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
-------
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
-------
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
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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
-------
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
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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
-------
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
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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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