PCB and PCN

PCB and PCNFate and Source

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

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

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)

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)

Homologue distribution in Ambient air

0.000

0.1000.200

0.3000.4000.5000.600


PCN

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

PCB

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 　　

Daily variation of PCB in ambient air

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 gase 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

’-

Isomer spescific analysis

Source estimation

production 60,000t in Japan

Source Fate Sediment Ambient air

PCB

source Fate Ambient air Congener profiles

PCN

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

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

Source Fate Sediment Ambient air

PCB

source Fate Ambient air Congener profiles

PCN

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 congener distribution in ambient air.

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 isomer distribution in air, dry-deposition, rain particle, Halowax, sediment and landfil sludge.

Air　Sampling

Water　Sampling　100L

　High　volume　water　sampler

•Qurtz　Micro　Fiber　for　particulate

•Poly　Urethane　Foam　for　dissolved

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


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 isomer distribution in air, dry-deposition, rain particle, Halowax, sediment and landfil sludge.

Analytical Method of Environmental Samples

Sampling

Extraction

Cleanup

Daily Variation

L/L -> SPE

Removal Interference

MeasurementGC/MS, LC/MS

Importance of Low chlorinated DD/DF

formation mechanism

PCB PCN PCDD PCDF

MCDF > TCDF

水系、大気系

degration mechanism

origin estimation

Monitoring of stack gas

Monitoring of Environment

on site analysis

Isomer distribution

Bio degradation pathway

Important information

２３４７８－PeCDF

２３４７８－PeCDF

３４５３’４’－ Co-PCB

３４５３’４’－ Co-PCB

２３７８－ TCDD２３７８－ TCDD

１２３５６７－HxCN

１２３５６７－HxCN

７５７５

７５７５１３５１３５

２０９２０９

Air depo sediment water soil

Contribution in TEQ value

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.

Precursor of PCDD/DF formation

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

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

Annual inventory of Dioxin from Incinerator

1. Hyogo pref 2. Japan

Hyogo pref

Japan

Emision (g-TEQ/year)

Emission (g-TEQ/year)

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

PCB concentration and TEQ valuePCB concentration and TEQ value

KC300KC300 KC400KC400 KC500KC500 KC600KC600

２ｘ１０－

５

２ｘ１０－

５0.7 ｘ１０

－５

0.7 ｘ１０－５

６ｘ１０－

５

６ｘ１０－

５３ｘ１０－

５

３ｘ１０－

５

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

環境試料中のコプラナ PCBの相対比環境試料中のコプラナ PCBの相対比

KC300KC300

Isomer distribution and Source estimationIsomer distribution and Source estimation

Sediment ASediment A Water AWater A

KC ４ 00KC ４ 00 KC ５ 00KC ５ 00

KC ６ 00KC ６ 00

Isomer distribution and Source estimationIsomer distribution and Source estimation

Co-PCB in sediment and PCA

P1 　：#118,#105,#180

P2 　： #180, #170

KC-600

P3 　：#77,#105,#180

Co-PCB isomer distribution and PCA

KC-600

KC-600

KC-500

KC-400

KC-300

Co-PCB isomer ratio and Source

KC-600

KC-500

KC-400

KC-300

Sediment A

Sediment B

flyash

Co-PCB isomer ratio in environmental sample

PCDFパルプ漂白　漂白パターン　 TeCDF (2,3,7,8-, 1,2,7,8-)クロルアルカリ : PCDF (2,3,7,8-, 1,2,7,8-, 1,3,4,6,8-, 1,2,4,7,8-, 1,2,3,7,8-, 1,2,3,4,8-, 2,3,4,7,8-)燃焼起源 ( 流動床炉 ) : PCDF (2,4,6,7‐, 3,4,6,7-, 2,3,6,7-, 2,3,4,6-, 2,3,4,6,8-, 2,3,4,6,7-, 2,3,4,7,8-)農薬 (CNP) : 24-F,246-F,248-F,2468-F,12468-F, 23468-F農薬 (PCP): OCDF, 1234689-F,1234678-F, 124689-F,12468-F農薬 (24-D) : TeCDF (2,4,6,8‐)

PCDFパルプ漂白　漂白パターン　 TeCDF (2,3,7,8-, 1,2,7,8-)クロルアルカリ : PCDF (2,3,7,8-, 1,2,7,8-, 1,3,4,6,8-, 1,2,4,7,8-, 1,2,3,7,8-, 1,2,3,4,8-, 2,3,4,7,8-)燃焼起源 ( 流動床炉 ) : PCDF (2,4,6,7‐, 3,4,6,7-, 2,3,6,7-, 2,3,4,6-, 2,3,4,6,8-, 2,3,4,6,7-, 2,3,4,7,8-)農薬 (CNP) : 24-F,246-F,248-F,2468-F,12468-F, 23468-F農薬 (PCP): OCDF, 1234689-F,1234678-F, 124689-F,12468-F農薬 (24-D) : TeCDF (2,4,6,8‐)

燃焼起源燃焼起源農薬起源農薬起源

特徴的な異性体特徴的な異性体

PCB Incineration and PCB product(KC,AC)#118/#77ratio、 #77/#126 ratio

PCN Incineration and PCN product(HALOWAX)(Incineration)1267-N, 12367-N, (PCN product)1248-N

PCB Incineration and PCB product(KC,AC)#118/#77ratio、 #77/#126 ratio

PCN Incineration and PCN product(HALOWAX)(Incineration)1267-N, 12367-N, (PCN product)1248-N

PCDDIncineration(FBI) : 2,6-PeCDD(xxx68, xxx79)pattern Incineration(stoker : 2,3-PeCDD patternPesticide(CNP) : PCDD(13-,136-,138-,137-,139-, 1368-,1379-,12479-, 12468-, 12368-, 12379-)Pesticide(PCP) : OCDD, HpCDD(1234678-)Pesticide(24-D) : D2CDD (2,7- , 2,8-)

PCDDIncineration(FBI) : 2,6-PeCDD(xxx68, xxx79)pattern Incineration(stoker : 2,3-PeCDD patternPesticide(CNP) : PCDD(13-,136-,138-,137-,139-, 1368-,1379-,12479-, 12468-, 12368-, 12379-)Pesticide(PCP) : OCDD, HpCDD(1234678-)Pesticide(24-D) : D2CDD (2,7- , 2,8-)

Important Isomer for origin estimationImportant Isomer for origin estimation

quick cleanup methodsquick cleanup methods

PCDDPCDD

PCDFPCDF

PCBPCB

PCNPCN

simultaneous analysis simultaneous analysis

analysis of low chlorinated DD/DFanalysis of low chlorinated DD/DF

origin estimationorigin estimation

Isomer distributionIsomer distribution

排出源毎の特徴的分布を蓄積排出源毎の特徴的分布を蓄積

Incineration Incineration

PCB （ KC ３～６００）

PCB （ KC ３～６００）

Pesticide Pesticide

PCN （ Halowax）

PCN （ Halowax）

Homologue distributionHomologue distribution

２３４７８－TCDF

２３４７８－TCDF

３４５３’４’－ Co-PCB

３４５３’４’－ Co-PCB

２３７８－ TCDD２３７８－ TCDD

１２３５６７－HxCN

１２３５６７－HxCN

７５７５

７５７５１３５１３５

２０９２０９

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

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

NAKANO (1979)

NAKANO (1979)


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

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 ( ｆ lyash)

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 ( ｆ lyash)

Ambient air

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)



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

Detail is as follows

T.NAKANO and R.WEBER

Organohalogen compounds, (2000)

ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED

DIBENZO-DIOXINS AND DIBENZOFURANS -

TABLE II Resulting main PCDF fragments from the chlorophenols by pyrolysis at 400C

Fragment in resulting PCDF used Phenol by H-Elimination Phenol by Cl-Elimination

0 Phenol 2-C-Phenol

1 3- C-Phenol 2,3-C-Phenol




12 3,4- C-Phenol 2,3,4-C-Phenol






123 3,4,5- C-Phenol 2,3,4,5-C-Phenol

124 2,4,5- C-Phenol 2,3,4,6-C-Phenol

134 2,3,5- C-Phenol 2,3,5,6-C-Phenol

234 2,3,4- C-Phenol 2,3,4,6-C-Phenol

1234 2,3,4,5- C-Phenol 2,3,4,5,6-C-Phenol

TABLE III Sources of the PCDDs and PCDFs with 1 to 3 chlorines

No. Isomer CA registry Sources and puritynumber

MCDDs1 1 39227-53-7 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)

(b) Pyrolysis(P+23-DiCP); 2 39227-54-8 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)

(b)Cambridge Isotope Lab., USA; (c) Pyrolysis(P+24-DiCP);

DiCDDs1 12 Pyrolysis(2-CP+234-TrCP);2 13 Pyrolysis(2-CP+246-TrCP);3 14 Pyrolysis(2-CP+236-TrCP);

4 16 Pyrolysis(23-DiCP);5 17 Pyrolysis(23-DiCP+24-DiCP);6 18 Pyrolysis(23-DiCP+24-DiCP);

7 19 Pyrolysis(23-DiCP);

8 23 29446-15-9 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)(b)Cambridge Isotope Lab., USA;

9 27 33857-26-0 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)(b) Pyrolysis(24-DiCP)

10 28 38964-22-6 (a)Wellington Lab., U.S.A. ; > 98%(GC/MS)(b) Pyrolysis(24-DiCP)

TrCDDs1 123 54536-17-3 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)

(b) Pyrolysis(2-CP+2345-TeCP)2 124 39227-58-2 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)

(b)Copyrolysis(2356-TeCP+2-CP)3 126 Pyrolysis(23-DiCP+234-TrCP)4 127 Pyrolysis(24-DiCP+234-TrCP)5 128 Pyrolysis(24-DiCP+234-TrCP)6 129 Pyrolysis(23-DiCP+234-TrCP)7 136 Pyrolysis(23-DiCP+246-TrCP)8 137 67028-17-5 Pyrolysis(24-DiCP+246-TrCP) 9 138 Pyrolysis(24-DiCP+246-TrCP) 10 139 Pyrolysis(23-DiCP+246-TrCP)11 146 Pyrolysis(23-DiCP+236-TrCP)12 147 Pyrolysis(24-DiCP+236-TrCP)13 178 Pyrolysis(23-DiCP+245-TrCP)

14 237 33857-28-2 (a)AccuStandard Inc., U.S.A. ; 100%(GC/MS)(b) Cambridge Isotope Lab., USA;

(c)Pyrolysis(24-DiCP+245-TrCP) Acronyms a CDD = chlorinated dibenzo-p-dioxins ; CDF = chlorinated dibenzofurans ; CP = chlorophenols; M= mono; Di = di; Tr = tri;

0

1000

2000

3000

4000

5000

6000

7000

24 25 23 26 35 34 235

246

245

234

236

345

2356

2346

2345 PCP

246-P/ 245-P　=２

0

20

40

60

80

100

120

140

24 25 23 26 35 34 235

246

245

234

236

345

2356

2346

2345 PCP

246-P/ 245-P　=７

0

2000

4000

6000

8000

10000

12000

14000

2 1

DCDD 13

27, 23, 28

14, 17 18 16 12 19

TrCDD

137

138

136

124

139, 237 147

123

178

127

128

146

126

129

246-P/ 245-P　=２

020004000600080001000012000140001600018000

2 1

DCDD 13

27, 23, 28

14, 17 18 16 12 19

TrCDD

137

138

136

124

139, 237 147

123

178

127

128

146

126

129

246-P/ 245-P　=10

MCDD-TrCDD

NMR 1,4,7-TrCDF

Authentic standard

H9

H6H8

H2 ; H3

PCB and PCN

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