June 2006
Environmental Technology
Verification Report
IDX TECHNOLOGIES, LTD.
RIMMPA-TOFMS
(Resonance lonization with Multi-Mirror
System Photon Accumulation Time-of-
Flight Mass Spectrometer)
Prepared by
Battelle
Baiteiie
//it? .Business of Innovation
Under a cooperative agreement with
U.S. Environmental Protection Agency
ET1/ET1/ET1/
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June 2006
Environmental Technology Verification
Report
ETV Advanced Monitoring Systems Center
IDXTECHNOLOGIES, LTD.
RIMMPA-TOFMS
(Resonance lonization with Multi-Mirror System
Photon Accumulation Time-of-Flight Mass
Spectrometer)
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 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.
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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/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
Notice ii
Foreword iii
Acknowledgments iv
List of Abbreviations vii
Chapter 1 Background 1
Chapter 2 Technology Description 2
Chapters 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 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 14
5.3 Data Completeness 15
5.4 Operational Factors 15
Chapter 6 Test Results 16
6.1 Relative Accuracy 18
6.2 Range 18
6.3 Data Completeness 19
6.4 Operational Factors 19
6.4.1 Ease of Use 19
6.4.2 Maintenance 19
6.4.3 Consumables/Waste Generation 21
Chapter 7 Performance Summary 22
Chapter 8 References 23
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Appendix A. IDX Technologies Summary Test Report A-l
Figures
Figure 2-1. Photograph of RIMMPA-TOFMS 2
Figure 3-1. Wetback Scotch Marine Package Boiler 5
Figure 3-2. Illustration of Flue Gas Dust 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. Activity Summary for RIMMPA-TOFMS 20
Table 7-1. Summary of Verification Test Results for RIMMPA-TOFMS 22
VI
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List of Abbreviations
AHD
AMS
APCS
CEM
dscm
EMS
EPA
ETV
HW
NIST
PCDD
PCDF
PE
QA
QC
QMP
RA
RIMMPA
RTF
SMPB
TEQ
TOFMS
ISA
adsorption and heat desorption
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
National Institute of Standards and Technology
polychlorinated dibenzo-p-dioxins
polychlorinated dibenzofurans
performance evaluation
quality assurance
quality control
quality management plan
relative accuracy
Resonance lonization with Multi-Mirror System Photon Accumulation
Research Triangle Park
Scotch Marine Packaged Boiler
toxic equivalent
time-of-flight mass spectrometer
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 IDX Technologies Resonance lonization with Multi-
Mirror System Photon Accumulation Time-of-Flight Mass Spectrometer (REVIMPA-TOFMS) 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 REVIMPA-TOFMS. The following is a description of the
REVIMPA-TOFMS, based on information provided by the vendor. The information provided
below was not verified in this test.
The REVIMPA-TOFMS (Figure 2-1) is a new laser-based mass spectrometry system that has
been developed for the real-time detection and quantification of PCDD/Fs. The REVIMPA-
TOFMS is based on a two-color-two-photon ionization scheme and employs a nanosecond pulse
duration, which promotes isomer selective soft ionization with high sensitivity. Briefly, the
technology consists of a Nd:YAG pumped dye laser including frequency doublers (tuning range
between 270 - 370 nanometers, 5-8 nanosecond pulse width, 10 Hz repetition rate, under 0.1
centimeter"1 at 285 nanometer optical linewidth, 2 ml maximum output energy) for exciting
sample molecules, a
frequency quintupled
Nd:YAGlaser(213nm
laser radiation, 3-5
nanosecond pulse width,
10 Hz repetition rate, 4
ml maximum output
energy) for ionizing
excited molecules, and a
multi-mirror system by
which an optical image
relaying system is
constructed using
14 reflective mirrors. A
pulsed valve that has
been developed for
operation under a high-
temperature condition is
used in the REVIMPA-
TOFMS to produce a
Figure 2-1. Photograph of RIMMPA-TOFMS supersonic jet under the
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choke-flow condition. This supersonic jet allows the sample gas to be cooled to cryogenic
temperatures and generates uniform ordering of the gaseous molecules so that the collisions
between particles are minimized, which extends the excitation lifetime of the target compounds.
The supersonic molecular beam interacts with the two multi-reflected synchronous laser beams
for about 40 nanoseconds in the ionization region, where the target molecules are selectively
ionized and accelerated into the time-of-flight mass spectrometer.
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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/F 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/Fs and may have the potential to provide more information on PCDD/F source
emissions than the relatively few samples required under federal or state regulations. 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 REVIMPA-TOFMS
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 REVIMPA-TOFMS
were determined through comparisons to the standard Method 23 integrated sampling method for
PCDD/Fs.(1) 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
REVIMPA-TOFMS was to be evaluated in terms of
Relative accuracy (RA),
Range,
Data completeness, and
Operational factors (ease of use, maintenance, and consumables/waste generated).
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RA and range was to be determined by comparing RIMMPA-TOFMS results to those from
Method 23 reference samples collected simultaneously. Range was to be determined from
measurements over a variety of defined operating conditions that produced differing levels of
PCDD/Fs. Data completeness was assessed as the percentage of maximum data return achieved
by the RIMMPA-TOFMS 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 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 ©2, 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 second 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
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
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boiler to allow for the simultaneous installation of multiple dioxin EMSs and operation of
duplicate Method 23 sampling trains. Figure 3-2 shows a schematic illustration of the duct,
identifying the sampling locations for the reference sample trains and the RIMMPA-TOFMS. As
this figure shows, one Method 23 train sampled from a port upstream in the flue gas flow from
the RIMMPA-TOFMS's sampling port, and the other sampled downstream.
^EXISTING
V3" HALF-COUPLING
TYP.
HALF-COUPLING
TYP. OF 4
Method 23 trains
RIMMPA-TOFMS
/
* 1
1 1 1 1
r
1
0 0 0
Figure 3-2. Illustration of Flue Gas Duct with Sampling Locations
A surrogate chlorinated chemical (1,2-dichlorobenzene) and a source of metal atoms (copper
naphthenate) were added to the boiler fuel to promote PCDD/F formation for the emission
monitoring system (EMS) testing.(4) A surrogate feed system was designed to safely tap the
surrogate 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 surrogate 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/F using Method 23, with the
following modifications established before any sample collection took place:
Analysis was completed by high-resolution gas chromatography/low-resolution mass
spectrometry.
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Mass locking was not used with the 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 dioxins and furans.
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 REVIMPA-TOFMS 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.
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 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.
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
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.
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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 Installation and Operation
Figure 3-2 shows an illustration of the duct indicating the locations of the Method 23 reference
sampling ports and the location of the RIMMPA-TOFMS 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 RIMMPA-TOFMS. The PCDD/Fs in the sample gas were collected on Tenax resin. After
collection, the Tenax was heated, releasing the PCDD/Fs, which were subsequently introduced to
the RIMMPA-TOFMS for analysis.
3.3 Test Design
Relative accuracy, range, data completeness, and operational factors for the REVIMPA-TOFMS
were evaluated.
3.3.1 Relative Accuracy
The RA of the REVIMPA-TOFMS 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 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
REVIMPA-TOFMS 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/F concentrations determined by the reference methods were compared to corresponding
results from the REVIMPA-TOFMS, averaged over the period of each Method 23 run. During
each of the 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 REVIMPA-TOFMS was evaluated.
Two sets of operating conditions were used for the runs to generate expected high and low dioxin
concentrations. 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
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boiler operating conditions for each of the nine runs. Two Method 23 trains were used to collect
each reference sample during each 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.
Upon completion of each 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 toxic equivalents per dry standard cubic meter
(TEQ/dscm), corrected to 7% O2. 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 REVIMPA-TOFMS results. If discrepancies of greater than 30% were
observed, the data were flagged and the samples treated as independent samples for comparison
to the REVIMPA-TOFMS. Discussion of the results of these comparisons is presented at the start
of Chapter 6.
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 Dioxin
Concentration1^1
Low
Low
High
High
High
Low
High
Expected concentrations based on results of baseline testing. "High" corresponds to expected total PCDb
TEQ of roughly 5-10 ng TEQ/dscm, and "low" corresponds to expected concentrations of roughly 1-2 ng
TFH/rlcr'm
TEQ/dscm.
3.3.2 Range
Range was to be assessed in terms of RA over the range of measured dioxin 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 REVIMPA-TOFMS 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
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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 REVIMPA-
TOFMS. It was reported in terms of the percentage of acceptable samples collected during the
verification test and in terms of percentage of time that the REVIMPA-TOFMS 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.
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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 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
Table 4-1.
The PE audit of the internal standard recovery was performed by spiking one blank Method 23
train with an NIST-traceable dioxin 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.
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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
Dioxin internal
standard recovery
Dioxin 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
dioxin standard
Field spike with an independent
dioxin standard
Acceptance Criteria
±5%
±2% absolute
temperature
±1% absolute pressure
40 to 130%fortetra-
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 dioxin 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 of 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.
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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.
13
-------
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 RIMMPA-TOFMS during this verification test.
5.1 Relative Accuracy
The RA of the REVIMPA-TOFMS with respect to the reference sample results was assessed to be
as a percent bias, using Equation (1):
(1)
RM
where:
= the absolute value of the mean of the differences between the REVIMPA-TOFMS and
reference sample results for each test run,
t0975 = the t- value,
Sd= the standard deviation of the differences between the REVIMPA-TOFMS and reference
sample results for each test run, and
RM = the mean of the reference method results.
5.2 Range
The measurement range of the REVIMPA-TOFMS was to be reported in terms of its accuracy
relative to the reference method under the variety of boiler operating conditions (i.e., PCDD/F
concentrations) and sampling durations used during the test runs.
14
-------
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 and information provided by
the vendor. No statistical comparisons of operational factors were made.
15
-------
Chapter 6
Test Results
The results of the verification test of the RIMMPA-TOFMS 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)
9/21/2005(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
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
The samples for Test Runs 3 and 4 and 7 and 8 were collected on a single cartridge for the RIMMPA-TOFMS
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
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 dioxin and
furan congeners. The lower portion of the table summarizes the TEQ values for each test run
according to dioxins, furans, and the total. All results were 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
Total PCDF
Total PCDD/F
Concentration fng/dscm (3j 7% O21
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?
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 dioxins 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 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, the average of the results was used in
all cases for evaluation of the REVIMPA-TOFMS.
Table 6-3. Results from the Method 23 Reference Samples
Test
Run
1
2
3
4
5
6
7
8
9
Dioxin TEQ
Port#l
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%
Furan TEQ
Port#l
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#l
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
No quantifiable results were obtained from the REVIMPA-TOFMS during the verification test so
no estimate of relative accuracy could be made. Various difficulties associated with sampling
and analysis using the REVIMPA-TOFMS arose during the verification testing. A discussion of
these problems is presented in Section 6.4. Additionally, Chart 2 in Appendix A shows the
congener intensities detected by the REVIMPA-TOFMS. IDX Technologies was able to detect
and identify several of the highly chlorinated dioxin congeners, but was not able to get the results
of the determination because of the influence of impurities that existed close to the dioxin mass
numbers. Appendix A is presented as received by Battelle from EOX Technologies and has not
been edited for inclusion in this report.
6.2 Range
No evaluation of range could be assessed during this verification test, for the reasons noted
above under Relative Accuracy.
18
-------
6.3 Data Completeness
RIMMPA-TOFMS sampling took place for a total of 42% of the total duration of the test runs.
Sampling was achieved during portions of seven of the nine test runs. No REVIMPA-TOFMS
sampling took place during two of the nine test runs.
Although sampling was successfully conducted during several of the sampling periods, no
quantitative data were generated from the REVIMPA-TOFMS to characterize PCDD/F
concentrations in the flue gas.
6.4 Operational Factors
Table 6-4 summarizes the activities performed on the REVIMPA-TOFMS 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. 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 REVIMPA-TOFMS operator may have continued to
perform activities until each test run commenced.
6.4.1 Ease of Use
Ease of use of the REVIMPA-TOFMS was not easily established during this verification because
of the difficulties encountered with the sampling system. Operation of the REVIMPA-TOFMS
during this verification test was conducted by a group of four representatives from IDX. It was
not apparent that the REVIMPA-TOFMS was operated under routine conditions because of
problems encountered during testing. Extensive maintenance activities meant that operators were
simultaneously working on separate portions of the REVIMPA-TOFMS during several periods
during the test. At least one operator was required during sample collection and analysis to
ensure proper operation. In general, operation of the REVIMPA-TOFMS requires extensive
knowledge of sophisticated laser systems and mass spectrometers including advanced electronic
data collection and manipulation equipment.
6.4.2 Maintenance
Significant maintenance activities were performed on the RIMMPA-TOFMS during this
verification test. This maintenance was the result of contamination issues and failures in the
sampling system employed for the verification test. These maintenance activities are not
expected to be routine, but resulted in the loss of significant amount of testing data while the
activities were performed.
19
-------
Table 6-4. Activity Summary for RIMMPA-TOFMS
Date
9/12/05
9/13/05
9/14/05
9/15/05
9/16/05
9/19/05
9/20/05
9/21/05
9/22/05
Duration
Approximately 9 hours
Approximately 10 hours
Approximately 10 hours
Approximately 12 hours
Approximately 10 hours
Approximately 9 hours
Approximately 12 hours
Approximately 12 hours
Approximately 12 hours
Activity
Instrument start-up, calibration, and testing preparations.
Sample collection for 240 minutes.
Sample desorption and analysis
Signal from the RIMMPA-TOFMS indicated that the sampling system had
become contaminated.
Glass wool from the sorbent tube became dislodged from the tube and was
introduced into the sample delivery lines along with a portion of the
TENAX resin.
Representatives from IDX technologies cleaned the sampling system and
the sample delivery system, including the replacement of the pulsed nozzle
for sample introduction.
No sample collected because of change of high-temperature gas valve unit.
Signal from the RIMMPA-TOFMS still indicated contamination in the
system. Sampling lines were cleaned.
Modifications were made to the sampling system to bypass the Adsorption
and Heat Desorption (AHD) unit and use a temporary sampling system.
Sample collected for 90 minutes near end of test run.
Stainless steel sampling lines and sample delivery lines were replaced. The
TENAX was cleaned and replaced in the sampling system with new glass
wool.
No sample collected because of change of high-temperature gas valve unit.
Instrument start-up, calibration, and testing preparations.
Sample collection for 90 minutes.
Sample desorption and analysis.
Sample collection for 70 minutes.
Sample desorption and analysis.
Instrument start-up, calibration, and testing preparations.
Sample collection.
Sample desorption and analysis.
Instrument start-up, calibration, and testing preparations.
An air leak was discovered and corrected prior to testing.
Sample collection for 120 minutes.
Sample desorption and analysis.
Sample collection for 240 minutes.
Sample desorption and analysis.
Sample inlet reconfigured to place TENAX resin closer to the filter.
Instrument start-up, calibration, and testing preparations.
Sample collection for 120 minutes.
Sample desorption and analysis.
Sample collection for 200 minutes.
Sample desorption and analysis.
Sampling approach was modified to decrease the amount of TENAX resin
used and decrease the sampling duration.
Instrument start-up, calibration, and testing preparations.
Sample collection for 15 minutes.
Sample desorption and analysis.
Sample collection for 15 minutes.
Sample desorption and analysis.
NA= Not applicable. Sample installation and recovery are performed outside of sampling period.
20
-------
6.4.3 Consumables/Waste Generation
Operation of the RIMMPA-TOFMS required use of compressed helium as a carrier gas for the
supersonic expansion, TENAX and glass wool for sample collection, as well as laser dye and
solvent for operation of the laser system. Only one batch of dye solution was required during this
verification test, which is treated as chemical waste for disposal.
21
-------
Chapter 7
Performance Summary
Table 7-1 presents a summary of the results of the verification of the RIMMPA-TOFMS system
during this verification test.
Table 7-1. Summary of Verification Test Results for RIMMPA-TOFMS
Parameter Evaluated
Accuracy
Range
Data completeness
Ease of use
Maintenance
Consumables/wastes
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
Operator observations
Operator observations
Results
Analysis of the collected samples could not
positively quantify PCDD/PCDFs.(a)
Analysis of the collected samples could not
positively quantify PCDD/PCDFs.
Samples were collected for 42% of the
duration of the test runs.
Samples were collected during portions of
seven of the nine test runs.
Routine operation of the sampling system
was not observed during this test.
Extensive training and experience with
advanced knowledge of mass spectrometry
and laser spectroscopy techniques is
required for operation of the RIMMPA-
TOFMS and interpretation of the results.
Extensive maintenance was required during
the verification test to rectify a number of
difficulties encountered during sampling.
Compressed helium was required during
testing to deliver collected sample from the
sorbent trap to the RIMMPA-TOFMS.
TENAX and glass wool were used in the
sorbent trap for collection of the gas
samples.
Laser dye and solvent were used for
operation of the RIMMPA-TOFMS laser
system.
1 See Chapter 6.
22
-------
Chapter 8
References
1. U.S. EPA Method 23Determination of Poly chlorinated Dibenzo-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 ofDioxin, Furan, and
PCB on a TEQ Basis Tested With a Model Industrial Boiler," Organohalogen Compounds,
40 (1999), 79-82.
23
-------
Appendix A
IDX Technologies Summary Test Report
NOTE: This document was prepared by IDX Technologies and is published as received. This
document was not edited or verified by Battelle.
-------
-------
March 22 2006
ETV REPORT
IDX-Technologies
1. Introduction
As we have reported in many occasions in the world that we have succeeded in the
development of RIMMPA (Resonance lonization with the jyMti-Mirror system Photon
Accumulation)-TOFMS. By the development of it, we have achieved the 2 color 2 photon
resonance ionization of tetra to octa chlorinated DDs and DFs with selective soft ionization of
PCDD's and PCDF's isomers.
Thus, the ETV for us is to verify the technical results on RIMMPA-TOFMS.
We have adopted two countermeasures upon this current situation. The first
countermeasure is to adopt an accumulation tube as a condenser for obtaining the high
density sample gas and to use helium gas for desorbing it as carrier gas.
The second is to adopt the fixed wavelength laser to make the size compact and to realize
easy operation and mobile-ability.
What we had achieved in the laboratory was to detect the PCDD's and PCDF's isomers of
2,3,4,7,8-PeCDF at 410 ppq sensitivity by changing the excitation wavelength and could
detect only objective parent ion without any fragmentation.
We haven't reached, however, the stage to detect the PCDD's and PCDF's isomers in the
real gas. This is one of the purposes of this ETV tests for us to establish the method and
verify the on-site and rapid analysis method in the real gas from boiler.
2. Target
What we have targeted through ETV test this time was that after filtering, adsorbing and
accumulating the exhausting gas into a TENAX column, desorption of PCDD's and PCDF's
are carried under the specifically controlled temperature and then is loaded to
RIMM PA-TOFMS with helium carrier gas. We aimed at the two kinds of analysis, one was the
Congener analysis and the other was the Isomer analysis.
Here, we mean that the congeners analysis is to calculate the TEQ from the relation
between the sum of the total ion signals of tetra to octa chlorinated DDs and DFs and that of
the Method 23(M23). The sum of the total ion signals of tetra to octa chlorinated DDs and
A-l
-------
DFs congener's ion is calculated as follows. Selecting and fixing an appropriate wavelength
of excitation laser wavelength as 310.99nm, we can get all the tetra to octa chlorinated DDs
and DFs congener's ion signals and sum up the amount of time variation.
And the isomer analysis is to calculate the TEQ from the correlation between the total
amount of target isomer's ion signal and that of M23 signals. Setting the excitation laser
wavelength for the target isomer and getting the isomer signal and integrating it by time, we
can get the total amount of target isomers.
3. Test circumstances
Terms: Sep. 12 2005 to Sep. 22 2005
Place: U.S. Environmental Protection Agency, Research Triangle Park
Test facilities: A 2.94 MBtu/hr, 3-Pass Wetback Scotch Marine Package Boiler
manufactured by Superior Boiler Works, Inc.,
(Details are in the ETV program report)
4. Test method
The schematic diagram of sampling is shown in Fig.1
The sampling steps are briefly divided into next four steps.
4.1 Adsorption
The exhausted gas flows in the Adsorption and JHeat Desorption (AMD) unit from sampling
port in flue gas duct heated at 160 degree C through sampling probe heated at 200 degree C,
glass fiber filter and 5m heated sampling line (Teflon tube). At the AMD, PCDD'sand PCDF's
in the exhausted gas are adsorbed in the 105 degree C heated TENAX column. The
exhausted gas is disposed lastly in APCS (Air Pollutant Control System) through Silica gel,
NaOH solution and pump.
4.2 Helium Substitution
To remove nitrogen, oxygen and low boiling point organic compounds that remain in
TENAX column, helium gas of 120 degree C is substituted for the gases in TENAX column of
105 degree C for 5 minutes with 3L/min.
4.3 Desorption
The column is heated up to 300 degree C after closing the entrance and exit of it. Keeping
it for 10 minutes after the temperature rises up to 300 degree C, the objective gas in helium
carrier gas is injected to RIMMPA-TOFMS at 200 degree C.
4.4 Analysis
Analysis of congeners and isomers by RIMMPA-TOFMS are carried out.
A-2
-------
X
Heated Transfer Line
(Stainless Steel Tube)
Heated Quartz
Probe Liner
Adsorption and Heat Desorption Unit
including four condensers
NaOH Solution
Sample Nozzle
Fig.1 Schematic diagram of the sampling train, adsorption and heat
desorption unit, and measurement by RIMMPA-TOFMS
5. Test conditions
Chart 1 shows the test conditions of each day during ETV tests.
A-3
-------
Chart 1
Test
Number
9/12
9/14
9/16-#1
9/16-#2
9/19
9/20-#1
9/20-#2
9/21 -#1
9/21 -#2
9/22-#1
9/22-#2
Sampling
time [min
240
90
70
90
240
120
240
120
200
15
15
rate [L/min]
2.739
4.85
17.083
16.562
15.19
13.76
12.51
17.19
19.3
16.19
16.33
volume [L]
657.36
436.5
1195.81
1490.58
3645.6
1651.2
3002.4
2062.8
3860
242.85
244.95
DXN-Desorption
temp. [deg.C]
300
280
300
300
300
300
300
300
300
300
200-300
flow rate [L/min]
1
1
1
1
1
0.5
0.5
0.5
0.5
0.5
0.5
Excitation Laser
Energy [mJ]
3
3
3
3
3
3
3
3
3
3
3
Wavelength [nm]
310.99
310.99
310.99
310.99
315.83
310.19
310.19
310.19
310.19
310.19
310.19
lonization Laser
Energy [mJ]
0.1
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
6. Test results
6.1 Congener Analysis Test Results
Chart 2 is the results of our ETV tests. The Test Number 9/19 is the result of isomer analysis
and the other all are congener analysis. The values in the chart show the signal strengths of
the dioxin congeners that RIMMPA-TOFMS detected. Although RIMMPA-TOFMS has
succeeded in congener identification of several high-chlorinated dioxins, RIMMPA-TOFMS
has not succeeded in determination of isomers due to the bad influence of impurities that
exist close to dioxins in mass numbers.
A-4
-------
Chart 2
TeCDD
PeCDD
HxCDD
HpCDD
OCDD
TeCDF
PeCDF
HxCDF
HpCDF
OCDF
9/12
1.7
1.3
9/14
9/16-#1
9/16-#2
9/19
9/20-#1
7.1
6.1
9/20-#2
9/21 -#1
12.1
5.1
9/21-#2
9/22-#1
9/22-#2
Blank=Not identified
6.2 Test result details
First half
The chart 3 below shows the results from Sep. 12 to Sep. 16.
A-5
-------
Charts
Sample transfer
Adsorption
Helium substitution
Desorption
RIMMPA-TOFMS
Others
Results
9/12
5m Teflon tube
105 degree C
3L/min, 5mm
300 degree C
310.99nm, 3mJ
213nm, 0.1mJ
Preheating of He gas
200 degree C
Congener analysis
Fig.2-12
Lots of impurity
TENAX decomposition
Impossible to identify
and determine
9/13
Pipe cleaning
by solvent
AHD unit cleaning
New HTPD
Abherence of TENAX
in inside of HTPD
Adherence of TENAX
in the pipe
9/14
5m Teflon tube
105 degree C
3L/min, 5mm
300 degree C
310.99nm, 3mJ
213nm, 0.1mJ
preheating of He gas
200 degreeC
Congener analysis
Fig 13
same as 9/1 2
Fig14, 15
stains in the AHD unit
9/15
Brand new pipe
TENAX cleaning
change of glass wool
Improvement
sampling unit
Cleaning and change
HTPD
Higher volume of
sampling rate by
changing glass wool
9/16
5m Teflon tube
105 degree C
3L/min, 5mm
300 degree C
310.99nm, 3mJ
213nm, 0.1mJ
New He bomb
Insert activate charcoal
between TENAX column
and He bonbe
No preheating of He gas
Congener analysis
Fig17, 18
spectrum quenching of
m/z320, 345
No changes in the others
Change from Helium to N2
for cleaning
Chamber baking
Sep. 122005
Figure 2 (Test number: 9/12) shows the mass spectrum of 270 to 500 measured by
RIMMPA-TOFMS. The ion signal was obtained by integrated value of 3 minutes
measurement. Although we recognized the PCDD's and PCDF's peaks, it was tough to
identify and determine PCDD's and PCDF's because the spectra of other impurities
overlapped the peak signals of the PCDD's and PCDF's. As indicated a and b in Fig.2, we
detected the spectrum of impurities that adhere to the TENAX, the mass number of which
increase by m/z 75 regularly, and the spectrum obstruct the measurements of PCDD's and
PCDF's. It was thought as impurity in TENAX and it disturbs the PCDD's and PCDF's
spectra.
A-6
-------
100
80
60
co
c
o
20
250
300
350
400
450
500
m/z
Fig.2 Mass spectrum (Test number: 9/12)
Figures 3 to 12 are the mass spectra which are expanded near PCDD's and PCDF's
congeners. The indicated values are relative intensity of each peak normalized by M+2 ion
signal in the case of TeCDF or M+4 ion signal in the case of OCDF. We recognized some
differences in the intensity ratio between the observed one and that estimated from
existence ratio of chlorine isotope. In the case of TeCDF, the observed ratios are 50.6/100
and 60.5/100, while the estimated ratios are 76/100 and 49/100. We assume that these
differences might be caused by the spectra overlapping.
c
gi
CO
c
o
295
300
305
mtz
310
315
Fig.3 TeCDF
100
80
3
i 60
"(5
c
o
40
20
310
A-7
315
320
mtz
325
330
Fig.4TeCDD
-------
q 3
To
CO
c
o 1
335
340
345
ra 3
0)
CO 2
s=
o
345
350
355
mlz
360
365
Fig.5 PeCDF
Fig.6 PeCDD
10
"55
c
O)
CO 4
360
365
370
mlz
375
380
3
_ro. q
To
c
gi
CO 0
380
385
390
mfz
395
400
Fig.7 HxCDF
Fig.8 HxCDD
20
15
TO
c 10
O)
CO
395 400 405 410 415 420
mfz
Fig.9 HpCDF
415
420
425
mfz
430
435
Fig.10 HpCDD
A-8
-------
,ca,
7i
O
435
OCDF
26.1 57.5 100 70.2 48.4
440
445
m/z
450
455
Fig.11 OCDF
"5
gi
450
455
460
m/z
465
470
Fig.12OCDD
Sep. 132005
To avoid the stains in the AMD unit, pipes and JHigh Temperature Pulsed gas Device
(HTPD), HTPD was changed to new one. We blow off TENAX in the AMD unit by the
compressed air. And we also cleaned pipes between the AMD unit by both of compressed air
and solvent.
Sep. 142005
Figure 13 is the mass spectrum (mass number: 270 to 500) measured by RIMMPA-TOFMS.
The ion signals are obtained by integrated value of 3 minutes measurement. The signals of
impurity, however, did not disappear even after cleaning and changing of HTPD to new one.
It was tough to identify and determine PCDD's and PCDF's because the spectra of the other
impurity overlapped the peak signal of the PCDD's and PCDF's although we recognized the
PCDD's and PCDF's peaks in our results.
A-9
-------
120
100
80
CD
60
gi
CO
c
.2 40
20
0
250 300 350 400 450 500
m/z
Fig. 13 Mass spectrum (Test number: 9/14)
Figure 14 and 15 show the two cases of helium gas pass through the AMD unit and the
case of not passes through the unit. From these results, we realized that the inside of the
AMD unit has stained, so that we newly created another way of sampling without using the
unit. (Refer Fig. 16). And we cleaned HTPD and changed the parts of the units. Also we
cleaned TENAX as well at 280 degree C for 16 hours assuming that TENAX itself has its
stain.
A-10
-------
80
70
60
d
«L 50
To
ra 40
CO
c 30
_o
20
10
0
1
250 300 350 400 450 500
mfz
Fig. 14 through the AMD unit
250
300
350 400
mfz
450
500
Fig. 15 not going through the AMD unit
A-ll
-------
3-way Valve
CilicaGel NaOH Solution
Sample Nozzle
Fig. 16 Schematic diagram of the sampling train, adsorption and heat
desorption by single condenser, and measurement by RIMMPA-TOFMS
Sep. 162005
We changed the glass wool to raise the sampling rate, and changed a helium cylinder to a
new one as well. And we inserted the activated charcoal filter between helium cylinder and
TENAX column to avoid impurity in the helium gas.
A-12
-------
Figure 17(Test number: 9/16-#1), Fig.18 (Test number: 9/16-#2) are the mass spectra
(mass number: 270 to 500) measured by RIMMPA-TOFMS and the mass spectra are
obtained by integrated value of 3 minutes measurement. If we compare with the Fig. 14, the
ion signal of mass number 320 and 345 are decreased. However, we could not identify and
determine the PCDD's and PCDF's due to the peaks of impurity.
100
80
iSi 60
"55
c
01
W 40
20
100
BO
3_
S, 60
15
c
01
W 40
20
250
300
350 400
mtz
450
500
250
300
350 400
mfz
450
500
Fig.17 Mass spectrum(Test number:9/16-#1) Fig.18 Mass spectrum(Test number: 9/16-#2)
We changed the cleaning solvents from helium to nitrogen and cleaned HTPD again at 200
degree C for a day. Baking in the chamber was also done for a day. Another way that we did
was to change to a 3/4 inch tube that doesn't require seal tape because we assumed that the
exhausted gas from seal tape might cause the noise in the spectra of PCDD's and PCDF's.
Second half
The chart 4 below shows the summary of the results of sep. 19 thru Sep.22
A-13
-------
Chart 4
Sample transfer
Adsorption
Helium substitution
Desorption
RIMMPA-TOFMS
Others
Results
9/19
5m Teflon tube
105 degree C
3L/min, 5mm
300 degree C
315.83nm, 3mJ
213nm, 0.1mJ
No preheating of He gas
Isomer analysis
(2,3,4,7,8-PeCDF)
Change the 3/4 inch tube
Fig. 19
Spectrum quenching of
m/z395, 410
Spectrum decreasing of
m/z470, 490
Fig.20
Detect the peak signals in
the m/z=338,340 and 342
2,3,4, 7,8-PeCDF isomer is
imposible to identify
9/20
5m Teflon tube
105degreeC
3L/min, 5mm
300 degree C
310.19nm, 3mJ
213nm, O.SmJ
Change to improve the sensitivity
No preheating of He gas
Leak check of sampling line
Doubled the volume the second
sampling of first volume
Congener analysis
Fig.21-32
TeCDD, PeCDD is
posible to identify
No detection of HpCDD,
OCDF.OCDD
Other congeners are
imposible to identify
9/21
No use
105 degree C
3L/min, 5mm
300 degree C
310.19nm, 3mJ
213nm, O.SmJ
No preheating of He gas
Congener analysis
Set TENAX column directly
after the filter
Fig.34-45
Same as previous day
There is a possibility
TENAX was broken
through due to the too
much sampling amount
9/22
No use
105degreeC
3L/min, 5mm
300 degree C
310.19nm, 3mJ
213nm, O.SmJ
No preheating of He gas
Congener analysis
Set TENAX column directly
after the filter
Fig .46-56
m/z278 signal increased
Congeners are
imposible to identify
Detection of mass spectrum
m/z260, 262
Fig.57
The flow rate 0.5 to 3 L/min
the ion signals increased
Sep. 19 2005
Though many kinds of material are ionized because we use the shorter wavelength of the
excitation laser in the congener analysis, the only selected isomers would be ionized in the
isomer analysis because the longer wavelength of excitation laser is applied.
Figure 19 (Test number: 9/19) is the mass spectrum (mass number: 270 to 500) when we
carried out the isomer analysis of 2,3,4,7,8-PeCDF. The ion signal is integrated value for 3
minutes measurement. The peak signals of mass number 395, 410 quenched, 470 and 490
decreased and peak signal of mass number 362 was increased. These materials are
resonantly ionized by the excitation laser wavelength of 2,3,4,7,8-PeCDF.
Figure 20 is the mass spectrum near the 2,3,4,7,8-PeCDF. Although there exist the peak
signals in the m/z=338, 340 and 342, we could not identify the 2,3,4,7,8-PeCDF isomer
because the ionization intensity is different from the ionization intensity ratio that can be
estimated by the isotope existence ratio.
A-14
-------
100
so
2L 60
"55
c
O)
" 40
20
5L
"in
2
250 300
350 400
m/z
450
500
Fig.19 Mass spectrum (Test number: 9/19)
330
335 340 345 350
mfz
Fig.202,3,4,7,8-PeCDF
Sep.20 2005
We changed from isomer analysis to congener analysis because we could not identify
2,3,4,7,8-PeCDF in isomer analysis. We did leak check of sampling port before tests. To rise
up the sensitivity, we changed the excitation laser wavelength to 310.19nm and ionization
laser energy to 0.5 mJ because we thought the PCDD's and PCDF's density was too low to
detect. We tested whether the peak signals become doubled when we sample the double
volume as first sampling volume.
Figure 21 (Test number: 9/20-#1), Fig.22 (Test number: 9/20-#2) are the mass spectra
(mass number: 270 to 500) measured by RIMMPA-TOFMS and the mass spectra are
obtained by integrated value of 3 minutes measurement. The second sampling volume was
double of the first one, however, the signals in the second sampling were lower than the first
one.
100
80
i 60
To
c
O)
CO 40
20
LA.
120
250
300
350 400
m/z
450
500
250
300
350 400
mfz
450
500
Fig.21 Mass spectrum (Test number:9/20-#1) Fig.22 Mass spectrum(Test number:9/20-#2)
A-15
-------
Figures 23 to 32 are the mass spectra which are expanded the near parent-ion spectrum of
the tetra to octa chlorinated DDs and DFs. The indicated values are relative intensity of each
peak normalized by M+2 ion signal in the case of TeCDD, PeCDD. We recognized some
differences in the intensity ratio between the observed one and that estimated from
existence ratio of chlorine isotope. In the case of TeCDD, the observed ratios are 71.2/100
and 57.6/100, while the estimated ratios are 77.4/100 and 48.7/100. But no detection was
made on HpCDD, OCDF and OCDD or of the other congeners.
20
15
ra
c 10
O)
295
300
305
mfz
310
315
Fig.23TeCDF
25
20
3
i is
75
c
CO 10
c
o
TeCDD
71.2 100 57.6
315 320 325
mfz
Fig.24 TeCDD
330
3D
20
g 15
CO
10
330
335
340
mfz
345
350
Fig.25 PeCDF
15
=1 10
CD
c
gi
CO
O 5
PeCDD
58 100 34.9
350 355 360
m/z
Fig.26 PeCDD
365
A-16
-------
10
J5L 6
"5
c
Ol
c
o
365 370
375
mfz
Fig.27 HxCDF
3
ni
To
c
as
CO
380 385
380 385
390
m/z
395 400
Fig.28 HxCDD
SL 3
"ro
!=
CO 2
c
o
0
400
405
410
mfz
2.5
II
ro 2
01
CO 1-5
0.5
415 420
415 420
425
mfz
430 435
Fig.29 HpCDF
Fig.30 HpCDD
2.5
"5
c
01
to 1.5
c
o
0.5
435
440
445
mfz
Fig.31 OCDF
450 455
A-17
470
Fig.32 OCDD
-------
Sep.21 2005
Knowing the fact that PCDD's and PCDF's are decreased to 1/2 during the gas moves
30cm in a 1/4 inch size Teflon tube, and that if a Teflon tube is heated at 200 degrees C, out
gas will occur and PCDD's and PCDF's will be denatured, the 5m heated sampling line
(Teflon tube) prepared before the experiment was removed. So the TENAX column was set
directly after the filter of filter oven (Fig.33). After sampling, the temperature of the TENAX
column was cooled down from 105 degree C and took it out from Filter Oven. And bringing it
to the site of RIMMPA-TOFMS and going into the steps of helium substitution, desorption
and analysis were curried out.
Figure 34 (Test number: 9/21-#1), Fig.35 (Test number: 9/21-#2) are the mass spectra
(mass number: 270 to 500) measured by RIMMPA-TOFMS and the mass spectra are
obtained by integrated value of 3 minutes measurement. The total trend of the results of
no-use of Teflon tube was not different from the case of use of it. The second sampling
volume was doubled as the previous day and the signals of impurity were decreased on this
day. We decided it had break through since there are too many amounts of samplings.
A-18
-------
RIMMPA-TOFMS
Sample Nozzle
Fig.33 Schematic diagram of the sampling train, with single condenser,
connected to filter directly, and measurement by RIMMPA-TOFMS
to
c
o
100
80
60
40
20
0
250 300
350 400
mfz
100
so
60
t?«
c
o
450 500
UK
250 300
350 400
mfz
450 500
Fig.34 Mass spectrum (9/21-#1)
Fig.35 Mass spectrum (9/21-#2)
A-19
-------
Figures 36 to 45 are the mass spectra which are expanded near parent-ion spectrum of the
tetra to octa chlorinated DDs and DFs. The indicated values are relative intensity of each
peak normalized by M+2 ion signal in the case of TeCDD, PeCDD. We recognized some
differences in the intensity ratio between the observed one and that estimated from
existence ratio of chlorine isotope. In the case of TeCDD the observed ratios are 67.2/100
and 38.8/100, while the estimated ratios are 77.4/100 and 48.7/100.
But the other congeners were impossible to identify.
"55
CO
c
o
40
35
30
25
20
15
10
5
295
gi
CO
c
o
20
15
10
300
305
mfz
310
315
TeCDD
67.2 100 38.8
Fig.36TeCDF
315 320 325
mfz
Fig.37 TeCDD
330
A-20
-------
20
15
3
re,
I 1°
CO
c
o
330
335
340
mfz
345
Fig.38 PeCDF
10
350
q
CD
g>
CO
PeCDD
70.5 100 81.4
350 355 360
mfz
Fig.39 PeCDD
365
10
co
c
o
365
370
375
mfz
380
385
a e -
ro
c
gi
CO
E
O
380
400
Fig.40 HxCDF
Fig.41 HxCDD
ro
c
D)
CO 2
C
O
0
400
405
410
mfz
415
Fig.42 HpCDF
420
2.5
=» 2
i
C 1.5
CO
i 1
0.5
415
420
425
430
435
Fig.43 HpCDD
-------
c
Dl
to
C
o
2 -
1 -
435
440
445
m/z
450
455
Fig.44OCDF
,55,
15
c
O)
CO 2
c
o
450
455
460
mtz
465
470
Fig. 45 OCDD
Sep.22 2005
To avoid the break through, we reduced the TENAX volume to 1 g and for the second
sampling 2.5g and the volume of sampling itself were reduced.
Figure 46(Test number: 9/22-#1) is the mass spectrum (mass number: 270 to 500)
measured by RIMMPA-TOFMS and the mass spectrum was obtained by integrated value of
3 minute measurements. Although the sampling volume was 1/8 of the previous day, the ion
signals of mass number 278 and 280 were increased, and the other signals are decreased.
We also measured the lower mass region from 250 to 270 and we recognized the spectra in
mass number 260 and 262. It was assumed that the PAH or chlorinated PAH from boiler.
A-22
-------
160
140
120
100
JO 80
O)
60
40
20
..Ilidi. ..i,..L .
ll
0
250 300 350 400 450 500
m/z
Fig.46 Mass spectrum (Test number:9/22-#1)
Figures 47 to 56 are the mass spectra which are expanded near parent-ion spectrum of the
tetra to octa chlorinated DDs and DFs. The signals of impurity were decreased because the
sampling volume was decreased and also the tetra to octa chlorinated DDs and DFs mass
signals are decreased and we could not identify it nor determinate it.
A-23
-------
14
10
ra
g>
CO 6
C
^
4
2
295
10
300
305
m/z
310
315
Fig.47TeCDF
ra
i
o
315 320 325
m/z
Fig.48 TeCDD
330
c
0]
0)
CO 2
c
o
330
350
TO
350
355 360
m/z
365
Fig.49 PeCDF
Fig.50 PeCDD
us
O)
CO
o
365
Fig.51 HxCDF
385
D)
CO 2
C
o
380
385
390
m/z
395
400
Fig.52 HxCDD
-------
2
D>
CO
C
o
400
gi
CO
c
405
410
m/z
415
420
Fig.53 HpCDF
415
420
425
m/z
430
435
Fig.54 HpCDD
"E
(D
Q)
to
435
440
445
mfz
450
455
Fig.55OCDF
gi
CO
450
455
460
m/z
465
470
Fig.56OCDD
It is because the some absorbed materials in TENAX were remained due to the low flow
rate of helium gas.
Figure 57 is the mass spectrum obtained by RI MM PA-TOMS in the case of increasing
helium flow rate to 3 L/min after the measurement end of Test number: 9/22-#2. Comparing
to the data of 0.5 L/min, the ion signals increased. We thought the sample remained in the
TENAX column not being pushed out.
A-25
-------
600
500
3 400
ra
co
c
Ol
300
200
100
250
300
350 400
mfz
450
500
Fig.57 Mass spectrum
7. Conclusion
What we have performed this time through the test is
1. We straggled for adjusting the Adsorption and Heated Desorption.
2. It has taken us much time to get rid of unexpected occurrence of PAH & Poly-Chlorinated
PAH that caused from Naphthalene Cu to generate Dioxin.
3. This PC-PAH causes the damages to break the congener ratio which is essential to
identification of PCDDs/PCDFs because they overlap with those of PCDDs/PCDFs.
Even under this situation, we tried two types of analysis of congeners and isomers.
In the congener analysis, the peaks detected in the vicinity of mass of TeCDF, TeCDD,
PeCDD, and OCDF were able to be identified. However, it was difficult to identify other
congeners because PAH and chlorinated PAH contained in exhaust gas came in succession
with spectra of PCDD's and PCDF's. With regard to the results of PAH or chlorinated PAH
that we have got in the experiment, are shown in chart 5.
In the case of isomer analysis 2,3,4,7,8-PeCDF, we detected mass peaks in the mass
number 338, 340 and 342. It was tough however, to identify and to measure because the
intensity ratio of the isotopes 338, 340, 342 observed is different from the signal calculated
by the existence ratio. It was not possible to identify the isotope signals of 2, 3,4, 7, 8- PeCDF,
because the mass spectra of impurities (PAH and chlorinated PAH etc.) that existed in the
mass neighborhood of 2, 3, 4, 7, 8- PeCDF came in succession, and detection was
obstructed.
A-26
-------
Through this ETV test this time, we realized that the toughness in the real gas but at the
same time we learned many things and eventually we have to the stage to convince that we
are very close to be able to detect the isomer analysis in real gas in the very near future.
A-27
-------
Chart 5
m/z
Compound
260
262
C18H1402
278
280
284
286
292
294
C12H10CI4
296
298
304
C18H2404
312
C18H10OCI2
314
318
C21H15OCI
320
328
334
336
344
C18H7OCI3
346
C18HgOCl3
360
» 22 n 1 o
362
^28^
2826
C26H15CI
^26^1802
368
380
C18H8OCI4
384
394
396
410
412
A-28
------- |