環境・生体試料中の PCB 異性体パターン

環境・生体試料中のPCB 異性体パターン

兵庫県立健康環境科学研究センター中野　武

2,3,4,7,8-PeCDF

3,4,5,3',4'-Co-PCB

2,3,7,8-TCDD

1,2,3,5,6,7-HxCN

75 congeners

75 congeners135 congeners

209 congeners

(t)使用量

02000400060008000

1000012000

54 55 56 57 58 59 1960 61 62 63 64 1965 66 67 68 69 1970 71 72

year

Trend of PCB Use in JapanTotal 58,000t

Amount of PCB use (t)

(1969-1971)製品別使用量

0

5,000

10,000

15,000

KC300 KC400 KC500 KC600

(t)

PCB product use in Japan

Ar-1242 1248 1254 1260

1969-1971

KC-300 400 500 600

(1969-1971)製品別使用量

0

5,000

10,000

15,000

KC300 KC400 KC500 KC600

(t)

KC300

01020

304050

M1CB

s

D2CB

s

T3CB

sT4

CBs

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

B

KC400

010

2030

4050

M1CB

s

D2CB

s

T3CB

sT4

CBs

P5CB

s

H6CB

s

H7CB

sO8

CBs

N9CB

s

D10C

B

KC500

0102030405060

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

B

KC600

0

10

2030

40

50

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

B

KC300

KC400

KC500

KC600

Japan

Japan

05

1015202530

MCBｓ

D2CB

s

T3CBs

T4CBs

P5CBs

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

B

日本

Homologue patternreflects product use

PCB

Homologue Distributionand

Source Estimation

KC300

0

10

2030

40

50

60M1

CBs

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs

KC400

05

101520253035404550

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs

KC500

05

101520253035404550

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs

KC600

05

1015202530354045

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs

(KC300 )底質由来

0102030405060

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs 05

1015202530354045

M1CB

s

D2CB

s

T3CB

s

T4CB

s

P5CB

s

H6CB

s

H7CB

s

O8CB

s

N9CB

s

D10C

Bs

(KC600 )底質由来

Source estimation

KC300

KC400

KC500

KC600

Sediment A Sediment B

Ship paint

N.C.P.

Insulator

Insulator

capacitor

capacitor

To evaluate environmental risk

Daily variation of PCDD/Fsand PCBs in ambient air

05

101520253035404550

8-1

8-2

8-3

8-4

8-5

8-6

8-7

8-8 8-9

8-10

8-

118-

128-

148-

158-

16

8-17

8-18

8-20

8-

218-

228-

238-

248-

258-

268-

278-

288-

308-

31

conc

entra

tion

(pg/

m3

)P CDFP CDD

Low- vol.PCDD+PCDF)（

Hi- vol.

Daily variation of Dioxin Concentration

Time trend of PCDD/F levels in ambient air

Time trend of PCDDs/PCDFs （ TEQ ）

0.0

0.2

0.4

0.6

0.8

1.0

1.219

8019

8119

8219

8319

8419

8519

8619

8719

8819

8919

9019

9119

9219

9319

9419

9519

9619

9719

9819

9920

0020

0120

02

PCDD

s/PC

DFs

TEQ

(pg-

TEQ/

m3 )

PCDDs/DFsTEQ

Matsumura et al, symposium of J.Env.Chem, 2003.6

Dioxin Emission Reduction Plan

0.00

0.10

0.20

0.30

0.40

0.50

0

1000

2000

3000

4000

5000

6000

7000

8000

Emission inventry (g-TEQ/year ）

PCD

Ds/

PCD

Fs（p

g-TE

Q/m

3)

1997

1998

1999

2000

2001

Emission inventry vs Level in air


0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

Co-P

CBs

TEQ

(pg-

TEQ/

m3 ) Co-PCBsTEQ


Time trend of Co-PCBs （ TEQ ）

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

Co-P

CBs

TEQ

(pg-

TEQ/

m3 ) Co-PCBsTEQ

Time trend of Co-PCBs （ TEQ ）PCB (t)

02000

400060008000

1000012000

1954

1955

1956

1957

1958

1959

1960

1961

1962

1963

1964

1965

1966

1967

1968

1969

1970

1971

1972

1973

1974

1975

1976

1977

1978

1979

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

year

PCB 使用量 (t)

PCB (t)

02000

400060008000

1000012000

1954

1955

1956

1957

1958

1959

1960

1961

1962

1963

1964

1965

1966

1967

1968

1969

1970

1971

1972

1973

1974

1975

1976

1977

1978

1979

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

year

0.01

0.1

1

10

100

1000

1970 1975 1980 1985 1990 1995 2000 20050.01

0.1

1

10

100

1000

1970 1975 1980 1985 1990 1995 2000 2005

Ambient airAmbient airPCB 濃度 (ng/m3)

Time trend of PCB levels in ambient air

(log scale)

0.01

0.1

1

10

100

1000

1970 1975 1980 1985 1990 1995 2000 2005

Time trend of PCBs concentration in ambient air (pg/m 3)Time trend of PCBs concentration in ambient air (ng/m 3)

(pg/m3)(ng/m3)

Ambient air

Time trend of PCB levels in

breast milk

Time trend of breast milk levels

Dioxins

PCB

pg TEQ/g-fat

µg g-fat

60

40

20

0 Year (1973-2000)Konishi et al. (2003)Konishi et al (2003) Organohalogen compds

pg TEQ/g-fat

µg / g-fat

Year (1973-2000)

60

40

20

0

0.3

0.2

0.1

0

Development of congener specific analysis for PCBs using HT8-PCB

Congener number number of isomer of peakmono 3 3di 12 10tri 24 23tetra 42 39penta 46 38hexa 42 40hepta 24 23octa 12 12nona 3 3deca 1 1 total 209 192

12 13 14 15 16 17 18 19 20 21 22 23Retention Time (min)

0

4000000

Inte

nsity

T3CB

Calculated Retention Time

#19

#30

#18

#17

#24

#27

#32

#16

#23

#34

#29

#26

#25

#31

#28

#21

#20

#33

#22

#36

#39

#38

#35

#37

12 13 14 15 16 17 18 19 20 21 22 23Retention Time (min)

0

Inte

nsity

13C-T3CB

Matsumura et al, J. Env. Chem. (2002)

GC/MS-SIM chromatogram of TrCB (HT8-PCB)

PCB product

13C-TrCB

20 22 24 26 28 30 32 34 36 38Retention Time (min)

0

400000

800000

Inte

nsity

P5CB

Calculated Retention Time

#104

#96

#103

#100

#94

#102

#93

#98

#95

#88

#91

#121

#92

#84

#89

#90

#101

#113

#99

#112

#119

#83

#108

#86

#117

#97

#125

#116

#87

#115

#111

#85

#120

#110

#82

#124

#109

#107

#123

#106

#118

#114

#122

#105

#127

#126

20 22 24 26 28 30 32 34 36 38Retention Time (min)

0

50000

Inte

nsity

13C-P5CB

Matsumura et al, J. Env. Chem. (2002)

GC/MS-SIM chromatogram of PeCB (HT8-PCB)

13C-PeCB

PCB product

Congener profiles of PCBsin environmental samples

01020304050

05

10152025303540

#4

#8/#

5

#11

#12/

#13

#15

#18/

#17

#16/

#32

#26

#25

#31/

#28

#33/

#20

#35

#37

0102030405060

01020304050

01020304050607080

KC300-600

Sediment

Water

Rain

Air (gas phase)

#35 (3,3’,4)#11 (3,3’)

01020304050

05

10152025303540

#4

#8/#

5

#11

#12/

#13

#15

#18/

#17

#16/

#32

#26

#25

#31/

#28

#33/

#20

#35

#37

0102030405060

01020304050

01020304050607080

KC300-600

Sediment

Water

Rain

Air (gas phase)

#35 (3,3’,4)#11 (3,3’)

Congener profiles of PCBs(Di-, Tri-) in environmental samples

Congener profiles of PCBsin environmental

and human samples

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 24Retention Time (min)

0

124328

Inte

nsity

HW1013+KC3-600

18 19 20 21 22 23 24

Retention Time (min)

0

32392In

tens

ity01Sed-55

18 19 20 21 22 23 24

992

5128

Inte

nsity

Portisland7/19-6L

18 19 20 21 22 23 24

0

47792

Inte

nsity

MM-44

18 19 20 21 22 23 24

0

162432

Inte

nsity

o-neck-fat

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

PCB productPCB product

sedimentsediment

sea watersea water

human milkhuman milk

adipose tissueadipose tissue

Congener profiles of PCBs(Hexa-) in environmental and human samples

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 25.5Retention Time (min)

0

74056

Inte

nsity

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

8744In

tens

ity01Sed-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

nsity

Portisland7/19-6L


944

16312

Inte

nsity

MM-44


0

42888

Inte

nsity

o-neck-fat

#180#180 #170#170

PCB productPCB product

sedimentsediment

sea watersea water

human milkhuman milk

adipose tissueadipose tissue

Congener profiles of PCBs(Hepta-) in environmental and human samples

Congener profiles of PCBsin human samples

(breast milk)

T4CBs

0

5

10

15

20

25

30

35

40

45

50

#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

#77

Isomers

MM44

T4CBs

0

2

4

6

8

10

12

14

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

#77

Isomers

KC3-600/MBP-CG

Isomer profiles of TeCB

PCB product

mother milk#74

#66

#74

#66#70

#52#44

#60

#60

#56

25-2525-23 25-34

245-4

24-34

234-4

23-34

245-4

P5CBs

0

5

10

15

20

25

30

35

40

45

50

#104

#96

#103

#100

#94

#102

, #93

#98,

#95

#88

#91

#121

#92

#84

#89

#90

#101

#113

#99

#112

, #11

9#8

3#1

15#8

6, #

117,

#97

#125

, #11

6#8

7, #

108

#111

#85

#120

, #11

0#8

2#1

24#1

09, #

107

#123

#106

#118

#114

#122

#105

#127

#126

Isomers

MM44

P5CBs

0

2

4

6

8

10

12

14

16

18

#104

#96

#103

#100

#94

#102

, #93

#98,

#95

#88

#91

#121

#92

#84

#89

#90

#101

#113

#99

#112

, #11

9#8

3#1

15#8

6, #

117,

#97

#125

, #11

6#8

7, #

108

#111

#85

#120

, #11

0#8

2#1

24#1

09, #

107

#123

#106

#118

#114

#122

#105

#127

#126

Isomers

KC3-600/MBP-CG

Isomer profiles of PeCB

PCB product

mother milk

#118

#118

#105

#105

#99

#99

#110#101

245-24

245-34

234-34

245-25

245-24

236-34

236-25#95

H6CBs

0

5

10

15

20

25

30

35

40

45

50

#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

, #16

3#1

38#1

60#1

58#1

29#1

66#1

59#1

28#1

62#1

67#1

56#1

57#1

69

Isomers

MM44

H6CBs

0

5

10

15

20

25

#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

, #16

3#1

38#1

60#1

58#1

29#1

66#1

59#1

28#1

62#1

67#1

56#1

57#1

69

Isomers

KC3-600/MBP-CG

Isomer profiles of HxCB

PCB product

mother milk

#153

#153

#138

#149

#138

236-245

234-245

234-245

245-245

245-245

H7CBs

0

5

10

15

20

25

30

35

40

45

#188

#184

#179

#176

#186

#178

#175

#182

, #18

7

#183

#185

#174

#181

#177

#171

#173

#172

#192

#180

#193

#191

#170

#190

#189

Isomers

MM44

H7CBs

0

5

10

15

20

25

30

#188

#184

#179

#176

#186

#178

#175

#182

, #18

7

#183

#185

#174

#181

#177

#171

#173

#172

#192

#180

#193

#191

#170

#190

#189

Isomers

KC3-600/MBP-CG

Isomer profiles of HpCB

PCB product

breast milk #180

#180

#170

#170

#187

#187 234-2345

234-2345

245-2345

245-2345245-2356

245-2356

Congener profiles of PCBsin human samples

(pooled blood)

＃ 28

＃ 31

＃ 74

＃ 80

＃ 99 ＃ 118

＃ 153

＃ 138＃ 163/＃ 164

＃ 187 ＃ 180

＃ 170

Tri-CBs

Tetra-CBs

Penta-CBs

Hexa-CBs

Hepta-CBs

Chromatogram of PCB in human blood （ 3~7Cl ）Hirai et al, (2003) Organohalogen compounds

#187 #180

#153

#138

#74

#99 #118

#28

245-2345

245-245245-234

245-34

245-2356

245-4

245-24

24-4

(n=24)

Congeners Mean ± 2S.D. Existence Ratio*(BZ#) (ng /g-lipid) (%)

#153 28.0 ± 28.0 22.3#180 14.9 ± 16.6 11.8#138 10.4 ± 9.2 8.3

#187 8.3 ± 8.5 6.6#118 6.9 ± 5.9 5.5

#163,164 6.4 ± 6.2 5.1#99 4.7 ± 4.2 3.8#74 4.6 ± 2.6 3.6

#146 4.1 ± 3.7 3.3#170 3.8 ± 4.1 3.0#156 2.8 ± 3.0 2.3Sum 75.6

* Mean is compare to total PCBs level

Levels of the predominant PCB congeners in human blood

Hirai et al, (2003) Organohalogen compounds

245-2345

2345-234

245-245

245-234

245-4

245-24

245-34245-2356

245-235

2345-34

22.334.142.449.054.559.663.467.070.373.375.6

cumulative(%)

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-)

#99 (2,2',4,4',5-)

#118 (2,3',4,4',5-)

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

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

#187(2,2',3,4',5,5',6-)

PCB congeners predominant in human samples

PCB levels and

Homologue profiles in

Environmental samples

0.01

0.1

1

10

100

1000

10000

Atmosphere

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/

m3 )

0.01

0.1

1

10

100

1000

10000

0.01

0.1

1

10

100

1000

10000

Atmosphere

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/

m3 )

0.01

0.1

1

10

100

1000

10000

100000

Water

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｌ

)

0.01

0.1

1

10

100

1000

10000

100000

0.01

0.1

1

10

100

1000

10000

100000

Water

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｌ

)0.1

1

10

100

1000

10000

100000

1000000

Sediment

aldr

in

chlo

rdan

e

DD

Ts

diel

drin en

drin

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｇ

-ｄｒｙ)

0.1

1

10

100

1000

10000

100000

1000000

0.1

1

10

100

1000

10000

100000

1000000

Sediment

aldr

in

chlo

rdan

e

DD

Ts

diel

drin en

drin

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｇ

-ｄｒｙ)

1

10

100

1000

10000

100000

1000000

Biota

aldr

in

chlo

rdan

e

DD

Tsdi

eldr

in

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/ｇ

)1

10

100

1000

10000

100000

1000000

1

10

100

1000

10000

100000

1000000

Biota

aldr

in

chlo

rdan

e

DD

Tsdi

eldr

in

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/ｇ

)

0.01

0.1

1

10

100

1000

10000

Atmosphere

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/

m3 )

0.01

0.1

1

10

100

1000

10000

0.01

0.1

1

10

100

1000

10000

Atmosphere

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/

m3 )

0.01

0.1

1

10

100

1000

10000

100000

Water

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｌ

)

0.01

0.1

1

10

100

1000

10000

100000

0.01

0.1

1

10

100

1000

10000

100000

Water

aldr

in

chlo

rdan

e

DD

Ts

diel

drin

endr

in

hept

achl

or

HC

B PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｌ

)0.1

1

10

100

1000

10000

100000

1000000

Sediment

aldr

in

chlo

rdan

e

DD

Ts

diel

drin en

drin

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｇ

-ｄｒｙ)

0.1

1

10

100

1000

10000

100000

1000000

0.1

1

10

100

1000

10000

100000

1000000

Sediment

aldr

in

chlo

rdan

e

DD

Ts

diel

drin en

drin

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%

Median

Con

cent

ratio

n(pg/ｇ

-ｄｒｙ)

1

10

100

1000

10000

100000

1000000

Biota

aldr

in

chlo

rdan

e

DD

Tsdi

eldr

in

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/ｇ

)1

10

100

1000

10000

100000

1000000

1

10

100

1000

10000

100000

1000000

Biota

aldr

in

chlo

rdan

e

DD

Tsdi

eldr

in

endr

in

hept

achl

or

HC

B

PCB

s

HC

Hs

Max

Min

75%

25%Median

Con

cent

ratio

n(pg/ｇ

)

PCB levels in air, water, sediment and biota (2002, 環境省 )

Air

Sediment

Water

Biota

0.1-10ng/m3 0.1-10ng/L

0.05-800ng/g-dry 0.1-800ng/g-wet

Homologue profiles of PCBsin human samples

PCB の同族体分布

Air

Water

Bird

Fish

Shellfish

Sediment

0

10

20

30

40

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Fish

0

10

20

30

40

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Shellfish

0

10

20

30

40

50

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Bird

0

10

20

30

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Sediment

0

10

20

30

40

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Water

0

10

20

30

40

MoCB

sDiC

Bs

TrCB

s T

eCBs

PeCB

s

HxC

BsHp

CBs

OcCB

sNo

CBs

Air

大気

水質

魚

貝類

底質鳥

0

10

20

30

40

MoCB

sDiC

BsTrC

Bs Te

CBs

PeCB

s Hx

CBs

HpCB

sOc

CBs

NoCB

s

Water

0

10

20

30

40

MoCB

sDiC

BsTrC

Bs Te

CBs

PeCB

s Hx

CBs

HpCB

sOc

CBs

NoCB

s

Air

0

10

20

30

40

50

MoCB

sDiC

BsTrC

Bs Te

CBs

PeCB

s Hx

CBs

HpCB

sOc

CBs

NoCB

s

Bird

Air

Water

Bird

ng/g-lipid

010203040506070

MCB

DiCB

TrCB

TeCB

PeCB

HxCB

HpCB

OcCB

NoCB

DeCB

05101520253035404550

abun

danc

e(%

)

Human blood

Breast milk

Congener profiles of TrCB,TeCBin human

and combustion sample (A)

02468

_19 _30 _18 _17 _32 _16 _31 _28 _22 _35 _37 _53 _51 _45_52

_69_43

_49_48

_47 _44 _64 _74 _70 _66 _79 _78 _81 _77

KC400

010203040506070

_19 _30 _18 _17 _32 _16 _31 _28 _22 _35 _37 _53 _51 _45_52

_69_43

_49_48

_47 _44 _64 _74 _70 _66 _79 _78 _81 _77

医療廃棄物

012345

_19 _30 _18 _17 _32 _16 _31 _28 _22 _35 _37 _53 _51 _45_52

_69_43

_49_48

_47 _44 _64 _74 _70 _66 _79 _78 _81 _77

母乳

PCB congeners predominant in human samples (TrCB, TeCB)

PCB product

Combustion

Breast milk

Combustion

PCB product

Breast milk

Congener profiles of TrCB,TeCBin combustion sample (B)

Compound View Page 1� � � � �DqData : C:\Documents and Settings\hyogo\My Documents\0404PCB ˆ— ƒf [ƒ^ ˆ— \DiokData\PCBN38Along-new\0404PCBN38Along-003

Injection : PCBGas-GeomeltTO-Exhaust

12 14 16 18 20 22 24 26 28 30 32Retention Time (min)

0

129564

Inte

nsity

T3CB / Average

12 14 16 18 20 22 24 26 28 30 32Retention Time (min)

0

172261

Inte

nsity

T4CB / Average

(stack gas)

TrCB

TeCB#68#51

#47

24-26

24-24

24-35

Congener profiles of PCBin human sample

0

5

10

15

77 81 105 114 118 123 126 156 157 167 169 170 180 189

ng/g-lipid

010

2030

40

#74

#66

#101

, #90

#99

#118

#105

#146

#153

#138

#167

#156

#186

, #178

#187

#183

#177

#180

#170

#199

#196

, #203

ng/g-lipid

12 DL-PCB(TEF)+di-ortho-PCB

Predominant PCB in product

Contribution of DL-PCBs in breast milk

Congener profiles of PCBin food sample

PCB congener profiles in food sample (Konishi et al )

0100200300400500

31_28 52 66 74 99 101 110 118 138 149 153 180 187

10-12_1982

0100200

300400500

31_28 52 66 74 99 101 110 118 138 149 153 180 187

10-12_20012001

1982ng/day

ng/day

Congener profiles of PCBin human sample

2000

0

10

20

30

40

50

60

70

80

90

100＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃

Figure 8. PCB congener composition in human breast milk fat mixture in 2000

＃

1973

0

10

20

30

40

50

60

70

80

90

100

110

＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃


＃

1973

2000

PCB congener composition in human breast milk


#187

#180

#153 #138

#74

#99

#118

#187 #180

#153 #138

#74 #99#118

Salmon

0102030405060708090

100

＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃

＃＃＃＃＃＃＃＃＃

＃＃＃＃

＃＃＃＃＃＃＃＃＃＃＃＃＃

＃＃＃＃

Figure 9. PCB congener composition in salmon＃

2000

0

10

20

30

40

50

60

70

80

90

100＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃＃


＃

Salmon

Breast milk


PCB congener composition in salmon

#187 #180

#153 #138

#66#101 #118

#187 #180

#153 #138

#74 #99#118

PCB product human

#74 　　 < 　 #66 #74 > #66 245-4 24-34 245-4 24-34

#99 < #101 #99 > #101245-24 245-25 245-24 245-25

#146 < #149 #146 > #149245-235 245-236 245-235 245-236

PCB metabolite OH-PCB, (OH)2-PCB

Thyroxine

4-OH-3,3',4',5-tetrachlorobiphenyl

Thyroxine & TTR binding OH-PCB

4-OH-CB-79

Thyroxine

4-OH-2,3,3',4',5-pentachlorobiphenyl

Thyroxine & TTR binding OH-PCB

4-OH-CB-107

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

OH

ClCl

Cl

Cl

Cl

4-OH-CB-107

CB-118

CB-105

4-OH-CB-146

CB-138

CB-153

OH

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

4-OH-CB-187

OH

ClCl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

CB-187

CB-183

SedimentOH-TrCB

OH-TeCB

OH-PeCB

Chromatogram of PCB-OH by methylation(Sakiyama et al. J.Env.Chem.)

OH-TrCB

OH-TeCB

OH-PeCB

Fish (Sea Bass)

4-OH-CB-107 ?

PCB metaboliteMeSO2-PCB

4-MeSO2-CB-149

Chiral metabolite

70 23/04/24

various PCB waste

capacitor reactor

waste sludge waste sludge (solid) activated carbon waste cloth

PCT

transformer stabilizer

PCB waste sludge （ outdoor ）solidified concrete ＋ asphalt pavement

soil adsorbent

Sealant containing PCB - material that is used for sealing of building- sealant of polysulfide polymer made during 1968-1972 contains PCB

glass window glass window sealant of building

joint department in buildingjoint department in floor

Homologue profiles of PCB in sealant and air龍野市庁舎シーリング材

0

10

2030

40

50

60M1

CBDi2

CB

Tr3C

BTe

4CB

Pe5C

B

Hx6C

BHp

7CB

O8CB

N9CB

De10

CB

%伊丹市庁舎シーリング材

0102030405060

M1CB

Di2CB

Tr3C

BTe

4CB

Pe5C

B

Hx6C

BHp

7CB

O8CB

N9CB

De10

CB

%

Air龍野市

0102030405060

M1CB

Di2CB

Tr3C

BTe

4CB

Pe5C

BHx

6CB

Hp7C

BO8

CBN9

CBDe

10CB

%

Air伊丹市

0102030405060

M1CB

Di2CB

Tr3C

BTe

4CB

Pe5C

BHx

6CB

Hp7C

BO8

CBN9

CBDe

10CB

%

Sealant （ Low-Cl) Sealant （ High-Cl)

Room air Room air

transformer and capacitor : 370,000stabilizer for Flu. lamp : 2,400,000non carbon paper : 644,000 kgwaste sludge : 117,000 kgwaste : 105,000,000 kgother equipments : 33,000waste PCB etc :

PCB waste stock

PCB waste stocktransformer and capacitor : 370,000stabilizer for Flu. lamp : 2,400,000non carbon paper : 644,000 kgwaste sludge : 117,000 kgwaste : 105,000,000 kgother equipments : 33,000waste PCB etc :

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

00.050.10.150.20.250.30.350.4

#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

nsit

y#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

nsity

#202 #201 #196 #203 #194#195#199

環境・生体試料中の PCB 異性体パターン

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