PCB and PCN in Environment -Fate and Source- Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci.)...

PCB and PCNin Environment

-Fate and Source-

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

[email protected]

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


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


0.0

5.0

10.0

15.0

20.0

25.0


Kobe

On the mountain

Industrial site

0.000

0.1000.2000.3000.4000.5000.600


Homologue distribution in Ambient air

0.000

0.1000.200

0.3000.4000.5000.600


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



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


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



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



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


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


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


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


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


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


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


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


28-28-

27-27-

238-238-128-128-

237-237-2-2-

124-124-

24-24-


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


248-248- 246-246-

124-124-24-24-

24-24-


Isomer distribution of pesticide CNP (MCDF-TrCDF)

pesticide CNP

Ambient air

PCB and PCN in Environment -Fate and Source- Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci.)...

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Transcript of PCB and PCN in Environment -Fate and Source- Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci.)...