HT8-PCBキャピラリーカラムによるPCB全異性体分析

HT8-PCBキャピラリーカラムに
よるPCB全異性体分析
平成14年11月11日(月):大阪府立公衆衛生研究所
松村千里1), 鶴川正寛1), 中野 武1),
江崎達哉2), 大橋 眞2)
1)
兵庫県立健康環境科学研究センター
2)
SGEジャパン株式会社
3,4,5,3’,4’-PeCB
【はじめに】
PCBの総生産量 58,000t (1954-1971)に対
して、回収され熱分解処理された液状PCB は5,500t(生産量の
10%以下)である。適正に管理・保管されているもの、過去に閉
鎖系で使用され、粗大ゴミの一部として廃棄物処分場にストック
されているもの、開放系で使用され環境へ放出されたもの、古い
電気製品のシュレッダーダスト、ノンカーボン紙、蛍光灯の安定
器、紙コンデンサー、船底塗料など、さまざまな地域で、さまざま
な形で環境へ移行し、大気系、水系、生態系に分布している。
PCBは低塩素化物中心のノンカーボン紙・紙コンデンサー由来
(KC300)から、高塩素化物中心の船底由来(KC600)まで、特異
的な異性体、同族体分布を呈する。
PCBは汚染拡散の重要な指標
環境中で分解しない。:難分解性
使用期間10~20年の環境負荷
異性体 209 : 情報量が多い
海域底質中PCBの鉛直分布
PCB汚染の時間的・経年変化
海域底質中PCBの水平分布
PCB汚染の空間的移動
熱安定性
化学的
生物学的
環境、ヒト、生態系において、PCBの挙
動と運命を把握するため、環境および
生体試料中のPCBの全異性体分析を実施
し、多面的な解析を試みた。
PCB Conc.(pg/m3)
1500
PCB(QMF)
PCB(PUF)
Temp.
30
25
20
1000
15
10
Air temp.(degC)
PCB濃度と気温
2000
500
5
Rain (mm)
0
0
100
降雨量
50
0
PCB(QMF)
PCB(PUF)
1030
Press.
1500
1020
1000
1010
1000
500
990
29
Dec.1
3
Oct.22
24
26
28
30
Nov.1
3
5
7
9
11
13
15
17
19
21
23
17
19
21
24
26
28
980
Sep.2
4
6
9
11
13
0
Aug.29
PCB Conc.(pg/m3)
1040
PCB濃度と気圧
Sampling Date
大気中PCB濃度変動と気温・降雨・気圧
Air Press.(hPa)
2000
大気中PCBの同族体分布
D10CB
N9CB
O8CB
Hp7CB
Hx6CB
P5CB
Te4CB
0
Tr3CB
30
D2CB
40
M1CB
D10CB
N9CB
O8CB
50
Hp7CB
Hx6CB
P5CB
Te4CB
Tr3CB
D2CB
M1CB
(ガス状)
(粒子状)
Nov.6.1996 PUF
30
20
20
10
10
0
#11
#12/#13
#15
#35
#37
#74
#70
#66
#80/#55
#56
#77
#107
#123
#118
#114
#105
#126
#156
#157
#169
#180
#193
#191
#170
#190
#189
30
KC300-600
Kanechlor300-600
20
10
0
30
Dec.3.1997 PUF
30
Dec.3.1997 QMF
大気中PCBの異性体分布
(ガス状)
20
10
0
(粒子状)
20
10
0
30
25
20
15
10
5
10
0
0
45
KC600
40
D10CBs
5
D10CBs
15
N9CBs
20
N9CBs
25
O8CBs
30
O8CBs
35
H7CBs
KC600
H7CBs
H6CBs
P5CBs
D10CBs
N9CBs
O8CBs
H7CBs
H6CBs
P5CBs
T4CBs
50
45
40
35
30
25
20
15
10
5
0
H6CBs
KC400
T3CBs
同族体分布と起源推定
P5CBs
0
T4CBs
底質 A
T4CBs
40
T3CBs
底質(KC300由来)
45
40
35
30
25
20
15
10
5
0
T3CBs
60
D2CBs
0
D2CBs
10
M1CBs
KC300
M1CBs
D10CBs
40
D2CBs
35
N9CBs
50
M1CBs
KC400
D10CBs
10
D10CBs
20
N9CBs
KC300
N9CBs
30
O8CBs
H7CBs
H6CBs
20
O8CBs
H7CBs
H6CBs
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
30
O8CBs
H7CBs
45
40
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
50
H6CBs
50
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
60
KC500
KC500
底質(KC600由来)
底質 B
母乳・脂肪組織
#74
(2,4,4',5-)
#99
(2,2’,4,4',5-)
#118
(2,3’,4,4',5-)
#153
(2,2',4,4',5,5'-)
#74 (4-245)
#153 (245-245)
#138
(2,2',3,4,4',5'-)
#99 (24-245)
#118 (34-245)
#138 (234-245)
23478-PeCDF
2378-TCDD
75
135
75
209
123567-HxCN
3453’4’-Co-PCB
ダイオキシン類
TEF
PCDD
7種
PCDF
10種
コプラナPCB
PCN
臭素化PCDD/DF
14種
7種
コプラナPCB
コプラナPCBは、PCB製品中の成分の一部としての側
面と、燃焼プロセスから発生するダイオキシンと同様
の非意図的生成物質としての側面があり、その起源を
推定する上で、環境中でのPCB異性体の個々の挙動は
重要である。
TEQ値に対する寄与
100%
80%
60%
PCB
PCDF
PCDD
40%
20%
TEQ寄与
土壌
河川水
底質
降下ばいじん
大気
0%
Co-PCBの異性体
•
•
•
•
•
•
•
•
•
•
•
•
•
•
3,3',4,4'-T4CB
3,4,4',5-T4CB
2,3',4,4',5'-P5CB
2,3',4,4',5-P5CB
2,3,4,4',5-P5CB
2,3,3',4,4'-P5CB
3,3',4,4',5-P5CB
2,3,3',4,4',5-H6CB
2,3,3',4,4',5'-H6CB
2,3',4,4',5,5'-H6CB
3,3',4,4',5,5'-H6CB
2,3,3',4,4',5,5'-H7CBs
2,2',3,4,4',5,5'-H7CB
2,2',3,3',4,4',5-H7CB
IUPAC
TEF
#77
#81
#123
#118
#114
#105
#126
#156
#157
#167
#169
#189
#180
#170
0.0001
0.0001
0.0001
0.0001
0.0005
0.0001
0.1
0.0005
0.0005
0.00001
0.01
0.0001
0
0
環境大気 TEQ値に対する寄与
1
pg-TEQ/m3
PCB
PCN
PCDD
PCDF
PCN
PCDD
PCDF
0.1
0.01
0.001
1000
pg/m3
100
10
1
PCB
ローボリウムサンプラー
前処理の簡素化・迅速分析
1 Sample
2 n-Hexane 100mL
3 20%DCM/
n-Hex. 60mL
Syringe
C1
C1
C2
C2
4 Reverse flow direction
Toluene 80mL
Acrobat•¶
‘
Syringe
Syringe
C2
C2
Fr. 1
Fr. 2
Fr. 3
Scheme 1.
Scheme of clean up system for environmental
samples. (C1: Multi layer Silica gel column (disposal
filtration tube). C2: Carboxen 1000 Reversing tube).
PCB異性体分析
PCBsのGC分析用カラム
→DB-5及びHT8が多く使用されている。
HT8は8%フェニル相当の微極性カラムであ
り、その固定相に、カルボランが化学結合され
ていることを特徴とし、従来の微極性カラムで
は分離しえなかった異性体を分離している。
しかし、
HT8においても主要な異性体であ
る#44、#74、#101、#118、#105 等の分離が不
十分である、#149のフラグメントイオンが#77に
重なるなどの問題点があった。
そこで、 新規なキャピラリーカラムである
HT8-PCB を用い、PCBs全209異性体の分離条件
を検討するとともに、各異性体の溶出順位の決
定を行ったので報告する。
試
薬
 PCBs各209異性体の標準物質
Accu Standards Inc.
Catalogue number : C-SET-100
Contents : PCB all 209 congeners
Solvent : isooctane in each 209 vials
 内標準混合溶液( 13Cラベル化体)
Wellington Laboratories
Catalogue number : MBP-CG
Contents : 13C12-labeled mono- to deca-PCB solution /mixture
( # 3, #15, #31, #52, #118, #153, #180, #194, #206, #209 )
Solvent : nonane
Bz#とIUPAC#
Bz#
107
108
109
199
200
201
structure
2,3,3‘,4’,5-PeCB
2,3,3',4,5'-PeCB
2,3,3',4,6-PeCB
2,2',3,3',4,5,6,6'-OcCB
2,2',3,3',4,5',6,6'-OcCB
2,2',3,3',4,5,5',6'-OcCB
IUPAC#
109
107
108
200
201
199
標準溶液
分離状況確認用
PCBs全209異性体の混合溶液(209-Mix、約
50ppb)と、KC300、400、500及び600の等量
混合溶液(KC-Mix、5ppm)を調製した。
溶出順位確定用
5%フェニルメチルシリコン系、HT8にお
けるPCB全209成分の分離挙動を参考に、13
~14異性体の混合標準液15種(CB-1~CB-15)
を調製した。
* CB-1~CB-15、209-Mix、KC-Mixの各標準混合溶液には、内標
準混合溶液を予め添加した。
Table2 PCB congeners (IUPAC number) included
in 15 type of standard mixture solutions
type
PCB congeners (IUPAC number)
CB-1
1
13
50
43
71
70
77
92
97
140
168
178
170
202
CB-2
2
18
28
49
64
76
84
86
105
126
154
143
171
190
CB-3
3
15
21
38
41
98
89
125
82
127
134
156
175
198
CB-4
4
17
33
47
68
102
101
116
151
133
141
166
173
200
CB-5
10
27
20
75
80
96
90
117
114
135
159
157
179
203
CB-6
9
24
53
48
40
66
113
87
122
144
137
182
199
196
CB-7
7
32
51
65
103
93
99
124
145
131
176
187
189
204
CB-8
6
16
22
62
57
79
81
95
147
142
130
183
172
208
CB-9
8
34
45
67
104
121
119
111
109
165
164
162
192
195
CB-10
5
23
36
35
100
88
115
108
150
163
128
188
197
207
CB-11
14
29
46
44
58
91
112
123
148
146
138
167
180
194
CB-12
19
39
54
59
63
55
83
120
149
161
158
185
193
205
CB-13
30
26
37
69
94
107
155
136
139
153
160
174
191
206
CB-14
11
25
52
42
74
56
78
85
118
184
186
181
201
209
CB-15
12
31
73
72
61
60
110
106
152
132
129
169
177
Included 13C12 labeled PCB (# 3, #15, #31, #52, #118, #153, #180, #194, #206, #209) in CB-1~CB-15
装置及び、測定条件
GC : HP5890(Agilent Technologies製)
Capillary Column: HT8-PCB 0.25mmID x 60m
(SGE製)
Injector: 280℃ Splitless
Injection amount: 1μL
Carrier Gas: He 1.0ml/min Constant Flow
Mode
MS : JMS-700(日本電子製)
Interface: 260℃
Chamber: 260℃
High Resolution Mode: Resolution ≧10000
分離条件と溶出順位
PCBs全209異性体の混合溶液209-Mixを用い、
異性体の分離状況と溶出時間からオーブン条件
を最適化した。
Oven : 120℃ - 20℃/min → 180℃ - 2℃/min
→ 260℃ - 5℃/min → 300℃ (4min hold)
この条件において混合標準液15種CB-1~CB15を測定しPCBs各異性体の溶出順位を確定す
るとともに、KC-300、400、500及び600の等量
混合溶液KC-Mixについても測定した。
Table4
The number of isomer and peak
congener
mono
di
tri
tetra
penta
hexa
hepta
octa
nona
deca
total
*<90%Valley
number of
number of peak*
isomer
3
3
12
10
24
23
42
39
46
38**
42
40
24
23
12
12
3
3
1
1
209
192
**#86:shoulder peak
Table5-1 PCB Retention Index with HT8-PCB
IUPAC#
#1
#2
#3*
#10
#4
#9
#7
#6
#8*
#5
#19
#14
#30
#18*
#11
#17
#13
#12
#24
#27
#15*
#32
#16
#54
#23
tR
8.395
9.771
9.926
10.351
10.443
11.449
11.555
12.164
12.426
12.461
13.058
13.187
13.459
14.308
14.420
14.510
14.799
14.811
14.834
15.016
15.166
15.451
15.615
15.881
16.075
RRTa)
0.275
0.320
0.325
0.339
0.342
0.374
0.378
0.398
0.406
0.408
0.427
0.431
0.440
0.468
0.472
0.475
0.484
0.484
0.485
0.491
0.496
0.505
0.511
0.519
0.526
IUPAC#
#34
#29
#26
#50
#25
#31*
#53
#28*
#51
#21
#20
#33*
#45
#22
#46
#36
#52*
#69
#73
#43
#49
#39
#104
#65
#75
tR
16.234
16.383
16.770
16.800
17.012
17.236
17.490
17.513
17.867
18.051
18.247
18.268
18.314
18.727
19.021
19.221
19.307
19.316
19.459
19.623
19.659
19.772
19.865
19.931
19.961
RRTa)
0.531
0.536
0.548
0.549
0.556
0.564
0.572
0.573
0.584
0.590
0.597
0.597
0.599
0.612
0.622
0.629
0.631
0.632
0.636
0.642
0.643
0.647
0.650
0.652
0.653
IUPAC#
#48
#47
#62
#38
#44*
#59
#42
#96
#35
#64
#72
#71
#103
#41
#37
#68
#100
#40
#57
#94
#67
#63
#58
#102
#93
tR
20.020
20.021
20.172
20.626
20.952
21.085
21.299
21.447
21.511
21.721
21.811
21.916
21.922
21.973
22.136
22.202
22.452
22.695
22.857
22.967
23.304
23.508
23.582
23.588
23.626
RRTa)
0.655
0.655
0.660
0.675
0.685
0.690
0.697
0.701
0.704
0.710
0.713
0.717
0.717
0.719
0.724
0.726
0.734
0.742
0.748
0.751
0.762
0.769
0.771
0.771
0.773
Table5-2 PCB Retention Index with HT8-PCB
IUPAC#
#98
#95*
#61
#74
#88
#91
#155
#121
#70*
#76
#80
#66*
#55
#92
#84
#89
#90
#150
#101*
#60
#56
#113
#152
#99
#112
tR
23.669
23.703
23.868
24.006
24.033
24.210
24.269
24.351
24.398
24.523
24.702
24.786
25.429
25.485
25.544
25.743
25.918
25.930
26.025
26.119
26.216
26.289
26.517
26.518
27.110
RRTa)
0.774
0.775
0.781
0.785
0.786
0.792
0.794
0.796
0.798
0.802
0.808
0.811
0.832
0.833
0.835
0.842
0.848
0.848
0.851
0.854
0.857
0.860
0.867
0.867
0.887
IUPAC#
#145
#119
#83
#79
#115
#136
#148
#86
#117
#97
#125
#116
#87
#108
#78
#111
#154
#85
#120
#110*
#81**
#151
#135
#144
#147
tR
27.132
27.156
27.350
27.451
27.463
27.698
27.815
27.828
27.895
27.956
28.041
28.048
28.265
28.274
28.388
28.520
28.592
28.736
29.090
29.147
29.196
29.388
29.731
29.910
30.005
RRTa)
0.887
0.888
0.894
0.898
0.898
0.906
0.910
0.910
0.912
0.914
0.917
0.917
0.924
0.925
0.928
0.933
0.935
0.940
0.951
0.953
0.955
0.961
0.972
0.978
0.981
IUPAC#
#82
#77**
#149*
#139
#140
#188
#124
#143
#134
#109
#107
#123**
#142
#184
#106
#131
#118**
#133
#165
#114**
#146
#132
#179
#161
#122
tR
30.214
30.315
30.476
30.543
30.919
31.071
31.138
31.185
31.374
31.437
31.445
31.676
31.795
31.810
31.872
31.891
32.035
32.037
32.536
32.698
32.712
32.850
32.893
32.990
33.186
RRTa)
0.988
0.991
0.997
0.999
1.011
1.016
1.018
1.020
1.026
1.028
1.028
1.036
1.040
1.040
1.042
1.043
1.048
1.048
1.064
1.069
1.070
1.074
1.076
1.079
1.085
Table5-3 PCB Retention Index with HT8-PCB
IUPAC#
#153*
#168
#176
#141
#186
#105**
#127
#137
#130
#178
#164
#163
#138*
#160
#158
#175
#182
#187*
#129
#166
tR
33.422
33.565
33.612
34.304
34.342
34.410
34.515
34.874
35.115
35.505
35.585
35.617
35.794
35.932
36.085
36.092
36.306
36.319
36.357
36.827
RRTa)
1.093
1.098
1.099
1.122
1.123
1.125
1.129
1.141
1.148
1.161
1.164
1.165
1.171
1.175
1.180
1.180
1.187
1.188
1.189
1.204
IUPAC#
#183
#126**
#185
#159
#202
#128
#174*
#162
#181
#201
#177
#204
#167**
#171
#197
#173
#200
#156**
#172
#192
tR
36.953
37.631
37.788
37.898
37.943
38.205
38.273
38.359
38.479
38.721
38.765
38.932
39.020
39.383
39.531
39.869
40.783
41.029
41.091
41.458
RRTa)
1.209
1.231
1.236
1.239
1.241
1.249
1.252
1.255
1.258
1.266
1.268
1.273
1.276
1.288
1.293
1.304
1.334
1.342
1.344
1.356
IUPAC#
#157**
#180**
#193
#191
#198
#199*
#170**
#196
#190
#203*
#169**
#208
#207
#195
#189**
#194*
#205
#206*
#209
tR
41.530
41.846
41.969
42.515
43.841
43.939
44.262
44.569
44.571
44.670
44.682
45.435
46.149
46.732
47.250
48.866
49.379
50.309
50.920
RRTa)
1.358
1.369
1.373
1.390
1.434
1.437
1.448
1.458
1.458
1.461
1.461
1.486
1.509
1.528
1.545
1.598
1.615
1.645
1.665
* : Predominant isomers in Kanechlor.
**: co-PCBs and diortho-substituted isomers.
RRT: Relative Retention Time vs average retention time of mass labeled-#52 and #180
(a)
Intensity
M1CB
Average Mass Chromatogram of M1CB (m/z=188.0393,190.0364)
40000
0
M1CB
7.2
(b)
7.6
8.0
8.4
8.8
9.2
Retention Time (min)
9.6
10.0
10.4
10.8
7.6
8.0
8.4
8.8
9.2
Retention Time (min)
9.6
10.0
10.4
10.8
7.6
8.0
8.8
9.2
Retention Time (min)
9.6
10.4
10.8
Intensity
1000000
Calculated Retention Time
#3
Calculated Retention Time
#2
7.2
#1
0
Intensity
13C-M1CB
100000
10.0
#3
8.4
#1
7.2
#2
0
13C-M1CB
Intensity
Fig. 1-1 Average Mass Chromatogram of monochlorinatedbiphenyl
(M1CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all 2098.0PCB standard
mixture
solution.
7.2
7.6
8.4
8.8
9.2
9.6
10.0
10.4
10.8
Retention Time (min)
Intensity
Average Mass Chromatogram of D2CB (m/z=222.0003, 223.9974)
(a)
D2CB
2000000
9.6
10.0
10.4
10.8
11.2
11.6
12.0 12.4 12.8 13.2
Retention Time (min)
13.6
14.0
14.4
14.8
15.2
15.6 16.0
10.0
10.4
10.8
11.2
11.6
12.0 12.4 12.8 13.2
Retention Time (min)
13.6
14.0
14.4
14.8
15.2
15.6 16.0
#15
(b)
9.2
#13
#12
D2CB
1000000
#11
0
10.8
11.2
13.6
14.0
14.4
14.8
15.2
Intensity
Calculated Retention Time
500000
#14
#8
#5
Calculated Retention Time
#6
9.6
#9
#7
9.2
#10
#4
0
Intensity
13C-D2CB
#15
#13
#12
12.0 12.4 12.8 13.2
Retention Time (min)
#14
11.6
#8
#5
10.4
#6
10.0
#9
#7
9.6
#10
#4
9.2
#11
0
15.6 16.0
13C-D2CB
Intensity
Fig. 1-2 Average Mass Chromatogram of dichlorinatedbiphenyl (D2CB)
in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b) all 209
0
PCB standard mixture solution.
9.2
9.6
10.0 10.4 10.8 11.2 11.6 12.0 12.4 12.8 13.2 13.6 14.0 14.4 14.8 15.2 15.6 16.0
Retention Time (min)
T3CB
Intensity
Average Mass Chromatogram of T3CB (m/z=255.9613,257.9587)
(a)
4000000
0
12
T3CB
(b)
13
14
15
16
17
18
Retention Time (min)
19
20
21
22
23
14
15
16
17
18
Retention Time (min)
19
20
21
22
23
Intensity
Calculated Retention Time
1000000
#37
#35
#38
#39
#36
#22
#21
#20
#33
#23
#34
#29
16
#26
#25
#31
#28
#32
#16
#32
#16
Calculated Retention Time
#30
13
#19
12
#18
#17
#24
#27
0
Intensity
13C-T3CB
22
#37
21
#35
20
#38
#39
19
#36
#22
#21
#20
#33
17
18
Retention Time (min)
#26
#25
#31
#28
15
#23
#34
#29
14
#18
#17
#24
#27
13
#19
12
#30
0
23
13C-T3CB
Intensity
Fig. 1-3 Average Mass Chromatogram of trichlorinatedbiphenyl (T3CB)
in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b) all 209
0
PCB standard mixture solution.
12
13
14
15
16
17
18
19
20
21
22
23
Intensity
Average Mass Chromatogram of T4CB (m/z=289.9221, 291.9195)
(a)
T4CB
2000000
0
15
T4CB
16
(b)
17
18
19
20
21
22
23
24
25
Retention Time (min)
26
27
28
29
30
31
32
17
18
19
20
21
22
23
24
25
Retention Time (min)
26
27
28
29
30
31
32
31
32
Intensity
Calculated Retention Time
1000000
16
#54
#50
#53
#51
#45
#46
#52
#69
#73
#43
#49
#65
#75
#48
#47
#62
#44
#59
#42
#64
#72
#71
#41
#68
#40
#57
#67
#63
#58
#61
#74
#70
#76
#80
#66
#55
#60
#56
#79
#78
#81
15
#77
0
Calculated Retention Time
Intensity
13C-T4CB
40000
16
17
18
19
20
21
22
23
24
25
Retention Time (min)
26
27
28
29
#54
#50
#53
#51
#45
#46
#52
#69
#73
#43
#49
#65
#75
#48
#47
#62
#44
#59
#42
#64
#72
#71
#41
#68
#40
#57
#67
#63
#58
#61
#74
#70
#76
#80
#66
#55
#60
#56
#79
#78
#81
15
30
#77
0
13C-T4CB
Intensity
Fig. 1-4 Average Mass Chromatogram of tetrachlorinatedbiphenyl
(T4CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all18 209
PCB
standard
mixture
solution.
15
16
17
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Retention Time (min)
Intensity
P5CB
800000
Average Mass Chromatogram of P5CB (m/z=325.8805,327.8776)
(a)
400000
0
20
(b)
P5CB
22
24
26
28
30
Retention Time (min)
32
34
36
38
22
24
26
28
30
Retention Time (min)
32
34
36
38
Intensity
1000000
Calculated Retention Time
500000
0
#104
#96
#103
#100
#94
#102
#93
#98
#95
#88
#91
#121
#92
#84
#89
#90
#101
#113
#99
#112
#119
#83
#115
#86
#117
#97
#125
#116
#87
#108
#111
#85
#120
#110
#82
#124
#109
#107
#123
#106
#118
#114
#122
#105
#127
#126
20
Calculated Retention Time
Intensity
13C-P5CB
50000
#104
#96
#103
#100
#94
#102
#93
#98
#95
#88
#91
#121
#92
#84
#89
#90
#101
#113
#99
#112
#119
#83
#115
#86
#117
#97
#125
#116
#87
#108
#111
#85
#120
#110
#82
#124
#109
#107
#123
#106
#118
#114
#122
#105
#127
#126
0
20
22
24
26
28
30
Retention Time (min)
32
34
36
38
13C-P5CB
Intensity
Fig. 1-5 Average Mass Chromatogram of pentachlorinatedbiphenyl
(P5CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all 20924PCB standard
mixture
solution.
20
22
26
28
30
32
34
36
38
Retention Time (min)
Average Mass Chromatogram of H6CB (m/z=359.8415, 361.8386)
(a)
H6CB
Intensity
1000000
500000
0
H6CB
800000
24
(b)
26
28
30
32
34
36
Retention Time (min)
38
40
42
44
46
26
28
30
32
34
36
Retention Time (min)
38
40
42
44
46
Intensity
Calculated Retention Time
400000
#155
#150
#152
#145
#136
#148
#154
#151
#135
#144
#147
#149
#139
#140
#143
#134
#142
#131
#133
#165
#146
#132
#161
#153
#168
#141
#137
#130
#164
#163
#138
#160
#158
#129
#166
#159
#128
#162
#167
#156
#157
24
#169
0
Calculated Retention Time
Intensity
13C-H6CB
40000
24
26
28
30
32
34
36
Retention Time (min)
38
40
42
44
#169
#155
#150
#152
#145
#136
#148
#154
#151
#135
#144
#147
#149
#139
#140
#143
#134
#142
#131
#133
#165
#146
#132
#161
#153
#168
#141
#137
#130
#164
#163
#138
#160
#158
#129
#166
#159
#128
#162
#167
#156
#157
0
46
13C-H6CB
Intensity
Fig. 1-6 Average Mass Chromatogram hexachlorinatedbiphenyl (H6CB)
in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b) all 209
0
PCB
standard
mixture
solution.
24
26
28
30
32
34
36
38
40
42
44
46
Retention Time (min)
Average Mass Chromatogram of H7CB (m/z=393.8024, 395.7996)
(a)
H7CB
Intensity
800000
400000
0
30
H7CB
800000
31
(b)
32
33
34
35
36
37
38
39
40
41
Retention Time (min)
42
43
44
45
46
47
48
49
32
33
34
35
36
37
38
39
40
41
Retention Time (min)
42
43
44
45
46
47
48
49
43
44
45
46
47
48
49
Intensity
Calculated Retention Time
400000
#189
#172
#192
#180
#193
#191
#172
#192
#180
#193
#191
#170
#190
#185
#174
#181
#177
#171
#173
#176
#176
#185
#174
#181
#177
#171
#173
#179
#179
#178
#175
#182
#187
#183
#184
#184
Calculated Retention Time
#178
#175
#182
#187
#183
#188
31
#188
30
#186
0
Intensity
13C-H7CB
20000
32
33
34
35
36
37
38
39
40
41
Retention Time (min)
42
#189
31
#170
#190
30
#186
0
13C-H7CB
Intensity
Fig. 1-7 Average Mass Chromatogram of heptachlorinatedbiphenyl
(H7CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all 209
PCB
standard
mixture
solution.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48 49
Retention Time (min)
Average Mass Chromatogram of O8CB (m/z=427.7636, 429.7606)
(a)
O8CB
Intensity
400000
200000
39
40
41
42
43
44
45
Retention Time (min)
46
47
48
49
50
51
38
39
40
41
42
47
48
49
50
51
#201
#204
#197
43
44
45
Retention Time (min)
46
#202
#198
#199
#196
#203
#201
#204
#197
42
#198
#199
#196
#203
37
O8CB
#202
0
38
43
44
45
Retention Time (min)
46
50
51
(b)
Intensity
800000
Calculated Retention Time
400000
#194
#205
#194
#205
Calculated Retention Time
#195
37
#200
0
Intensity
13C-O8CB
40000
38
39
40
41
#195
37
#200
0
47
48
49
13C-O8CB
Intensity
Fig. 1-8 Average Mass Chromatogram of octachlorinatedbiphenyl
(O8CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all 209
PCB
standard
mixture
solution.
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
Retention Time (min)
Average Mass Chromatogram of N9CB (m/z=461.7246, 463.7216)
(a)
N9CB
Intensity
80000
40000
0
N9CB
44.0
44.5
(b)
45.0
45.5
46.0
46.5
47.0
47.5
48.0
48.5
Retention Time (min)
49.0
49.5
50.0
50.5
51.0
51.5 52.0
45.0
45.5
46.0
46.5
47.0
47.5
48.0
48.5
Retention Time (min)
49.0
49.5
50.0
50.5
51.0
51.5 52.0
45.0
45.5
46.5
47.0
47.5
48.0
48.5
Retention Time (min)
49.0
49.5
50.0
51.0
51.5 52.0
Intensity
Calculated Retention Time
400000
Calculated Retention Time
#206
44.5
#207
44.0
#208
0
Intensity
13C-N9CB
40000
46.0
#206
44.5
#207
44.0
#208
0
50.5
13C-N9CB
Intensity
Fig. 1-9 Average Mass Chromatogram of nonachlorinatedbiphenyl
(N9CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all45.520946.0PCB
standard
mixture
solution.
44.0
44.5
45.0
46.5
47.0
47.5
48.0
48.5
49.0
49.5
50.0
50.5
51.0
51.5 52.0
Retention Time (min)
Intensity
Average Mass Chromatogram of D10CB (m/z=497.6826, 499.6797)
(a)
D10CB
4000
2000
D10CB
800000
(b)
49.4
49.6
49.8
50.0
50.2
50.4
50.6
50.8 51.0 51.2
Retention Time (min)
51.4
51.6
51.8
52.0
52.2
52.4
52.6
49.8
50.0
50.2
50.4
50.6
50.8 51.0 51.2
Retention Time (min)
51.4
51.6
51.8
52.0
52.2
52.4
52.6
49.8
50.0
50.2
50.4
50.6
50.8 51.0 51.2
Retention Time (min)
51.4
51.6
51.8
52.0
52.2
52.4
52.6
Intensity
Calculated Retention Time
400000
49.4
49.6
#209
0
Calculated Retention Time
Intensity
13C-D10CB
40000
49.4
49.6
#209
0
13C-D10CB
Intensity
Fig. 1-10 Average Mass Chromatogram of decachlorinatedbiphenyl
(D10CB) in (a) KC-300, 400, 500, 600 equivalent mixture solution and (b)
0
all 209 PCB standard mixture solution.
49.4 49.6 49.8 50.0 50.2 50.4 50.6 50.8 51.0 51.2 51.4 51.6 51.8 52.0 52.2 52.4 52.6
Retention Time (min)
(#100)
#68
#64
#72
#71
#41 (#103)
(#96)
#42
#44
#59
#62
#65
#75
#48/47
(#104)
#73
#43
#49
#52
#69
#64
Intensity
T4CB / Average
1511918
0
18.8
19.2
19.6
20.0
20.4
20.8
Retention Time (min)
21.2
21.6
22.0
22.4
(#99/152)
(#90/150)
(#101)
#60
#56
(#113)
(#92)
(#84)
(#89)
#55
#80
#66
#70(#121)
#76
(#88)
(#91)
(#155)
#61
#74
#63
#58
(#102/93)
(#98/95)
(#94)
Intensity
T4CB / Average
902989
#67
Fig. 2-1 Average Mass Chromatogram of T4CB in all 209 PCB standard mixture
solution (1)
0
23.0
23.2
23.4
23.6
23.8
24.0
24.2
24.4 24.6 24.8 25.0
Retention Time (min)
25.2
25.4
25.6
25.8
26.0
26.2
Fig. 2-2 Average Mass Chromatogram of T4CB in all 209 PCB standard mixture
solution (2)
26.4
(#137)
#105
#127
(#186)
(#141)
(#176)
(#153)
(#168)
#122
(#179) (#161)
#114(#146)
(#132)
(#165)
#123
(#142/184)
#106(#131)
#118(#133)
#124
(#143)
(#134) #109
/107
(#140)
(#188)
Intensity
(#149/139)
P5CB / Average
1189181
0
30.8
31.2
31.6
32.0
32.4
32.8
33.2
Retention Time (min)
33.6
34.0
34.4
34.8
(#183)
#166
#138
#160
#158(#175)
(#182/187)
#129
#164
#163
(#178)
#130
#137
(#176)
#141
(#186)
#153
#168
Intensity
H6CB / Average
774418
#165
#146
#132(#179)
#161
Fig. 2-3 Average Mass Chromatogram of P5CB in all 209 PCB standard mixture
solution
0
32.4
32.8
33.2
33.6
34.0
34.4
34.8
35.2
Retention Time (min)
35.6
36.0
36.4
36.8
Fig. 2-4 Average Mass Chromatogram of H6CB in all 209 PCB standard mixture s olution
37.2
Table6 The congeners were eluting near by
3)
coplanar-PCB on HT8-PCB and DB-5MS .
co-PCB
HT8-PCB
DB-5MS3)
#77
((#147)), (#82, #149), ((#139))
(#136, #154, #110, #151)
#126
((#183)), (#185), ((#159, 202))
#175, (#182, #187)
#169
(#196, #190), #203
((#191, #200, #170, #190))
#189
((#195))
((#203, #208))
Congener : ⊿RT was under 3 seconds.
(congener) : ⊿RT was from 3 to 10 seconds.
((congener)) : ⊿RT was over 10 seconds.
⊿RT : The deference of retention time from coplanar-PCB to the congener.
要
約
• PCBs全209異性体の混合溶液を用いて、
キャピラリーカラム(HT8-PCB ) の オ
ーブン条件を最適化した。
• 塩素化物ごとのマスクロマトグラムにお
いて計192本のピークが確認された。
• この条件を用いて、全209異性体の溶出順
位を確定した。