Post on 13-Dec-2015
PCB and PCNin Environment
-Fate and Source-
Takeshi Nakano(Hyogo Pref. Inst. of Env. Sci.)
ntakeshi@pref.hyogo.jp
Dr. Imagawa / Dioxin symposium in Kyoto (1994)
Sudden Deathof Dr. Imagawa
on 19th Feb. 2001
It is truly a shame to lose him at such
a young age,and
I thank for hishelp to my study
２３４７８－PeCDF
２３４７８－PeCDF
３４５３’４’－Co-PCB
３４５３’４’－Co-PCB
２３７８－ TCDD２３７８－ TCDD
１２３５６７－HxCN
１２３５６７－HxCN
７５７５７５７５
１３５１３５
２０９２０９
PCB issue in
Japan
PCB in Japanca 60,000t
National Project in 1985-1989Decomposition in Takasago, Hyogo pref.
Liquid-PCB 5,500t90% of PCB still remain in Environment
DD/DF/PCB Levels in AirChemosphere (1986)
Daily Variation of DD/DF/PCBAtmospheric Environment(1990)
PCN in Combustion ProcessOrganohalogen compounds (1994)
PCB in Water EnvironmentIWPRC(1990)
1995.1.17 5:46amGreat Earthquake
0
10
20
30
40
50
60
70
ng/L
6 40 68 89 104
震災後 経過日数 ( 日 )
PCN(ng/L)
ng/L
The progress number of days after the earthquake disaster
PCN
(day)
PC
N c
on
ce
ntr
ati
on
in r
ain
wa
ter
PCN in rain water after great fire
TEQ Level of
technical PCB
PCB concentration and TEQ valuePCB concentration and TEQ value
KC300KC300
TEQ
co-PCB
PCB
0.0001
0.001
0.01
0.1
1
10
100
1000 KC400PCB
co-PCB
TEQ
0.0001
0.001
0.01
0.1
1
10
100
1000 KC300PCB
co-PCB
TEQ
0.0001
0.001
0.01
0.1
1
10
100
1000 KC500
TEQ
co-PCB
PCB
0.0001
0.001
0.01
0.1
1
10
100
1000 KC600
KC400KC400 KC500KC500 KC600KC600
２ｘ１０－
５
２ｘ１０－
５0.7 ｘ１０
－５
0.7 ｘ１０－５
６ｘ１０－
５
６ｘ１０－
５３ｘ１０－
５
３ｘ１０－
５
0.7 ｘ１０ 7
0.7 ｘ１０ 7
pg-TEQ/gpg-TEQ/g
2 ｘ１０7
2 ｘ１０7
6 ｘ１０7
6 ｘ１０7
3 ｘ１０7
3 ｘ１０7
PCB
90% of PCB still remain in Environment
•Transformer (Japan Railway, Power company )
•Carbon free Paper(Non Carbon Paper)
•Sealant PCB (old building before 1972)•Fluorescent
PCB
Homologue Distributionand
Source Estimation
KC300
0
10
20
30
40
50
60M
1CBs
D2CBs
T3CBs
T4CBs
P5CBs
H6CBs
H7CBs
O8CBs
N9CBs
D10
CBs
KC400
0
510
15
20
2530
35
4045
50
M1C
Bs
D2CB
s
T3CB
s
T4CB
s
P5CB
s
H6CB
s
H7CB
s
O8C
Bs
N9CB
s
D10C
Bs
KC500
05
101520253035404550
M1CBs
D2CBs
T3CBs
T4CBs
P5CBs
H6CBs
H7CBs
O8CBs
N9CBs
D10
CBs
KC600
0
5
10
15
20
25
30
35
40
45
M1C
Bs
D2CB
s
T3CB
s
T4CB
s
P5CB
s
H6CB
s
H7CB
s
O8C
Bs
N9CB
s
D10C
Bs
(KC300 )底質 由来
0
10
20
30
40
50
60
M1C
Bs
D2C
Bs
T3C
Bs
T4C
Bs
P5C
Bs
H6C
Bs
H7C
Bs
O8C
Bs
N9C
Bs
D10
CB
s 05
1015202530354045
M1CBs
D2CBs
T3CBs
T4CBs
P5CBs
H6CBs
H7CBs
O8CBs
N9CBs
D10
CBs
(KC600 )底質 由来
Source estimationSource estimation
KC ３００
KC ３００
KC ４００
KC ４００
KC ５００
KC ５００
KC ６００
KC ６００
Sediment ASediment A Sediment BSediment B
Ship paintShip paint
N.C.P.N.C.P.
InsulatorInsulator
InsulatorInsulator
capacitorcapacitor
capacitorcapacitor
99ED (%)辰巳底
0
0.2
0.4
0.6
0.8
1
1.2
1.4
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
0
0.2
0.4
0.6
0.8
1
1.2
1.4
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
KC300 (%)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
KC300KC300
Isomer distribution and Source estimationIsomer distribution and Source estimation
Sediment ASediment A Water AWater A
KC400 (%)
0
0.5
1
1.5
2
2.5
3
3.5
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
KC ４ 00KC ４ 00 KC500 (%)
0
1
2
3
4
5
6
7
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
KC600 (%)
0
2
4
6
8
10
12
#81
#77
#123
#118
#114
#105
#126
#167
#156
#157
#169
#180
#170
#189
KC ５ 00KC ５ 00
KC ６ 00KC ６ 00
Isomer distribution and Source estimationIsomer distribution and Source estimation
PCN TEQ Levelin
Ambient Air
0.00001
0.0001
0.001
0.01
0.1
1
0 1 2 3 4 5 6 7 8 9 10
Atmospheric PCN (pg-TEQ/m3) in Japan (JEPA)
PCN Profilesin
Ambient air
Homologue distribution of PCN in Ambient air
0.000
0.100
0.200
0.300
0.400
0.500
0.600
Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8
Homologue distribution of PCN in Ambient air
0.01.02.03.04.05.06.0
Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8
0.0
5.0
10.0
15.0
20.0
25.0
Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8
Kobe
On the mountain
Industrial site
0.000
0.1000.2000.3000.4000.5000.600
Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8
Homologue distribution in Ambient air
0.000
0.1000.200
0.3000.4000.5000.600
Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8
PUF
0
10
20
30
40
50
M1C
B
D2C
B
Tr3
CB
Te4
CB
P5C
B
Hx6
CB
Hp
7CB
O8C
B
N9C
B
D10
CB
PCN (vapor+particle)
PCB(gas phase)
Atmospheric level of PCB/PCN/PCDD/PCDF
1
10
100
1000
PCB PCN PCDD PCDF 0.001
0.01
0.1
1PCB PCN PCDD PCDF
Ambient air (pg/m3) Ambient air (pg-TEQ/m3)
Total concentration TEQ concentration
0.0
2.0
4.0
6.0
8.0
10.0
12.0
42
37/3
3/34
44/4
7
45/3
6
28/4
3
27/3
0 39 32
48/3
5
38/4
0 46 31 41
TeCN
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.452
/60 58 61 50 51 54 57 62
53/5
5 59 49 56
66/6
7
64/6
8 69
71/7
2 63 65 70
PeCN HxCN
0.0
2.0
4.0
6.0
8.0
10.0
12.0
4
5/7
6/12
11/8 3 10 9
20/1
9
21/2
4 14 15 16 17
25/2
6 13 22 23 18
DiCN TrCN
PCN Profiles in
Ambient Air.
(Kobe)
0
5
10
15
20
25
4
5/7
6/12
11/8 3 10 9
20/1
9
21/2
4 15 16 17
25/2
6/13 22 23 18 42
37/3
3/34
44/4
7
45/3
6
30/2
7 32
35/4
8
38/4
0 46 41
52/6
0 58 61 50 51 54 57 62
53/5
5 59 49 56
66/6
7
64/6
8 69
71/7
2 63 65 70
PCN congener distribution in ambient air.
PCN # MCN 1,2 PeCN 49-62 DiCN 3-12 HxCN 63-72 TrCN 13-26 HpCN 73,74 TeCN 27-48 OCN 75
HxCNPeCNTeCNTrCNDiCN
Landfil
4
5/7
6/1211/8 310
9 20/19
21/24
15 16 1725/26/1322
23
1842
37/33/34
4447
45/3628/43
30/27 39 32 35/48
38/40
463141
52/60
58
61
5051 54
5762
53/55 59
49 5666/67
64/68
69 71/72
63 6570
0
20
40
60
80
4
5/7
6/1
2
11/
8 3 10 9
20
/19
21
/24
15
16
17
25/2
6/1
3
22
23
18
42
37/3
3/3
4
44
47
45
/36
28
/43
30
/27
39
32
35
/48
38
/40
46
31
41
52
/60
58
61
50
51
54
57
62
53
/55
59
49
56
66
/67
64
/68
69
71
/72
63
65
70
Sediment
4
5/7
6/12
11/8 3
10 920/19
21/24
15 16 1725/26/132223
18
4237/33/34
44
47
45/3628/43
30/27 39 32 35/4838/40
46 3141
52/60
58
6150
51 5457 6253/55 59
49 5666/67
64/68
69
71/72 6365
700
20
40
60
80
HALOWAX
4
5/7
6/1211/83
10 9 20/19
21/24
15 16 1725/26/1322
23
18 42
37/33/34
4447
45/3628/43
30/27 39 3235/48
38/40
46
314152/60
58
61
50 51 54
57 6253/55
59
49 5666/6764/68
69
71/72
6365
700
20
40
60
80
dry-depos i ti o n
4
5/7
6/1211/8 3
10 920/19
21/24
15
16
1725/26/1322
23
18 42
37/33/34
44 4745/3628/43
30/27 39 3235/48
38/40
463141
52/60 5861 50
51
5457 6253/55
59
49 56
66/6764/6869
71/72
63 6570
0
20
40
60
80
rain particle
4
5/7
6/1211/8
3
10 9 20/19
21/24
15 161725/26/13
2223
18 42
37/33/34
444745/3628/4330/27
39 3235/48
38/4046
314152/60
5861
5051
54 57 6253/55 5949 56
66/67
64/6869
71/72
63 6570
0
20
40
60
80
Air
4
5/7
6/1211/83
10 920/19
21/24
15 1617
25/26/13
2223 18 42
37/33/34
44 4745/3628/43
30/27
39 3235/4838/4046 3141
52/60
58 61
50
51 5457 6253/5559 49 56
66/67
64/6869
71/72
63 6570
0
20
40
60
80
PCN isomer distribution
Air
Wa
ter
Technical
Air
Depo
Rain
Sediment
Landfill
Air, Rain
1,2,6,7- (#39)
1,2,3,4,6- (#50)1,2,3,6,7- (#54)
1,6,7- (#25)
2,3,6- (#26)1,2,3,4- (#27)
2,3- (#10) 1,2,3,7- (#30)
Air ・ Rain
Air
1,4,6- (#24) 1,3,7- (#21)
Water ・ sediment
β
Selected PCN isomers from result of PCA
236-
23-
1234-
1237-
1267-
12346-12367-
146- 137-167-
TEQ contribution of
PCDD/PCDFPCB/PCNin
Ambient Air
Ambient airAmbient air
0.001
0.01
0.1
1PCB PCN PCDD PCDF
pg-TEQ/m3
1
10
100
1000
PCB PCN PCDD PCDF
pg/m3
Contribution in TEQ value
TEQ value
Total conc.
Annual inventory of Dioxin from
Municipal Incinerator
100
3015
70
20
40
60
80
100
120
1996 1997 1998 1999 2000 2001 2002
TEQ
/ｇ－
年
兵庫県
ダイオキシンの年間総排出量TEQ/（ｇ－ 年）
4300
1320
0
1000
2000
3000
4000
5000
1996 1997 1998 1999 2000 2001 2002
TEQ
/ｇ－
年
全国
ダイオキシンの年間総排出量TEQ/（ｇ－ 年）
Hyogo pref
Japan
Emision (g-TEQ/year)
Emission (g-TEQ/year)
TEQ contribution of
PCDD/PCDFPCB/PCNin
environmental samples
0%
20%
40%
60%
80%
100%
大気
降下
ばい
じん
底質
河川
水
土壌
PCBPCDFPCDD
TEQ寄与
Air depo sediment water soil
Contribution in TEQ value
Daily variation of PCB in ambient air
Air Sampling 1000m3
High volume air sampler
•Quartz Micro Fiber for particulate
•Poly Urethane Foam for gas phase
0
5 0 0
10 0 0
15 0 0
20 0 0
PC
B C
onc
.(pg
/m3)
0
5
1 0
1 5
2 0
2 5
3 0
Air
tem
p.(d
egC
)
PC B (Q MF)
PCB (P UF)
T emp.
0
5 0
1 0 0
Ra
in (m
m)
0
5 0 0
10 0 0
15 0 0
20 0 0
4 9
19
24
24 3
13
23 3
S ampl ing Date
PC
B C
onc
.(pg
/m3)
9 8 0
9 9 0
10 0 0
10 1 0
10 2 0
10 3 0
10 4 0
Air
Pre
ss.(
hPa)
PC B (Q MF)
PCB (P UF)
Pres s .
Figure 1. Changes of PCB concentrations in air with average temperature (°C), atmospheric pressure(hPa), and precipitation (mm) on the sampling date.
R2 = 0 .1 7 93
R2 = 0 .0 0 77
0
10
20
30
40
50
60
10 1 00 1 0 00 1 0 0 00
g as eous -PC B (PUF)(pg / m3)
(°C)
9 80
9 90
1 0 00
1 0 10
1 0 20
1 0 30
1 0 40
(h Pa)
T em p.( °C) P ress ure(h Pa)
R2 = 0 .3 2 74
R2 = 0 .3 3 15
0
10
20
30
40
50
60
0.1 1 10 1 00 1 0 00
parti cu late -PCB (Q M F)(pg / m3)
(°C)
9 80
9 90
1 0 00
1 0 10
1 0 20
1 0 30
1 0 40
(h Pa)
T em p.( °C) P ress ure(h Pa)
Relation between distribution of gas and particulate-PCB with temperature (C) and atmospheric pressure (hPa).
KC 300-600
0
10
20
30
PUF
0
10
20
30
QMF
0
10
20
30
#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
Co-PCB in air and technical PCB
Gas phase
particulate
HeptaHexaPentaTetraTriDi
3,4,
3’-
3,4,
4’-
3,3’
-
4,4’
-
3,4-
/ 3,4
’-
3,4,
3’,4
’-
Importance of Low chlorinated DD/DF
formation mechanism
PCB PCN PCDD PCDF
MCDF >> TCDF
Air, Water
degradation mechanism
Source estimation
Monitoring of stack gas
Monitoring of Environment
on site analysis
Isomer distribution
Biodegradation pathway
Important information
0.00
0.10
0.20
0.30
0.40
0.50
PUF-1 PUF-2 PUF-3
2-F
0.00
0.20
0.40
0.60
0.80
1.00
PUF-1 PUF-2 PUF-3
23-F
0.00
0.20
0.40
0.60
0.80
1.00
PUF-1 PUF-2 PUF-3
248-F
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
2378-F
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
12 3 78 - F
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
234 6 78 - F
0.00
0.10
0.20
0.30
0.40
0.50
PUF-1 PUF-2 PUF-3
2-D
0.00
0.20
0.40
0.60
0.80
PUF-1 PUF-2 PUF-3
23-D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
237-D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
2378-D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
12 3 78 - D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
123789-D
0.00
0.20
0.40
0.60
0.80
1.00
PUF-1 PUF-2 PUF-3
12346 78 - D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
12346789 - D
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
12346 78 - F
0.00
0.20
0.40
0.60
0.80
1.00
1.20
PUF-1 PUF-2 PUF-3
12346789 - F
13C12-MCDF
13C12-OCDF
13C12-HpCDF
13C12-DiCDF
13C12-TrCDF
13C12-TeCDF
13C12-PeCDF
13C12-HxCDF
13C12-MCDD
13C12-OCDD
13C12-HpCDD
13C12-DiCDD
13C12-TrCDD
13C12-TeCDD
13C12-PeCDD
13C12-HxCDD
Breakthrough from PUF plug using High volume air sampler
Water Sampling 100L
High volume water sampler
•Quartz Micro Fiber for particulate
•Poly Urethane Foam for dissolved
２３４７８－PeCDF
２３４７８－PeCDF
３４５３’４’－Co-PCB
３４５３’４’－Co-PCB
２３７８－ TCDD２３７８－ TCDD
１２３５６７－HxCN
１２３５６７－HxCN
７５７５７５７５
１３５１３５
２０９２０９
PCDD/PCDF
Homologue Distributionand
Source Estimation
Water and Sedimentin
River and Coastal Sea
PCDD/DF in Waterfrom
Impurity of Pesticide in paddy soil
PCDD/DF in Airfrom
mainly combustion process
in Japan
Herbicide in the past
in Japan
•CNP 1368- and 1379-TCDD (condensation of 2,4,6-TCP)•PCP OCDD, HpCDD
•2,4-D 2,7- and 2,8- DiCDD
still using
Homologue Distribution Homologue Distribution
十五社橋
020406080
100120140
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
River water River water
PCDD PCDD PCDF PCDF
PCDD PCDD
脇田橋
0100200300400500600700800900
1000
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
PCDF PCDF
River sediment River sediment
Homologue Distribution Homologue Distribution
辰巳橋
0
200400
600
8001000
1200
14001600
1800
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
PCDD PCDD PCDF PCDF
Incineration pattern Incineration pattern
Homologue Distribution Homologue Distribution
River sediment River sediment
脇田橋
0100200300400500600700800900
1000
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
Pesticide pattern Pesticide pattern CNP CNP
PCP PCP
辰巳橋
0
200400
600
8001000
1200
14001600
1800
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
PCDD PCDD PCDF PCDF
Incineration pattern Incineration pattern
Homologue Distribution Homologue Distribution
River sediment River sediment
PCP PCP
CNP CNP
Pesticide pattern Pesticide pattern
PCDD PCDD PCDF PCDF
燃焼系 燃焼系
神戸市東部沖
0
200
400
600
800
1000
1200
1400
1600
T4C
DDs
P5C
DDs
H6C
DDs
H7C
DDs
O8C
DD
T4C
DFs
P5C
DFs
H6C
DFs
H7C
DFs
O8C
DF
Homologue Distribution Homologue Distribution
Sea sediment Sea sediment
Importance of Low chlorinated DD/DF
formation mechanism
PCB PCN PCDD PCDF
MCDF >> TCDF
Air, Water
degradation mechanism
Source estimation
Monitoring of stack gas
Monitoring of Environment
on site analysis
Isomer distribution
Biodegradation pathway
Important information
020
4060
80
M1C
l
D2C
l
Tr3
Cl
Te4
Cl
P5C
l
Hx6
Cl
Hp
7Cl
O8C
l
(pg/
L)
020
4060
80
M1C
l
D2C
l
Tr3
Cl
Te4
Cl
P5C
l
Hx6
Cl
Hp
7Cl
O8C
l
(pg/
L)
PCDFPCDD
Kako river
Homologue profiles of PCDD/Fs in river water
Σ=20pg/LΣ=100pg/L
PCDFPCDD
Homologue profiles of PCDD/Fs in river water
0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
Di-D
Tri-D
Tetra-D
Penta-D
Hexa-D
Hepta-D
OCDD
Mono-F
Di-F
Tri-F
Tetra-F
Penta-F
Hexa-F
Hepta-F
OCDF
Hudson river
(pg/g)
suspended particulate
matter (SPM)
R. Lohmann et al (1999)
020
4060
80
M1C
l
D2C
l
Tr3
Cl
Te4
Cl
P5C
l
Hx6
Cl
Hp
7Cl
O8C
l
(pg/
L)
020
4060
80
M1C
l
D2C
l
Tr3
Cl
Te4
Cl
P5C
l
Hx6
Cl
Hp
7Cl
O8C
l
(pg/
L)
PCDFPCDD
Kako river
Homologue profiles of PCDD/Fs in river water
Σ=20pg/LΣ=100pg/L
010
2030
MC
B
DiC
B
TrC
B
TeC
B
PeC
B
HxC
B
Hp
CB
OC
B
NC
B
DeC
B
(pg/
L)
River water
PCB
Homologue profiles of PCBs in river water
Σ=100pg/L
01
23
45
67
M1C
l
D2C
l
Tr3
Cl
Te4
Cl
P5C
l
Hx6
Cl
Hp
7Cl
O8C
l
(pg/
L)
Homologue profiles of PCNs in river water
PCN
River water
Σ=20pg/L
PCB contamination in
Sea sediment
海域底質中 PCB の鉛直分布海域底質中 PCB の鉛直分布
海域底質中 PCB の水平分布海域底質中 PCB の水平分布
PCB 汚染の時間的・経年変化PCB 汚染の時間的・経年変化
PCB は汚染拡散の重要な指標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 年の環境負荷使用期間 10～ 20 年の環境負荷
PCB 汚染の空間的移動PCB 汚染の空間的移動
異性体 209 ： 情報量が多い異性体 209 ： 情報量が多い
熱安定性熱安定性
化学的化学的
生物学的生物学的
PCB: important index for Pollutant dispersion
Vertical distribution of PCB in sediment core
Horizontal distribution of PCB in sediment
Historical trend of PCB pollution
Spatial migration of PCB
209 congeners : much information
Stable in environment : persistent
Environmental loading : 10-20 years
Thermal
chemical
biological
海域底質の水平分布と鉛直分布
Production of N.C.P
Annual production Sediment core
PCB concentration
Annual production and Vertical distribution in sediment
海底の地形・水深海底の地形・水深
播磨灘播磨灘大阪湾大阪湾
スープ皿のような地形スープ皿のような地形 東半分：陸、西半分：海東半分：陸、西半分：海
Horizontal distribution in sea sediment
Osaka Bay Harima nada
Sea bottom and water depth
like a soup dish Independent area
western and eastern part
siltsilt
sandsand
sandsand
Channel : fast streamChannel : fast stream
Central part: slow stream Central part: slow stream
siltsilt
Horizontal distribution in sea sediment
Particle size in sea sediment
海域底質の粒度分布を考慮しない場合海域底質の粒度分布を考慮しない場合
High
High
Low
Low
LowLow
High
High
High
High
濃度の単調減少濃度の単調減少
Inmost part
Inmost part
鳴門鳴門 Osaka Bay
Osaka Bay
coastcoast
Central part : High
Central part : High
channelchannel
Horizontal distribution in sea sediment
Harima nada
Harima nada
Before normalization by particle size distribution
海域底質の粒度分布を考慮した場合海域底質の粒度分布を考慮した場合
海域底質中 PCB の水平分布海域底質中 PCB の水平分布
恒流図と濃度分布恒流図と濃度分布
粒径・微細粒子・比表面積で規格化粒径・微細粒子・比表面積で規格化
Constant flow map and PCB distribution
After normalization by particle size distribution
Horizontal distribution in sea sediment
海域底質の水平分布海域底質の水平分布
大阪湾大阪湾
PCB 濃度の距離減衰PCB 濃度の距離減衰
神戸港周辺神戸港周辺
Horizontal distribution in sea sediment
Osaka bay
Around Kobe port
PCB concentration and Distance from source
T.NAKANO and R.WEBER
Organohalogen compounds,Vol.46, 558-561 (2000)
ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED
DIBENZO-DIOXINS AND DIBENZOFURANS -
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
3-MCP 17/37/19-F 18/27-F 167/347-F 168/247-F 147/149-F
4-MCP 28-F 267-F 248-F 148-F
Precursor of PCDD/DF formation
O
Cl
ClCl
O
ClCl
Cl
OH
Cl
OH
Cl
Cl
2,3,8-
1,2,8-+
4-MCP
3,4-DCP 2,3,8-TrCDF
1,2,8-TrCDF
O
Cl
O
OH
OH
Cl
1,4,7-
1,4,9- Cl
Cl
Cl
Cl
Cl
Cl
Cl
OH
OH
O
Cl
1,4,6- Cl
O
Cl
1,4,8- Cl
Cl
Cl
Cl
Cl
Synthesis of 1,4,X-T3CDF isomers from chlorophenol
Authentic standard (1,4,7- : NMR)
2,5-DCP
4-MCP
3-MCP
2-MCP
O-m-
p-
1,4,6-TrCDF
1,4,8-TrCDF
1,4,9-TrCDF
1,4,7-TrCDF
NMR 1,4,7-TrCDF
Authentic standard
H9
H6H8
H2 ; H3
9 10 11 12 13 14 15 16 17 18 19 20 21 22
9 10 11 12 13 14 15 16 17 18 19 20 21 22
9 10 11 12 13 14 15 16 17 18 19 20 21 22
1
4
2
3
MCDF
13 17
1418
1612
3727
36
46
3426
28
24
19
23
137
DiCDF
TrCDF
138
346
129
267
347/
236
137
237/
149
246
248
136 16
813
412
4/14
7
178
148
126
128
247
167
139/
127
146
123
環境大気環境大気Ambient air
環境大気
0
0.05
0.1
0.15
0.2
0.25
0.3
1 3 2 4 13 17 14 18 16
12, 24 37 27 23
36, 28 26
19, 34 46 137
138
136
168
134
124,
147
178
148
123
139,
127
146
167
247
128
126
248
246
237,
149
234,
238
347,
236
267
129
346
燃焼起源
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
1 3 2 4 13 17 14 18 16
12, 24 37 27 23
36, 28 26
19, 34 46 137
138
136
168
134
124,
147
178
148
123
139,
127
146
167
247
128
126
248
246
237,
149
234,
238
347,
236
267
129
346
環境大気の異性体分布 (MCDF ～ TrCDF)環境大気の異性体分布 (MCDF ～ TrCDF)
Ambient air
Incineration (flyash)
Isomer distribution of ambient air(MCDF-TrCDF)
環境大気
00.10.20.30.40.50.60.70.8
2 1 13
27, 2
3, 2
8
14, 1
7 18 16 12 19 137
138
136
124
139,
237 147
123
178
127
128
146
126
129
燃焼起源
0
0.1
0.2
0.3
0.4
0.5
0.6
2 1 13
27, 2
3, 2
8
14, 1
7 18 16 12 19 137
138
136
124
139,
237 147
123
178
127
128
146
126
129
環境大気の異性体分布 (MCDD ～ TrCDD)環境大気の異性体分布 (MCDD ～ TrCDD)Isomer distribution of ambient air(MCDD-TrCDD)
Incineration (flyash)
Ambient air
塩素漂白パターンの異性体分布 (MCDF ～ TrCDF)塩素漂白パターンの異性体分布 (MCDF ～ TrCDF)
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
1 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
137
138
136
168
134
124
147
178
148
123
139
127
146
167
247
128
126
248
246
237/
149
234/
238
347/
236
267
346
28-28-
23-23-
27-27-37-37-
2-2-
238-238-
128-128-
237-237-
1278-TCDF1278-TCDF
2378-TCDF2378-TCDF
238-TrCDF238-TrCDF
237-TrCDF237-TrCDF
128-TrCDF128-TrCDF
37-DiCDF37-DiCDF
27-DiCDF27-DiCDF
23-DiCDF23-DiCDF
28-DiCDF28-DiCDF
Isomer distribution of bleaching process(MCDF-TrCDF)
塩素漂白パターンの異性体分布 (MCDF ～ TrCDF)塩素漂白パターンの異性体分布 (MCDF ～ TrCDF)
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.701 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
137
138
136
168
134
124
147
178
148
123
139
127
146
167
247
128
126
248
246
237/
149
234/
238
347/
236
267
346
環境大気
0
0.05
0.1
0.15
0.2
0.25
0.3
1 3 2 4 13
17
14
18
16
12,
24
37
27
23
36,
28
26
19,
34
46
137
138
136
168
134
124, 1
47
178
148
123
139, 1
27
146
167
247
128
126
248
246
237, 1
49
234, 2
38
347, 2
36
267
129
346
環境大気の異性体分布 (MCDF ～ TrCDF)環境大気の異性体分布 (MCDF ～ TrCDF)
28-28-
27-27-
238-238-128-128-
237-237-2-2-
124-124-
24-24-
Isomer distribution of ambient air(MCDF-TrCDF)
Isomer distribution of bleaching process(MCDF-TrCDF)
Ambient air
0
0. 5
1
1. 5
2
2. 5
1 3 2 4 13 17 14 18 16
12,
24 37 27 23
36,
28 26
19,
34 46 137
138
136
168,
134
124,
147 178
148
123
139,
127
, 14
6
167
247
128
126
248
246
237,
149
234,
238
347,
236 267
129
346
農薬 CNP 中の異性体分布 (MCDF ～ TrCDF)農薬 CNP 中の異性体分布 (MCDF ～ TrCDF)
環境大気
0
0.05
0.1
0.15
0.2
0.25
0.3
1 3 2 4 13
17
14
18
16
12,
24
37
27
23
36,
28
26
19,
34
46
137
138
136
168
134
124, 1
47
178
148
123
139, 1
27
146
167
247
128
126
248
246
237, 1
49
234, 2
38
347, 2
36
267
129
346
環境大気の異性体分布 (MCDF ～ TrCDF)環境大気の異性体分布 (MCDF ～ TrCDF)
248-248- 246-246-
124-124-24-24-
24-24-
Isomer distribution of ambient air(MCDF-TrCDF)
Isomer distribution of pesticide CNP (MCDF-TrCDF)
pesticide CNP
Ambient air