環境中ダイオキシン類の
異性体分析と起源推定
兵庫県立公害研究所 中野 武
２３４７８－PeCDF
２３７８－TCDD
７５
１３５
７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB
500000
450000
PCB production
World : 1,200,000t
Japan :
59,000t
400000
350000
300000
250000
200000
150000
Harima-nada
Osaka-Bay
Japan
100000
Osaka
700
50000
Spain
others
600
Italy
Japan
UK
Germany
USA
France
0
1962-1971
1962-1971
500
Hyogo
400
300
25000
Kinki
1962-1971
1962-1971
20000
200
100
15000
Kyusyu
Shikoku
Chugoku
Kinki
Tokai
Hokuriku
Kanto
Tohoku
Hokkaido
0
Kyoto
5000
Shiga
Hyogo
10000
Osaka
0
Osaka Bay
Harima nada
Map of enclosed coastal sea
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
Vertical distribution
of PCB in sea sediment
Production of N.C.P
Annual production
PCB concentration
Sediment core
海域底質の水平分布と鉛直分布
Annual production and Vertical distribution in sediment
Horizontal distribution
of PCB in sea sediment
Horizontal distribution in sea sediment
播磨灘 nada
Harima
大阪湾
Osaka Bay
スープ皿のような地形
like a soup dish
Independent area
東半分：陸、西半分：海
western and eastern part
Sea
bottom and water depth
海底の地形・水深
Horizontal distribution in sea sediment
Channel : fast stream
sand
silt
silt
sand
Central part: slow stream
Particle size in sea sediment
Before海域底質の粒度分布を考慮しない場合
normalization by particle size distribution
coast
High
High
Low
Inmost part
channel
High
Harima nada
Central part : High
鳴門
Low
Osaka Bay
NAKANO (1979)
Horizontal distribution in sea sediment
海域底質の粒度分布を考慮した場合
After
normalization by particle size distribution
Constant
flow map and PCB distribution
恒流図と濃度分布
海域底質中PCBの水平分布
Horizontal
distribution in sea sediment
Horizontal distribution in sea sediment
海域底質の水平分布
神戸港周辺
Around Kobe port
Osaka bay
大阪湾
PCB濃度の距離減衰
PCB concentration
and Distance from source
Source estimation
of PCB in samples
0
45
KC４００
Insulator
10
5
capacitor
40
KC６００
Ship paint
5
0
H6CBs
D10CBs
10
D10CBs
15
N9CBs
20
N9CBs
25
O8CBs
30
O8CBs
35
H7CBs
KC600
H7CBs
H6CBs
0
D10CBs
N9CBs
O8CBs
H7CBs
H6CBs
P5CBs
T4CBs
T3CBs
KC５００
50
45
40
35
30
25
20
15
10
5
0
P5CBs
10
D2CBs
Source estimation
P5CBs
20
T4CBs
30
T4CBs
底質(KC300由来)
Sediment
A
T3CBs
60
capacitor
D2CBs
20
M1CBs
KC３００
M1CBs
N.C.P.
D10CBs
40
T3CBs
15
D10CBs
50
D2CBs
20
N9CBs
KC300
M1CBs
30
25
N9CBs
0
D10CBs
35
O8CBs
10
N9CBs
KC400
O8CBs
H7CBs
H6CBs
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
30
O8CBs
H7CBs
H6CBs
40
H7CBs
45
40
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
50
H6CBs
50
P5CBs
T4CBs
T3CBs
D2CBs
M1CBs
60
KC500
Insulator
底質(KC600由来)
Sediment
B
45
40
35
30
25
20
15
10
5
0
KC300 (%)
KC300
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
#189
#170
#180
#169
#157
#156
0
#167
0
#126
0.2
#189
0.2
#105
1.2
#170
0.4
#114
0.4
#180
0.6
#118
0.6
#169
0.8
#123
0.8
#157
1
#77
1
#156
#81
Sediment A
#167
0.8
#189
#170
#180
#169
#157
#156
99ED辰巳底 (%)
#126
0.9
#105
#114
#118
#123
#77
#81
#167
1.2
#126
1.4
#105
#114
#118
#123
#77
#81
Isomer distribution and Source estimation
1.4
Water A
12
KC６00
KC600 (%)
8
6
4
2
0
#189
#170
#180
#169
#157
0
#156
0
#167
6
#126
7
#189
1
#105
0.5
#170
2
#114
1
#180
3
#118
1.5
#169
4
#123
2
#157
5
#77
2.5
#156
#81
KC４00
#167
#189
#170
#180
#169
#157
#156
KC400 (%)
#126
10
#105
#114
#118
#123
#77
#81
3
#167
3.5
#126
#105
#114
#118
#123
#77
#81
Isomer distribution and Source estimation
KC５00
KC500 (%)
-0.4
0.8
P3
2
-0.4
1
1
120
10
8
KC600 (%)
#170
#170
KC500 (%)
5
4
#189
#170
#180
#169
#157
#189
#170
#180
#169
#157
#156
#167
#126
KC400 (%)
#156
#167
#105
0.5
#189
#180
#180
0
#169
2
#169
-0.2
#157
4
#157
0
#156
0.2
#156
KC-600
#167
6
#167
#126
#105
#114
#118
#123
#180
#170
#189
#167
#157
#156
#123
#118
#114
#105
#169
0.6
#189
-0.2
#114
07
#126
0
#77
0
3.5
#126
0.2
#105
6
#105
P2
#114
KC-600
#114
0.8
#118
1
#118
0
#118
2
#123
0.2
#123
2.5
#77
0.4
#77
3
#81
0.6
#123
0.4
P1
#81
0.8
#81
1
#77
0.6
#126
Co-PCB isomer distribution and PCA
#81
0.6
#81
#77
0.9
0.8
KC300 (%)
0.7
0.4
KC-300
0.3
0.2
0.1
KC-400
1.5
1
0.5
0.4
KC-500
3
Co-PCB isomer ratio in environmental
sample
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
大気
0.107
0.028
0.190
0.020
0.005
0.008
兵庫県
1998
大気
0.133
0.035
0.184
0.025
0.007
0.010
環境庁調査
1998
公共用水域水質
0.222
<0.001
0.116
0.026
<0.001
0.026
環境庁調査
1998
ばいじん
0.129
<0.001
0.269
0.035
<0.001
0.023
環境庁調査
1998
地下水
<0.001
<0.001
0.197
<0.001
<0.001
<0.001
環境庁調査
1998
底質
0.110
0.061
0.126
0.014
0.008
0.013
環境庁調査
1998
土壌
0.157
0.053
0.238
0.037
0.013
0.028
環境庁調査
1998
Co-PCB isomer ratio and Source
0.45
0.4
KC-300
0.35
KC300
0.3
1.2
0.25
flyash
flyash
1
0.8
0.2
0.15
0.1
0.05
0
0.6
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
0.4
0.2
0
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
0.4
0.35
底質A
0.3
0.2
0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
KC-400
KC400
#126/#77
0.25
0.2
0.15
Sediment A
0.1
0.05
0
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
0.8
0.2
0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
#77/#118
#126/#118
#169/#118
#189/#118
KC500
KC-500
#126/#77
0.7
Sediment B
#169/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
底質B
0.6
0.5
0.8
0.7
0.4
0.6
0.3
0.5
0.2
0.4
0.1
0.3
KC600
KC-600
0.2
0
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
0.1
0
#126/#77
#169/#77
#77/#118
#126/#118
#169/#118
#189/#118
Isomer specific analysis
of PCB using GC/MS
5%PhMeSilicone
MCB,DiCB
780
880
980
1
1, 2 CB (HP-5)
2
1080
3
4
1180
9
7
1280
6
8
1380
5
14
1480
11
12
13
RRT
15
TrCB
780
880
980
19
3 CB (HP-5)
30
18
17
1080
24
27
32
1180
16
34
23
1280
29
26
25
1380
31
28
59
1280
42
21
33
20
1480
22
36
39
38
35
37
RRT
TeCB
780
880
4 CB (HP-5)
54
50
53
51
980
45
46
69
73
1080
52 43
49
70
76
80
66
55
56
60
79
78
77
81
47
48
1180
75 65
62
44
72
92
107
84
123
1280
101
90
106
118
71
41
89
114
113
122
131
1380
64 68
40
57
67
1480
58 63
112
126
83
1480
108
146
161
74
61 RRT
PeCB
780
880
5 CB (HP-5)
104
125
96
111
103
87
980
100
117
155
150
152
141
137
130
188
184
179
94
116
102
115
98
120
145
148
136
154
164
163
138
160
1080
93
85
95
110
121
82
1180
88
91
124
109
151
135
144
147
139
149
140
143
134
133
158
129
166
159
162
128
167
156
157
169
1380
99
119
105
127
97
86
RRT
168
132
RRT
190
189
HxCB
780
880
6 CB (HP-5)
980
1080
1180
1280
1380
142
1480
165
153
HpCB
780
7 CB (HP-5)
880
980
176
1080
186
178
175
182
1180
187
183
185
1280
174
181
177
171
1380
173
192
172
1480
180
193
191
170
RRT
KC-600
#1
#2
#3
#4/#10
#7/#9
#6
#5/#8
#14
#11
#12/#13
#15
#19
#30
#18
#17
#24/#27
#16/#32
#23
#34
#29
#26
#25
#28/#31
#20/#33
#22
#35
#37
#54
#50
#53
#51
#45
#46
#69(sh)/#73/#52
#43/#49
#47/#48/#75
#65/#62
#44
#59/#42
#72
#71(sh)/#41/#64/#68
#40/#57
#67
#58
#63
#74/#61
#70
#76/#80/#66
#55
#56/#60
#79
#78
#81
#77
#104
#96
#103
#100
#94
#102/#98
#93/#95
#121/#88
#91
#92
#84
#101/#90/#89(sh)
#113(sh)/#99
#119
#112
#83/#108
#97/#86
#125/#111/#87/#117/
#120/#85
#110
#82
#124
#107/#109
#123
#118/#106
#114
#122
#105/#127
#126
#155
#150
#152
#145
#148
#136
#154
#151
#135/#144
#147
#139/#149
#140
#143
#134/#133
#131/#142/#165
#146/#161
#153
#168/#132
#141
#137
#130
#164/#163/#138/#160
#158
#129
#166
#159
#162
#128/#167
#156
#157
#169
#188
#184
#179
#176
#186
#178
#175
#187/#182
#183
#185
#174/#181
#177
#171
#173
#192/#172
#180
#193
#191
#170/#190
#189
#202
#201
#204
#197
#200
#198
#199
#196/#203
#195
#194
#205
#208
#207
#206
#209
(%)
6
8
10
0
(%)
5
KC-500
4
10
0
5
(%)
KC-400
2
10
15
0
(%)
10
KC-300
0
20
0
(%)
10
Air
20
PSAir (Room air)
KC300 (1ppm)
KC400 (1ppm)
KC500 (1ppm)
KC600 (1ppm)
PCB Congeners
２３４７８－PeCDF
２３７８－TCDD
７５
１３５
７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
#188
#188
0.3
0.2
0.1
0
#179
#176
#186
#178
#175
#187,
#182
#183
#185
#174,
#181
#177
#171
#173
#192,
#172
#180,
#193
#191
#170,
#190
#189
#179
#176
#186
#178
#175
#187,
#182
#183
#185
#174,
#181
#177
#171
#173
#192,
#172
#180,
#193
#191
#170,
#190
#189
#179
#176
#186
#178
#175
#187, #182
#183
#185
#174, #181
#177
#171
#173
#192, #172
Isomer distribution (H7CB, Port Island in June,2001)
#189
#180
#170, #190
#191
KC300-600
#174
#180, #193
#184
Mussel
#184
Sea Water
#184
#188
Intensity
0.6
0.4
0.2
0
#170
4000
KC300-600
2000
0
0.001
Sea Water
0
0.02
0.015
0.01
0.005
0
#202
#201
#199
#196
#203
#195
#205
#194
#195
#196,
#203
#199
#198
#200
#197
#201
Mussel
#202
Intensity
0.002
#194
Isomer distribution (O8CB, Port Island in June, 2001)
Isomer distribution
of PCB in samples
Isomer distribution（TeCB）
PCB product
Intensity
HW1013+KC3-600
357936
0
14
15
16
17
18
19
Retention Time (min)
sediment
Intensity
01Sed-55
68784
0
14
15
16
17
18
19
Retention Time (min)
sea water
Intensity
Portisland7/19-6L
20656
1000
14
15
16
17
18
human milk
Intensity
MM-44
14512
952
14
15
16
17
18
19
adipose tissue
o-neck-fat
41200
Intensity
19
0
14
15
16
#74 (2,4,4',5-)
17
18
19
Isomer distribution （PeCB）
PCB product
Intensity
HW1013+KC3-600
122592
0
16
17
18
19
20
21
22
Retention Time (min)
sediment
Intensity
01Sed-55
33272
0
16
17
18
19
20
21
22
Retention Time (min)
sea water
Intensity
Portisland7/19-6L
8520
984
16
17
18
19
20
21
human milk
Intensity
MM-44
22336
0
16
17
18
19
20
21
22
adipose tissue
o-neck-fat
19448
Intensity
22
992
16
17
#99 (2,2’,4,4',5-)
18
19
20
21
22
#118 (2,3’,4,4',5-)
Isomer distribution （HxCB）
PCB product
Intensity
HW1013+KC3-600
124328
0
18
19
20
21
22
23
24
Retention Time (min)
sediment
Intensity
01Sed-55
32392
0
18
19
20
21
22
23
24
Retention Time (min)
sea water
Intensity
Portisland7/19-6L
5128
992
18
19
20
21
22
23
human milk
Intensity
MM-44
47792
0
18
19
20
21
22
23
24
adipose tissue
o-neck-fat
162432
Intensity
24
0
18
19
#153 (2,2',4,4',5,5'-)
20
21
22
23
24
#138(2,2',3,4,4',5'-)
Isomer distribution （HpCB）
PCB product
Intensity
HW1013+KC3-600
74056
0
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0 25.5
Retention Time (min)
sediment
Intensity
01Sed-55
8744
960
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0 25.5
Retention Time (min)
sea water
Intensity
Portisland7/19-6L
2080
984
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
human milk
MM-44
Intensity
25.0 25.5
16312
944
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0 25.5
Retention Time (min)
Intensity
o-neck-fat
42888
adipose tissue
0
20.0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0 25.5
Retention Time (min)
#187
#180
#170
human milk/adipose tissue
#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)
#138 (234-245)
#187
(2,2',3,4’,5,5’,6-)
#118 (34-245)
#187 (2356-245)
新たなPCBの起源
50
KC300-600
40
30
20
10
0
#11 (3,3’)
60
50
40
30
20
10
0
Sediment
#35 (3,3’,4)
50
Water
40
30
20
10
0
80
70
60
50
40
30
20
10
0
Isomer distribution of Di-TrCB
in PCB product and environmental samples
#10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-),
#18(2,2',5-)/#17(2,2',4-), #16(2,2',3-)/#32(2,4',6-), #26(2,3',5-), #25(2,3',4-),
#31(2,4',5-)/#28(2,4,4'-),#33(2',3,4-)/#20(2,3,3'-),#35(3,3',4-), #37(3,4,4'-)
#37
#35
#33/#20
#31/#28
#25
#26
#16/#32
#18/#17
#15
#12/#13
#11
#8/#5
Air (gas phase)
#4
40
35
30
25
20
15
10
5
0
Rain
Cl
Cl
Cl
H2N
＃11
Cl
NH2
4,4‘-Diamino-3,3’-dichlorobiphenyl
Isomer distribution
of PCN in samples
80
Air
60
40
20
66/67
50
21/24
5/7
4
25/26/13
3
6/1211/8
10
9 20/19
15 16
17
30/27
28/43
38/40
4745/36
39 3235/48
46 31
41
44
37/33/34
23 18 42
22
52/60
58 61
51
54
0
71/72
64/68
69
57 6253/5559 49 56
63 65
70
80
60
5/7
dry-deposition
21/24
51
40
71/72
6/12 11/8
20
3
4
10
0
9
23
16
20/19
22
1725/26/13
15
38/40
37/33/34
28/43
41
31
35/48
18 42
44 47 45/36 30/27 39 32
46
80
5/7
4
3
10
6/12 11/8
80
21/24
5/7
60
69
63 65
70
49 56
3
4
0
10
9 20/19
80
18 42
15 16 1725/26/13
22
44
47
62 53/55 59
54 57
64/68
49 56
69
63 65
21/24
70
71/72
59
46
28/43
35/48
45/36 30/27 39 32
52/60
41
31
61
57 62 53/55
50 51 54
58
69
65
64/68
49 56 66/67
63
70
Sediment
5/7
60
71/72
51
61
58
38/40
37/33/34
23
6/12 11/8
20
50
52/60
HALOWAX
40
40
69
6/12
11/8
4
10
23
15 16 17
18
25/26/13
22
9
37/33/34
42
47
44
52/60
38/40
28/43
45/36
35/48
46 31
30/27 39 32
41
61
50
58
51 54
57
62 53/55 59
70
Landfil
63 65
70
70
56
49
59
62
PCN isomer distribution
53/55
57
54
49 56
69
53/55 59
71/72
64/68
66/67
64/68
57
51 54
51
50
61
58
41
52/60
31
46
50
58
41
31
62
66/67
61
52/60
46
38/40
32
35/48
39
30/27
28/43
45/36 30/27 39 32 35/48
28/43
47
44
42
44
45/36
47
42
37/33/34
18
23
22
17
25/26/13
16
15
21/24
15 16 1725/26/13
22
18
9 20/19
9
10
20/19
3
11/8 3
10
6/12
4
69
38/40
23
11/8
6/12
65
37/33/34
40
63
60
4
65
49 56 66/67
21/24
5/7
5/7
71/72 63
64/68
71/72
80
20/19
3
0
0
64/68
66/67
66/67
38/40
37/33/34
25/26/13 23
28/43
46
35/48
47 45/36 30/27
15 16 17
18 42
22
41
31
44
39 32
9 20/19
0
20
59
21/24
40
20
54
57 62 53/55
rain particle
60
20
52/60 58
61 50
Contribution in
TEQ value of
PCDD/PCDF/PCB
PCN in samples
PCB concentration and TEQ value
1000
KC300
PCB
1000
PCB
KC400
10
coPCB
10
PCB
100
100
100
1000
coPCB
KC500
coPCB
1000
PCB
100
10
10
1
1
1
1
0.1
0.1
0.1
0.1
KC600
coPCB
TEQ
0.01
0.01
TEQ
0.01
0.01
TEQ
TEQ
0.001
0.001
0.001
0.001
0.0001
0.0001
0.0001
0.0001
KC300
KC400
KC500
KC600
0.7ｘ１０－５
２ｘ１０－５
６ｘ１０－５
３ｘ１０－５
Contribution in TEQ value
Ambient air
1
pg-TEQ/m3
PCB
PCN
PCDD
PCDF
PCN
PCDD
PCDF
0.1
TEQ value
0.01
0.001
1000
pg/m3
100
Total conc.
10
1
PCB
Contribution in TEQ value
100%
80%
60%
PCB
PCDF
PCDD
40%
20%
depo
sediment
water
土壌
Air
底質
大気
0%
soil
Source estimation
of
PCDD/F in samples
120
100
ｇ－TEQ/年
Hyogo
兵庫県 pref
100
ダイオキシンの年間総排出量
（ｇ－TEQ/年）
80
Emission (g-TEQ/year)
60
30
40
15
20
7
0
1996
5000
1997
1998
1999
2000
4300
2002
全国
Japan
4000
ｇ－TEQ/年
2001
ダイオキシンの年間総排出量
（ｇ－TEQ/年）
3000
Emision (g-TEQ/year)
2000
1320
1000
0
1996
1997
1998
1999
2000
2001
2002
Homologue Distribution
140
120
100
80
60
40
20
0
PCDD
PCDF
O8CDF
H7CDFs
H6CDFs
P5CDFs
T4CDFs
O8CDD
H7CDDs
H6CDDs
P5CDDs
T4CDDs
十五社橋
River
water
Homologue Distribution
1000
900
800
700
600
500
400
300
200
100
0
PCDD
PCDF
O8CDF
H7CDFs
H6CDFs
P5CDFs
T4CDFs
O8CDD
H7CDDs
H6CDDs
P5CDDs
T4CDDs
脇田橋
River
sediment
Homologue Distribution
1800
1600
1400
River
sediment
辰巳橋
1200
1000
800
600
Incineration pattern
400
200
PCDD
PCDF
O8CDF
H7CDFs
H6CDFs
P5CDFs
T4CDFs
O8CDD
H7CDDs
H6CDDs
P5CDDs
T4CDDs
0
River sediment
Homologue Distribution
PCP
CNP
O8CDF
H7CDFs
H6CDFs
PCP
1800
1600
1400
Pesticide pattern
1200
1000
800
600
P5CDFs
T4CDFs
O8CDD
H7CDDs
H6CDDs
脇田橋
Pesticide
pattern
P5CDDs
T4CDDs
1000
900
800
700
600
500
400
300
200
100
0
辰巳橋
Incineration pattern
CNP
400
200
PCDD
PCDF
O8CDF
H7CDFs
H6CDFs
P5CDFs
T4CDFs
O8CDD
H7CDDs
H6CDDs
P5CDDs
T4CDDs
0
Homologue Distribution
1600
1400
1200
Sea
sediment
神戸市東部沖
1000
800
600
400
PCDD
PCDF
O8CDF
H7CDFs
P5CDFs
燃焼系
T4CDFs
O8CDD
H7CDDs
H6CDDs
P5CDDs
T4CDDs
0
H6CDFs
200
Incineration
Pesticide
PCDF
bleaching pattern TeCDF (2,3,7,8-, 1,2,7,8-)
Chloralkali : PCDF (2,3,7,8-, 1,2,7,8-, 1,3,4,6,8-,
1,2,4,7,8-, 1,2,3,7,8-, 1,2,3,4,8-, 2,3,4,7,8-)
Incineration(FBI) : PCDF (2,4,6,7‐, 3,4,6,7-, 2,3,6,7-,
2,3,4,6-, 2,3,4,6,8-, 2,3,4,6,7-, 2,3,4,7,8-)
Pesticide(24-D) : TeCDF (2,4,6,8‐)
(CNP) : 24-F,246-F,248-F,2468-F,12468-F, 23468-F
(PCP): OCDF, 1234689-F,1234678-F, 124689-F,12468-F
Important Isomer for origin estimation
PCDD
Incineration(FBI) : 2,6-PeCDD(xxx68, xxx79)pattern
Incineration(stoker : 2,3-PeCDD pattern
Pesticide(CNP) : PCDD(13-,136-,138-,137-,139-, 1368-,1379,12479-, 12468-, 12368-, 12379-)
Pesticide(PCP) : OCDD, HpCDD(1234678-)
Pesticide(24-D) : D2CDD (2,7- , 2,8-)
PCB
Incineration and PCB product(KC,AC)
#118/#77ratio、#77/#126 ratio
PCN Incineration and PCN product(HALOWAX)
(Incineration)1267-N, 12367-N, (PCN product)1248-N
Importance of Low chlorinated DD/DF
Isomer distribution
formation mechanism
Bio degradation pathway
degration mechanism
Important information
origin estimation
on site analysis
Monitoring of stack gas
MCDF > TCDF
PCB PCN PCDD PCDF
Monitoring of Environment
水系、大気系
Detail is as follows
ISOMER SPECIFIC ANALYSIS OF
MONO- TO TRICHLORINATED
DIBENZO-DIOXINS AND
DIBENZOFURANS -
T.NAKANO and R.WEBER
Organohalogen compounds, (2000)
Precursor of PCDD/DF formation
表 クロロフェノール各異性体の縮合反応および加熱過程で生成するPCDF/PCDD異性体
Phenol
2-MCP
3-MCP
4-MCP
23-DCP
24-DCP
25-DCP
Phenol
4-F
1/3-F
2-F
34-F
24-F
2-MCP
46-F
16/36-F
26-F
346-F
17/37/19-F
18/27-F
28-F
3-MCP
4-MCP
34-DCP
35-DCP
234-TrCP
235-TrCP
14-F
12/23-F
13-F
234-F
134-F
246-F
146-F
126/236-F
136-F
2346-F
1346-F
167/347-F
168/247-F
147/149-F
137/139-F
2347/1678-F
1347/1349-F
267-F
248-F
148-F
128/238-F
138-F
2348-F
1348-F
3467-F
16/19-D
2467-F
1467-F
1267/2367-F
1367-F
23467-F
13467-F
2468-F
27/28-D
1468-F
1268/2368-F
1368-F
23468-F
13468-F
1469-F
27/28-D
1269/1478-F
1369-F
14678-F
13469-F
23-DCP
1-D
24-DCP
2-D
17/18-D
25-DCP
2-D
17/18-D
27/28-D
26-DCP
1-D
16/19-D
17/18-D
17/18-D
26-DCP
178/127/237/129-F
16/19-D
236-TrCP
Precursor of PCDD/DF formation
Phenol
2-MCP
3-MCP
4-MCP
23-DCP
24-DCP
25-DCP
Phenol
4-F
1/3-F
2-F
34-F
24-F
14-F
2-MCP
46-F
16/36-F
26-F
346-F
246-F
146-F
17/37/19-F
18/27-F
167/347-F
168/247-F
147/149-F
28-F
267-F
248-F
148-F
3-MCP
4-MCP
Authentic standard
H2 ; H3
H9
H6
NMR 1,4,7-TrCDF
H8
9
10
11
12
129
123
13
14
15
17
16
18
19
20
21
346
347/236
19
267
137
12
24
19
237/149
18
248
46
37
27
36 23
28
26
19
34
18
18
246
247
17
128
16
17
126
15
139/127
14
16
167
TrCDF
15
146
13
14
178
148
12
13
124/147
11
12
138
136
168
134
10
11
137
9
10
16
14
9
17
13
4
3
1
2
環境大気air
Ambient
MCDF
DiCDF
20
21
22
20
21
22
22
環境大気の異性体分布(MCDF～TrCDF)
Isomer
distribution of ambient air(MCDF-TrCDF)
346
237, 149
246
248
126
128
247
346
0
129
0.05
129
0.1
267
0.15
267
0.2
347, 236
0.25
347, 236
燃焼起源
Incineration
(ｆlyash)
234, 238
0.35
234, 238
237, 149
246
248
126
128
247
167
146
139, 127
123
148
178
124, 147
134
168
136
138
137
46
19, 34
26
36, 28
23
27
37
12, 24
16
18
14
17
13
4
2
3
1
0.25
167
146
139, 127
123
148
0.3
178
124, 147
134
168
136
138
137
46
19, 34
26
36, 28
23
27
37
12, 24
16
18
14
17
13
4
2
3
1
0.3
環境大気 air
Ambient
0.2
0.15
0.1
0.05
0
129
air
126
128
127
178
123
147
139, 237
124
136
138
137
19
12
16
18
14, 17
27, 23, 28
13
1
2
Ambient
環境大気
146
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.6
0.5
0.4
Incineration
(ｆlyash)
燃焼起源
0.3
0.2
0.1
環境大気の異性体分布(MCDD～TrCDD)
Isomer
distribution of ambient air(MCDD-TrCDD)
129
126
146
128
127
178
123
147
139, 237
124
136
138
137
19
12
16
18
14, 17
27, 23, 28
13
1
2
0
0.70
28-
2-
0.60
37-DiCDF
23-
0.50
0.40
27-DiCDF
27-
0.30
23-DiCDF
37-
0.20
0.10
28-DiCDF
34
26
28
23
27
37
24
12
16
18
14
17
13
4
2
3
1
0.00
128-TrCDF
238-
0.4
0.35
237-TrCDF
128-
0.3
0.25
238-TrCDF
237-
0.2
0.15
0.1
0.05
1278-TCDF
346
267
347/236
234/238
237/149
246
248
126
128
247
167
146
127
139
123
148
178
147
124
134
168
136
138
137
0
2378-TCDF
塩素漂白パターンの異性体分布(MCDF～TrCDF)
Isomer
distribution of bleaching process(MCDF-TrCDF)
238-
0.4
2-
28-
0.50
0.25
0.40
0.2
27-
346
267
347/236
234/238
246
237/149
248
126
128
247
167
146
127
139
123
148
178
147
124
137
34
26
28
23
27
37
24
12
16
18
14
17
13
0
4
0.00
2
0.05
3
0.1
0.10
134
0.15
0.20
1
237-
168
0.30
128-
0.3
136
0.60
138
0.70
0.35
塩素漂白パターンの異性体分布(MCDF～TrCDF)
Isomer
distribution of bleaching process(MCDF-TrCDF)
0.3
環境大気
Ambient air
0.25
24-
0.2
124-
0.15
0.1
0.05
Isomer
distribution of ambient air(MCDF-TrCDF)
環境大気の異性体分布(MCDF～TrCDF)
346
129
267
347, 236
234, 238
237, 149
246
248
126
128
247
167
146
139, 127
123
148
178
124, 147
134
168
136
138
137
46
19, 34
26
36, 28
23
27
37
12, 24
16
18
14
17
13
4
2
3
1
0
Isomer
distribution of ambient air(MCDF-TrCDF)
環境大気の異性体分布(MCDF～TrCDF)
346
129
267
347, 236
346
129
267
347, 236
234, 238
237, 149
246
248
126
128
247
167
248-
234, 238
237, 149
246
248
126
128
247
167
139, 127, 146
123
148
178
124, 147
168, 134
136
138
137
24-
146
0.3
139, 127
123
148
178
0.2
124, 147
24-
134
168
136
138
46
19, 34
26
36, 28
23
27
37
12, 24
16
18
0.5
137
46
19, 34
26
36, 28
23
27
37
0.25
12, 24
16
14
17
13
4
2
3
1
2
18
14
17
13
4
2
3
1
2.5
Isomer農薬CNP中の異性体分布(MCDF～TrCDF)
distribution of pesticide CNP (MCDF-TrCDF)
246-
1.5
1
pesticide CNP
0
Ambient
環境大気 air
124-
0.15
0.1
0.05
0
PCP
2345
2346
2356
345
80
236
100
234
PCP
2345
2346
2356
345
236
234
5000
245
246
235
34
35
26
23
25
24
6000
245
246
235
34
35
26
23
25
24
7000
246-P/245-P =２
4000
3000
2000
1000
0
140
120
246-P/245-P =７
60
40
20
0
MCDD-TrCDD
129
126
146
128
127
18000
16000
14000
12000
10000
8000
6000
4000
2000
0
129
126
146
128
127
178
123
147
139, 237
124
136
138
137
TrCDD
19
12
16
18
14, 17
27, 23, 28
13
DCDD
1
2
12000
178
123
147
139, 237
124
136
138
137
TrCDD
19
12
16
18
14, 17
27, 23, 28
13
DCDD
1
2
14000
10000
246-P/245-P =２
8000
6000
4000
2000
0
246-P/245-P =10
Map of Osaka-Bay
(http://www.jhd.go.jp/)

ダイオキシン類による環境汚染の現状と分析上の課題