFs PCDD/Fs
RA 48.2% 49.0% 48.2%
Intel-method RSD 37.4% 20.9% 21.9%
Intramethod RSD . io.0% 8.4% 8.4%
No dependence of accuracy on PCDD/F TEQ over
range of approximately 1 to 6 ng TEQ/dscm
No dependence of accuracy on sample duration over
range of 4 to 16 hours
100% completeness in number of samples collected
Installation of the AMESA system was completed
by a representative of becker messtechnik within 48
hours
Effectively operated after 2 hours of training in
basic operation
Installation of sampling media and removal of
sampling media completed in approximately 15
minutes each(a)
Approximately 3% down time
No maintenance was required during the verification
test.
XAD-2 and glass wool were used in the sampling
cartridges for sample collection. Methylene chloride,
acetone, and toluene were used to rinse the probe liner
and sampling tube.(a)
(~
Installation and removal of sampling media were not typical of normal installation. The small duct diameter on
the boiler required a special installation and included routine removal and rinsing of the probe liner and sampling
line, which is not typically performed after each sampling period in a normal installation.
25
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Chapter 8
References
1. U.S. EPA Method 23Determination of Poly chlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzofurans 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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