Transcript Document

Environmental Occurrence
POPs in Environmental and
Human samples
Takeshi NAKANO
(Hyogo Pref. Inst. of Env. Sci.)
[email protected]
２３４７８－PeCDF
２３７８－TCDD
７５
１３５
７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB
PCB issue
in
Japan
PCB in Japan
ca 60,000t
National Project in 1985-1989
Decomposition in Takasago, Hyogo pref.
Liquid-PCB
5,500t
90% of PCB still remain in Environment
TEQ Level
of
technical PCB
PCB concentration and TEQ value
1000
PCB
KC300
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
2 ｘ１０7
6 ｘ１０7
3 ｘ１０7
pg-TEQ/g
0.7ｘ１０7
90% of PCB still remain in Environment
PCB
•Transformer (Japan Railway, Power company )
•Carbon free Paper(Non Carbon Paper)
•Sealant PCB (old building during 1968-72)
•Fluorescent lamp stabilizer (old type)
•etc
PCB
Homologue Distribution
and
Source Estimation
30
25
20
15
Insulator
10
5
0
capacitor
45
40
KC６００
Ship paint
5
0
D10CBs
10
D10CBs
15
N9CBs
20
N9CBs
25
O8CBs
30
O8CBs
35
H7CBs
KC600
H7CBs
H6CBs
P5CBs
D10CBs
N9CBs
O8CBs
H7CBs
H6CBs
P5CBs
T4CBs
T3CBs
KC５００
50
45
40
35
30
25
20
15
10
5
0
H6CBs
KC４００
D2CBs
Source estimation
P5CBs
0
T4CBs
Sediment A
T4CBs
40
T3CBs
底質(KC300由来)
45
40
35
30
25
20
15
10
5
0
T3CBs
60
capacitor
D2CBs
20
M1CBs
KC３００
M1CBs
40
D2CBs
35
N.C.P.
D10CBs
50
M1CBs
KC400
D10CBs
KC300
D10CBs
10
N9CBs
0
N9CBs
20
O8CBs
H7CBs
H6CBs
10
N9CBs
30
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
Insulator
底質(KC600由来)
Sediment B
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 (%)
PCB contamination
in
Sea sediment
PCBは汚染拡散の重要な指標
PCB:
important index for Pollutant dispersion
環境中で分解しない。：難分解性
Stable
in environment : persistent
使用期間10～20年の環境負荷
Environmental
loading : 10-20 years
209
congeners
information
異性体
209 ：: much
情報量が多い
海域底質中PCBの鉛直分布
Vertical
distribution of PCB in sediment core
PCB汚染の時間的・経年変化
Historical
trend of PCB pollution
海域底質中PCBの水平分布
Horizontal
distribution of PCB in sediment
PCB汚染の空間的移動
Spatial
migration of PCB
Thermal
熱安定性
化学的
chemical
生物学的
biological
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Bay
Osaka
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海底の地形・水深
bottom and water depth
Horizontal distribution in sea sediment
Channel : fast stream
sand
silt
silt
sand
Central part: slow stream
Particle size in sea sediment
海域底質の粒度分布を考慮しない場合
Before normalization
by particle size distribution
coast
High
High
Low
Inmost part
channel
High
濃度の単調減少
Harima nada
鳴門
Low
Osaka Bay
Central part : High
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恒流図と濃度分布
flow map and PCB distribution
粒径・微細粒子・比表面積で規格化
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
PCB congener profile
in Environmental
and Human 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
MM-44
Intensity
19
14512
952
14
15
16
17
18
19
adipose
tissue
Intensity
o-neck-fat
41200
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
MM-44
Intensity
22
22336
0
16
17
18
19
20
21
22
adipose
tissue
Intensity
o-neck-fat
19448
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
MM-44
Intensity
24
47792
0
18
19
20
21
22
23
24
adipose
tissue
Intensity
o-neck-fat
162432
0
18
19
20
#153 (2,2',4,4',5,5'-)
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
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
adipose
tissue
human milk/adipose tissue
#74
(2,4,4',5-)
#99
(2,2’,4,4',5-)
#153
(2,2',4,4',5,5'-)
# 7 4 (4 -2 4 5 )
# 1 5 3 (2 4 5 -2 4 5 )
#138
(2,2',3,4,4',5'-)
# 9 9 (2 4 -2 4 5 )
# 1 3 8 (2 3 4 -2 4 5 )
# 1 1 8 (3 4 -2 4 5 )
#187
(2,2',3,4’,5,5’,6
-)
# 1 8 7 (2 3 5 6 -2 4 5 )
#118
(2,3’,4,4',5-)
CYP1A,CYP2
A
Cl
Cl
Cl
HO
Cl
Cl
4-OH
Cl
Cl
CYP2B
HO
Cl
Cl
3-OH
Cl Cl
Cl
Cl
Cl
Cl
#153 (2,4,5,2',4',5')
PCB #153 代謝
イヌ
モルモット
>
ヒト
ラット
ハムスター
サル
HO
Cl Cl
Cl
Cl
Cl
dog (CYP2B11)
guinea pig (CYP2B18)
Cl
>
human (CYP2B6)
rat, hamster
POPs
in Human Breast Milk
POPs in Human Breast Milk
70
ng/g-fat
YM
MM
60
50
40
30
20
#153-PCB
#118-PCB
HCB
p,p'-DDE
beta-HCH
0
transnonachlor
10
PCBs in Human Breast Milk
60
ng/g-fat
MM
50
YM
40
30
20
10
DeCB
NoCB
OcCB
HpCB
HxCB
PeCB
TeCB
TrCB
DiCB
MCB
0
PCB
in Water and Mussel

Polychlorinated biphenyl(PCB) is well-known
environmental pollutants. In Japan,
approximately 58,000t of PCB was produced
and imported from overseas by 1972 . Despite
of the ban and restriction of PCB usage since
1972, 90% of total products has still been
untreated.
 PCB is transported in the environment(water,
air, and ecosystem) in various forms.
Sampling Points
Himeji
Kako River
Akashi
Muko River
Yodo River
Port Island Nanko
Hokutan
Izumiotsu
Yura
Around Harima-nada and Osaka
Bay, this investigation have been
done once a month
from May, 2001 to Aug, 2001
500000
450000
PCB production
World : 1,200,000t
Japan :
59,000t
400000
350000
300000
250000
200000
150000
Harima-nada
Osaka-Bay
Japan
100000
Osak
a
1962-1971
1962-1971
700
50000
Spain
others
600
Italy
Japan
UK
Germany
USA
France
0
500
Hyog
o
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
Level
10 ng/g-dry
100 ng/g-dry
Harima-nada
Osaka-Bay
PCB in sea sediment
0
Sea Water
0
Mussel
average
The range of total PCBs concentration
(May,2001~July,2001)
Izumiotsu
35 ng/g-wet
Nanko
200
Yodo River
2
Harima-nada
Muko River
4
Port Island
6
Hokutan
160
Yura
8
180
Akashi
5 ng/L
Kako River
10
concentratino(ng/L)
14
Himeji
Izumiotsu
Nanko
1 ng/L
Yodo River
Muko River
Port Island
Hokutan
Yura
Akashi
12
Kako River
Himeji
concentratino(ng/L)
Harima-nada Osaka-Bay
Osaka-Bay
80 ng/g
140
120
100
80
60
40
20
Harima-nada Osaka-Bay
Harima-nada Osaka-Bay
0.9
0.06 ng/L
0.3 ng/L
9
8
4
Sea Water
Izumiotsu
Nanko
Yodo River
Muko River
Izumiotsu
Nanko
Yodo River
Muko River
0
Port Island
0
Hokutan
1
Yura
0.1
Akashi
2
Kako River
0.2
Port Island
3
Hokutan
0.3
5
Yura
0.4
6
Akashi
0.5
7
Kako River
0.6
Himeji
concentratino(ng/L)
0.7
Himeji
concentratino(ng/L)
0.8
5 ng/g
2 ng/g-wet
10
Mussel
The range of total co-PCBs concentration
average
(May,2001~July,2001)
Sea Water
1
20
0.5
10
0
0
Mussel
Fig #11/ΣDiCBｓ in June, 2001
Izumiotsu
30
Nanko
1.5
Yodo river
40
Muko river
2
Port Island
50
Yura
2.5
Hokudan
60
Akashi
3
Kako river
70
Himeji
Izumiotsu
Nanko
Yodo river
Muko river
Port Island
Yura
Hokudan
Akashi
Kako river
Himeji
3.5
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
#189
#180
#170, #190
#191
#180, #193
KC300-600
#174
#192, #172
#184
Mussel
#184
Sea Water
#184
#188
Intensity
0.6
0.4
0.2
0
#170
Isomer distribution (P7CB, Port Island in June,2001)
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)
Sea Water
Mussel
Homologue Distribution in June,2001
P2CB
P3CB
P4CB
P5CB
P6CB
P7CB
P8CB
Izumiotsu
Nanko
Yodo river
Muko river
Port Island
0%
Seidan
0%
Yura
50%
Akashi
50%
Kako river
100%
Himeji
Izumiotsu
Nanko
Yodo river
Muko river
Port Island
Seidan
Yura
Akashi
Kako river
Himeji
100%
PCB #11
New Source
Cl
Cl
Cl
H 2N
＃11
Cl
NH 2
4,4‘-Diamino-3,3’-dichlorobiphenyl
PCN TEQ Level
in
Ambient Air
Atmospheric PCN (pg-TEQ/m3) in Japan (JEPA)
1
0.1
0.01
0.001
0.0001
0.00001
0
1
2
3
4
5
6
7
8
9
10
TEQ contribution of
PCDD/PCDF/PCB/PCN
in
Ambient Air
Ambient air (pg-TEQ/m3)
Ambient air (pg/m3)
1
1000
PCB
100
PCN
PCDD
0.1
10
0.01
1
PCB
PCN
PCDD
PCDF
Total concentration
0.001
TEQ concentration
Atmospheric level of PCB/PCN/PCDD/PCDF
PCDF
Air, Rain
Air ・ Rain
1237-
236-
1,2,3,4- (#27)
2,3,6- (#26)
β
1,2,3,7- (#30)
23-
2,3- (#10)
Water ・ sediment
1234-
1,6,7- (#25)
167-
1,4,6- (#24)
146-
1,2,6,7- (#39)
1267-
Air
1,2,3,4,6- (#50)
12346-
1,2,3,6,7- (#54)
12367-
Selected PCN isomers from result of PCA
1,3,7- (#21)
137-
Unintentional Formation
(HCB, PCN, PCB, Dioxins)
FIRE
1995.1.17 5:46am
Great Earthquake
(Kobe)
PCN concentration in rain water
ng/L
ng/L
PCN in rain water after great fire
70
PCN(ng/L)
PCN
60
50
40
30
20
10
0
6
40
68
89
104
(day)
after
the経過日数(日)
earthquake disaster
震災後
Annual inventory of Dioxin
from
Municipal Incinerator
120
100
ｇ－TEQ/年
Hyogo
pref
兵庫県
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 (g1320
TEQ/year)
2000
1000
0
1996
1997
1998
1999
2000
2001
2002
TEQ contribution of
PCDD/PCDF/PCB/PCN
in
environmental samples
Contribution in TEQ value
100%
80%
60%
PCB
PCDF
PCDD
40%
20%
TEQ寄与
water
土壌
sediment
河川水
depo
底質
Air
降下ばいじん
大気
0%
soil
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
PCB Conc.(pg/m3)
1500
30
25
20
1000
15
10
Air temp.(degC)
PCB(QMF)
PCB(PUF)
Temp.
2000
500
5
Rain (mm)
0
0
100
50
0
PCB(QMF)
1040
PCB Conc.(pg/m3)
PCB(PUF)
1500
1030
Press.
1020
1000
1010
1000
500
Air Press.(hPa)
2000
990
3
23
13
3
24
24
19
9
980
4
0
Sampling Date
F igure 1. C hanges of P C B concentrations in air with average tem perature (°C ), atm ospheric pressure
(hP a), and precipitation (m m ) on the sam pling date.
(°C)
(hPa)
(°C)
(hPa)
60
1040
60
1040
2
2
R = 0.0077
50
R = 0.3315
1030
50
1030
40
1020
40
1020
30
1010
30
1010
20
1000
20
1000
990
10
10
2
R = 0.1793
0
R = 0.3274
980
10
100
1000
gaseous-PCB(PUF)(pg/m3)
Temp.(°C)
Pressure(hPa)
990
2
10000
0
980
0.1
1
10
100
1000
particulate-PCB(QMF)(pg/m3)
Temp.(°C)
Pressure(hPa)
Relation between distribution of gas and particulate-PCB
with temperature ( C) and atmospheric pressure (hPa).
20
30
30
Tri
3,4,3’,4’-
3,4,4’-
Di
3,4,3’-
4,4’-
3,4-/ 3,4’-
10
3,3’-
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
Tetra
Penta
Hexa
Hepta
KC 300-600
0
20
10
0
PUF
Gas phase
QMF
particulate
20
10
0
Importance of Low chlorinated DD/DF
formation mechanism
Isomer distribution
degradation mechanism
Biodegradation pathway
Source estimation
Important information
on site analysis
Monitoring of stack gas
MCDF >> TCDF
PCB PCN PCDD PCDF
Monitoring of Environment
Air, Water
0.50
0.40
13C
12-MCDF
0.20
0.20
0.10
0.10
0.00
1.00
0.80
12-DiCDF
0.40
0.30
PUF-2
PUF-3
0.20
PUF-3
0.20
PUF-2
PUF-3
1.20
1.00
2378-F
0.80
0.60
0.40
0.20
0.40
0.20
0.00
13C
12-PeCDF
PUF-2
PUF-3
1.20
12378-F
1.00
0.80
0.60
0.60
0.40
0.40
0.20
0.20
0.00
13C
12-HxCDF
PUF-3
1.00
0.80
0.60
0.60
0.40
0.40
0.20
0.20
0.00
0.00
1.00
PUF-2
PUF-3
0.80
0.20
0.20
0.00
0.00
PUF-1
13C
12-OCDF
PUF-3
13C
PUF-2
12-PeCDD
PUF-3
123789-D
13C
PUF-2
PUF-2
PUF-3
1234678-D
13C
PUF-1
1.20
12346789-F
1.00
0.80
0.80
0.60
0.60
0.40
0.40
0.20
0.20
0.00
12-HxCDD
PUF-3
0.40
0.40
1.00
PUF-2
0.60
0.60
1.20
12-TeCDD
12378-D
PUF-1
1.00
1234678-F
0.80
12-HpCDF
13C
PUF-1
1.20
234678-F
PUF-1
13C
PUF-2
0.80
1.20
PUF-3
0.00
PUF-1
1.00
PUF-2
12-TrCDD
2378-D
PUF-1
0.80
1.20
13C
0.00
PUF-1
1.00
12-DiCDD
PUF-3
237-D
PUF-1
0.80
0.60
1.20
PUF-2
0.60
0.40
0.20
0.00
0.40
PUF-1
12-TeCDF
PUF-1
1.20
1.00
0.80
248-F
0.00
13C
13C
0.00
PUF-2
0.60
1.20
1.00
23-D
0.20
PUF-1
12-TrCDF
12-MCDD
PUF-3
0.40
0.00
13C
PUF-2
0.60
0.40
0.80
13C
PUF-1
0.80
23-F
0.60
1.00
2-D
0.00
PUF-1
13C
0.50
2-F
0.30
PUF-2
12-HpCDD
PUF-3
12346789-D
13C
12-OCDD
0.00
PUF-1
PUF-2
PUF-3
PUF-1
PUF-2
PUF-3
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
２３７８－TCDD
７５
１３５
７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB
PCDD/PCDF
Homologue Distribution
and
Source Estimation
Water and Sediment
in
River and Coastal Sea
PCDD/DF in Air
from
mainly combustion process
in Japan
PCDD/DF in Water
from
Impurity of Pesticide in paddy soil
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
Homologue profiles of PCDD/Fs in river water
O8Cl
Hp7Cl
Hx6Cl
P5Cl
20
40
(pg/L)
60
60
80
80
Kako river
Te4Cl
Tr3Cl
D2Cl
0
20
PCDD
M1Cl
O8Cl
Hp7Cl
Hx6Cl
P5Cl
Te4Cl
Tr3Cl
D2Cl
M1Cl
0
(pg/L)
40
Σ=100pg/L
Σ=20pg/L
PCDF
in Japan
Herbicide in the past
•CNP
1368- and 1379-TCDD
(condensation of 2,4,6-TCP)
•PCP OCDD, HpCDD
still using
•2,4-D
2,7- and 2,8- DiCDD
PCDF
PCDD
Hudson river
suspended particulate
Homologue profiles of PCDD/Fs in river water
R. Lohmann et al (1999)
OCDF
Hepta-F
Hexa-F
Penta-F
Tetra-F
Tri-F
Di-F
Mono-F
OCDD
Hepta-D
Hexa-D
Penta-D
Tetra-D
matter (SPM)
Tri-D
Di-D
(pg/g)
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
Source estimation
of PCDD/DF
9
10
11
12
13
14
129
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
123
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)
0
234, 238
237, 149
246
248
126
128
247
167
346
0.05
346
0.1
129
0.15
129
0.2
267
0.25
267
燃焼起源
Incineration
(flyash)
347, 236
0.35
347, 236
234, 238
237, 149
246
248
126
128
247
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
178
0.3
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
237/149
246
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
air
環境大気
124-
0.15
0.1
0.05
0
Env. Level (1998 survey)

Conc. range
 Air
０～1.8 pg-TEQ/m3
 deposition 0.2～170 pg-TEQ/m2/d
 water
0～12 pg-TEQ/L
 groundwater 0～5.3 pg-TEQ/L
 sediment 0～230 pg-TEQ/g
 soil
10-3～110 pg-TEQ/g
 biota
0～11 pg-TEQ/g-wet
average medium Co-PCB（%)
0.22
21
0.36
0.086
6.8
6.2
0.64
0.15
17
0.089
0.0073
0.23
2.3
0.32
5.7
8.3
12
10
11
7.7
70
Dioxin monitoring
in Hyogo pref.
 Air 30 stations, Soil 30 stations
 water 20 stations, sediment 20 stations




total 250 samples in 2000
Air 20 stations x 4 seasons, soil 20 stations
water 42 stations, sediment 42 stations
Stack gas 44, effluent water 44