Environmental Occurrence

POPs in Environmental and Human samples

Takeshi NAKANO(Hyogo Pref. Inst. of Env. Sci.)

ntakeshi@elis.pref.hyogo.jp

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

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 during 1968-72)

•Fluorescent lamp stabilizer (old type)

•etc

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

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

Vertical distribution

of PCB in sea sediment

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

Horizontal distribution

of PCB in sea 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

PCB congener profile in Environmental

and Human samples

Isomer distribution （ TeCB ）Isomer distribution （ TeCB ）

14 15 16 17 18 19

Retention Time (min)

0

357936

Inte

nsi

ty

HW1013+KC3-600

14 15 16 17 18 19

Retention Time (min)

0

68784

Inte

nsi

ty01Sed-55

14 15 16 17 18 19

1000

20656

Inte

nsi

ty

Portisland7/19-6L

14 15 16 17 18 19

952

14512

Inte

nsi

ty

MM-44

14 15 16 17 18 19

0

41200

Inte

nsi

ty

o-neck-fat

#74 (2,4,4',5-)#74 (2,4,4',5-)

PCB product

sediment

sea 　 water

human milk

adipose tissue

Isomer distribution （ PeCB ）Isomer distribution （ PeCB ）

#99 (2,2’,4,4',5-)

#99 (2,2’,4,4',5-)

16 17 18 19 20 21 22

Retention Time (min)

0

122592

Inte

nsi

ty

HW1013+KC3-600

16 17 18 19 20 21 22

Retention Time (min)

0

33272

Inte

nsi

ty01Sed-55

16 17 18 19 20 21 22

984

8520

Inte

nsi

ty

Portisland7/19-6L

16 17 18 19 20 21 22

0

22336

Inte

nsi

ty

MM-44

16 17 18 19 20 21 22

992

19448

Inte

nsi

ty

o-neck-fat

#118 (2,3’,4,4',5-)

#118 (2,3’,4,4',5-)

PCB product

sediment

sea 　 water

human milk

adipose tissue

Isomer distribution （ HxCB ）Isomer distribution （ HxCB ）

#153 (2,2',4,4',5,5'-)#153 (2,2',4,4',5,5'-)

18 19 20 21 22 23 24

Retention Time (min)

0

124328

Inte

nsi

ty

HW1013+KC3-600

18 19 20 21 22 23 24

Retention Time (min)

0

32392

Inte

nsi

ty01Sed-55

18 19 20 21 22 23 24

992

5128

Inte

nsi

ty

Portisland7/19-6L

18 19 20 21 22 23 24

0

47792

Inte

nsi

ty

MM-44

18 19 20 21 22 23 24

0

162432

Inte

nsi

ty

o-neck-fat

#138(2,2',3,4,4',5'-)#138(2,2',3,4,4',5'-)

PCB product

sediment

sea 　 water

human milk

adipose tissue

Isomer distribution （ HpCB ）Isomer distribution （ HpCB ）

#187#187

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)

0

74056

Inte

nsi

ty

HW1013+KC3-600

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)

960

8744

Inte

nsi

ty01Sed-55

20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0 25.5

984

2080

Inte

nsi

ty

Portisland7/19-6L

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)

944

16312

Inte

nsi

ty

MM-44

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)

0

42888

Inte

nsi

ty

o-neck-fat

#180#180 #170#170

PCB product

sediment

sea 　 water

human milk

adipose tissue

human milk/adipose tissue

human milk/adipose tissue

#74 (4-245)

#99 (24-245)

#118 (34-245)

#153 (245-245)

#138 (234-245)

#187 (2356-245)

#74 　(2,4,4',5-)

#74 　(2,4,4',5-)

#99 (2,2’,4,4',5-)

#99 (2,2’,4,4',5-)

#118 　(2,3’,4,4',5-)

#118 　(2,3’,4,4',5-)

#153(2,2',4,4',5,5'-)

#153(2,2',4,4',5,5'-)

#138(2,2',3,4,4',5'-)

#138(2,2',3,4,4',5'-)

#187(2,2',3,4’,5,5’,6

-)

#187(2,2',3,4’,5,5’,6

-)

CYP1A,CYP2A

CYP2B

4-OH

3-OH

Cl

Cl

Cl

Cl

Cl

HO

Cl

Cl

Cl

ClHO

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

HO

#153 (2,4,5,2',4',5')

guinea pig (CYP2B18)

dog (CYP2B11) human (CYP2B6)rat, hamster>

PCB 　 #153 　代謝

イヌモルモッ

ト

>ヒト

ラットハムスタ

ーサル

POPs in Human Breast Milk

POPs in Human Breast Milk

0

10

20

30

40

50

60

70

beta

-HC

H

p,p'

-DD

E

tran

s-no

nach

lor

HC

B

#118

-PC

B

#153

-PC

B

YMMM

ng/g-fat

PCBs in Human Breast Milk

0

10

20

30

40

50

60M

CB

DiC

B

TrC

B

Te

CB

Pe

CB

Hx

CB

Hp

CB

Oc

CB

No

CB

De

CB

MM

YM

ng/g-fat

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 PointsSampling Points

Himeji

AkashiPort Island

Muko RiverYodo River

Nanko

IzumiotsuHokutan

Yura

Kako River

Around Harima-nada and Osaka Bay, this investigation have been done once a month from May, 2001 to Aug, 2001

0

50000

100000

150000

200000

250000

300000

350000

400000

450000

500000

USA

Fra

nce

Ger

man

y

UK

Japan

Ital

y

Spai

n

oth

ers

0

5000

10000

15000

20000

25000

Hokk

aido

Tohoku

Kan

to

Hoku

riku

Toka

i

Kin

ki

Chugoku

Shik

oku

Kyu

syu

1962-1971

0

100

200

300

400

500

600

700

Hyog

o

Osaka Shiga

Kyoto

1962-1971

Japan

Kinki

Hyogo

Osaka 1962-1971

PCB productionWorld : 1,200,000t Japan : 59,000t

1962-1971

Harima-nadaOsaka-Bay

Harima-nadaOsaka-Bay

PCB in sea sediment

10 ng/g-dry 100 ng/g-dryLevel

The range of total PCBs concentration (May,2001~July,2001)

0

2

4

6

8

10

12

14H

ime

ji

Ka

ko

Riv

er

Ak

as

hi

Yu

ra

Ho

ku

tan

Po

rt Is

lan

d

Mu

ko

Riv

er

Yo

do

Riv

er

Na

nk

o

Izu

mio

tsu

co

nc

en

tra

tin

o(n

g/L

)

0

20

40

60

80

100

120

140

160

180

200

Him

eji

Ka

ko

Riv

er

Ak

as

hi

Yu

ra

Ho

ku

tan

Po

rt Is

lan

d

Mu

ko

Riv

er

Yo

do

Riv

er

Na

nk

o

Izu

mio

tsu

co

nc

en

tra

tin

o(n

g/L

)

average

Harima-nada Harima-nada Osaka-BayOsaka-Bay

1 ng/L 35 ng/g-wet

Sea Water

5 ng/L 80 ng/g

Mussel

The range of total co-PCBs concentration (May,2001~July,2001)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9H

ime

ji

Ka

ko

Riv

er

Ak

as

hi

Yu

ra

Ho

ku

tan

Po

rt Is

lan

d

Mu

ko

Riv

er

Yo

do

Riv

er

Na

nk

o

Izu

mio

tsu

co

nc

en

tra

tin

o(n

g/L

)

0

1

2

3

4

5

6

7

8

9

10

Him

eji

Ka

ko

Riv

er

Ak

as

hi

Yu

ra

Ho

ku

tan

Po

rt Is

lan

d

Mu

ko

Riv

er

Yo

do

Riv

er

Na

nk

o

Izu

mio

tsu

co

nc

en

tra

tin

o(n

g/L

)

average

Harima-nada Osaka-Bay Harima-nada Osaka-Bay

Sea Water Mussel

0.06 ng/L 0.3 ng/L5 ng/g2 ng/g-wet

0

0.5

1

1.5

2

2.5

3

3.5

Him

eji

Kak

o rive

r

Aka

shi

Hok

udan

Yur

a

Por

t Is

land

Muk

o rive

r

Yod

o rive

r

Nan

ko

Izum

iots

u

0

10

20

30

40

50

60

70

Him

eji

Kak

o rive

r

Aka

shi

Hok

udan

Yur

a

Por

t Is

land

Muk

o rive

r

Yod

o rive

r

Nan

ko

Izum

iots

u

Sea Water Mussel

Fig #11/ΣDiCB ｓ in June, 2001　

00.20.40.6

#188

#184

#179

#176

#186

#178

#175

#187, #182 #183

#185

#174, #181 #177

#171

#173

#192, #172

#180, #193 #191

#170, #190 #189

00.10.20.3

#188 #184 #179 #176 #186 #178 #175 #187, #182 #183 #185 #174, #181 #177 #171 #173 #192, #172 #180, #193 #191 #170, #190 #189

00.050.1

0.150.2

0.250.3

0.350.4

#188

#184

#179

#176

#186

#178

#175

#187

, #18

2 #183

#185

#174

, #18

1 #177

#171

#173

#192

, #17

2

#180

, #19

3 #191

#170

, #19

0 #189

Isomer distribution (P7CB, Port Island in June,2001)

KC300-600

Sea Water

Mussel

Inte

nsi

ty

#174 #180#170

Isomer distribution (O8CB, Port Island in June, 2001)

0

0.001

0.002

00.0050.01

0.0150.02

#202

#201

#197

#200

#198

#199

#196

,#2

03

#195

#194

#205

0

2000

4000

KC300-600

Sea Water

MusselInte

nsi

ty

#202 #201 #196 　　　 #203 #194#195#199

P2CB P3CB P4CB P5CB P6CB P7CB P8CB

MusselSea Water

Homologue Distribution in June,2001

0%

50%

100%

Him

eji

Kak

o rive

r

Aka

shi

Yur

a

Sei

dan

Por

t Is

land

Muk

o rive

r

Yod

o rive

r

Nan

ko

Izum

iots

u

0%

50%

100%Him

eji

Kak

o rive

r

Aka

shi

Yur

a

Sei

dan

Por

t Is

land

Muk

o rive

r

Yod

o rive

r

Nan

ko

Izum

iots

u

PCB #11

New Source

ClCl

NH2H2N

ClCl

4,4‘-Diamino-3,3’-dichlorobiphenyl＃ 11

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)

TEQ contribution of

PCDD/PCDF/PCB/PCNin

Ambient Air

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

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-

Unintentional Formation(HCB, PCN, PCB, Dioxins)

FIRE 　

1995.1.17 5:46amGreat Earthquake

(Kobe)

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

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

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/PCDF/PCB/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

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

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

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

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

Tet

ra-D

Pen

ta-D

Hex

a-D

Hep

ta-D

OC

DD

Mon

o-F

Di-F

Tri-

F

Tet

ra-F

Pen

ta-F

Hex

a-F

Hep

ta-F

OC

DF

Hudson river

(pg/g)

suspended particulate

matter (SPM)

R. Lohmann et al (1999)

Source estimation

of PCDD/DF

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

Conc. range average medium Co-PCB（ %)

Air ０～ 1.8 pg-TEQ/m3 0.22 0.15 5.7 deposition 0.2 ～ 170 pg-TEQ/m2/d 21 17 8.3 water 0 ～ 12 pg-TEQ/L 0.36 0.089 12 groundwater 0 ～ 5.3 pg-TEQ/L 0.086 0.0073 10 sediment 0 ～ 230 pg-TEQ/g 6.8 0.23 11 soil 10-3 ～ 110 pg-TEQ/g 6.2 2.3 7.7 biota 0 ～ 11 pg-TEQ/g-wet 0.64 0.32 70

Conc. range average medium Co-PCB（ %)

Air ０～ 1.8 pg-TEQ/m3 0.22 0.15 5.7 deposition 0.2 ～ 170 pg-TEQ/m2/d 21 17 8.3 water 0 ～ 12 pg-TEQ/L 0.36 0.089 12 groundwater 0 ～ 5.3 pg-TEQ/L 0.086 0.0073 10 sediment 0 ～ 230 pg-TEQ/g 6.8 0.23 11 soil 10-3 ～ 110 pg-TEQ/g 6.2 2.3 7.7 biota 0 ～ 11 pg-TEQ/g-wet 0.64 0.32 70

Env. Level (1998 survey)

Dioxin monitoring in Hyogo pref.Dioxin monitoring in Hyogo pref.

Air 30 stations, Soil 30 stationswater 20 stations, sediment 20 stations

total 250 samples in 2000Air 20 stations x 4 seasons, soil 20 stationswater 42 stations, sediment 42 stationsStack gas 44, effluent water 44

Air 30 stations, Soil 30 stationswater 20 stations, sediment 20 stations

total 250 samples in 2000Air 20 stations x 4 seasons, soil 20 stationswater 42 stations, sediment 42 stationsStack gas 44, effluent water 44