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.

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                                                         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 Multi-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

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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

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Heated Quartz
Probe Liner
Sample Nozzle
                                                                Heated Transfer Line
                                                              >" (Stainless Steel Tube)
                                           Adsorption and Heat Desorption Unit
                                           including four condensers
                                       NaOH Solution
       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

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                                 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

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                                    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

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                                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

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           100
            80
            60
        CD
            20
250       300       350       400
                         m/z
                                                    450
                        500
                      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.
CO   2
c
^

    1
    295
                   T |  I I  T ,
                    TeCDF
                 50.6 100 BO.5
            300
                   305
                   m/z
                           310
              Fig.3 TeCDF
                                           100
                                  315
A-7
                                    330
                                           Fig.4TeCDD

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  q  3
  g>
  CO
      335
                     340
                     mfz
                                     345
                                                :>! 'j
                                                                              365
               Fig.5 PeCDF
                                                     Fig.6 PeCDD
    10
  "(5
  c
  CO  4
  c
  o
      360
             36!
                     370
                     m/z
                             375
                                     380
                                       en
                                       c
                                       Dl
                                       to
                                       C
                                       O
                                               380
                                                       385
                                                          390
                                                          mfz
                                                                       395
1
                                                                              400
                Fig.7 HxCDF
                                                     Fig.8 HxCDD
gi
to
c
o
    15
    10
395    400    405    410    415    420
                mfz
               Fig.9 HpCDF
                                       SM   3
                                       "in


                                       CO   2

                                       o
                                                415
                                                                425
                                                                mfz
                                                                        '•fir
                                                                                435
                                                      Fig.10 HpCDD
                                            A-8

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,(O,
75
n
CO
5
     435
                  OCDF
             26.1  57.5 100  70.2 48.4
            440
                   445
                   m/z
                          450
                                 455
              Fig.11 OCDF
                                      "ra
                                      gi
                                      CO  2
                                          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

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               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

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   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

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                                          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

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  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

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                                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

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   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

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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

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     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

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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

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                                                                        RIMMPA-TOFMS
Sample Nozzle
      Fig.33   Schematic diagram  of the sampling train, with single condenser,

      connected to filter directly, and measurement by RIMMPA-TOFMS
CO

c
o
   100
    80
    60
    40
    20
     250     300
                   350     400

                      mfz
                                              100
                                               60
C?

c
                                               20
                                 450     500
                                                      U«L
                                                250     300
                  350     400


                     mfz
                                                                           450     500
         Fig.34 Mass spectrum (9/21-#1)
       Fig.35 Mass spectrum (9/21-#2)
                                         A-19

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  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

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     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

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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

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           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

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    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

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    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

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               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

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  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

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                    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

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