[PPT]PCB and PCN - MS-JSWE · Web viewPCB and PCN Fate and Source Takeshi Nakano (Hyogo Pref. Inst....

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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 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

Cl1 Cl2 Cl3 Cl4 Cl5 Cl6 Cl7 Cl8

Homologue distribution of PCN in Ambient air

0.01.02.03.04.05.06.0

0.05.0

10.015.020.025.0

On the mountain

Industrial site

0.0000.1000.2000.3000.4000.5000.600

Homologue distribution in Ambient air

0.0000.1000.2000.3000.4000.5000.600

PCN (vapor+particle)

PCB(gas phase)

Homologue distribution in Ambient air

0.0000.1000.2000.3000.4000.5000.600

Atmospheric level of PCB/PCN/PCDD/PCDF

PCB PCN PCDD PCDF 0.001

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

1,4,6- (#24) 1,3,7- (#21)

Water 　　・ sediment

Selected PCN isomers from result of PCA 　　

Daily variation of PCB in ambient air

10 0 0

15 0 0

20 0 0

PC B (Q MF)PCB (P UF)T emp.

10 0 0

15 0 0

20 0 0

4 9 19

24 3 13

S ampl ing Date

10 0 0

10 1 0

10 2 0

10 3 0

10 4 0

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 .0 077

10 1 00 1 0 00 1 0 0 00

g as eous -PC B (PUF)(pg / m3)

( °C)

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 .3 315

0.1 1 10 1 00 1 000

parti cu late -PCB (Q M F)(pg / m3)

( °C)

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

Co-PCB in air and technical PCB

Gas phase

particulate

HeptaHexaPentaTetraTriDi

3,3’

4,4’

,4’-

3’,4

Isomer spescific analysis

Source estimation

production 60,000t in Japan

Source Fate Sediment Ambient air

source Fate Ambient air Congener profiles

2,3,8-

1,2,8-+

3,4-DCP 2,3,8-TrCDF

1,2,8-TrCDF

1,4,7-

1,4,9- Cl

1,4,6- Cl

1,4,8- Cl

Synthesis of 1,4,X-T3CDF isomers from chlorophenol

Authentic standard (1,4,7- : NMR)

2,5-DCP

3-MCP2-MCP

1,4,6-TrCDF

1,4,8-TrCDF

1,4,9-TrCDF

1,4,7-TrCDF

0.000.100.200.300.400.50

PUF- 1 PUF-2 PUF- 3

0.000.200.400.600.801.00

PUF- 1 PUF-2 PUF- 3

0.000.200.400.600.801.00

PUF-1 PUF-2 PUF-3

0.000.200.400.600.801.001.20

PUF-1 PUF- 2 PUF-3

2378- F

0.000.200.400.600.801.001.20

PUF- 1 PUF-2 PUF- 3

12 3 78 - F

0.000.200.400.600.801.001.20

PUF- 1 PUF- 2 PUF- 3

234 6 78 - F

0.000.100.200.300.400.50

PUF- 1 PUF-2 PUF-3

PUF- 1 PUF- 2 PUF-3

0.000.200.400.600.801.001.20

PUF-1 PUF- 2 PUF-3

0.000.200.400.600.801.001.20

PUF-1 PUF- 2 PUF- 3

2378- D

0.000.200.400.600.801.001.20

PUF- 1 PUF-2 PUF- 3

12 3 78 - D

0.000.200.400.600.801.001.20

PUF- 1 PUF-2 PUF-3

123789-D

0.000.200.400.600.801.00

PUF- 1 PUF-2 PUF-3

12346 78 - D

0.000.200.400.600.801.001.20

PUF- 1 PUF-2 PUF-3

12346789 - D

0.000.200.400.600.801.001.20

PUF-1 PUF- 2 PUF-3

12346 78 - F

0.000.200.400.600.801.001.20

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

source Fate Ambient air Congener profiles

0 39 32

0 46 31 41

/60 58 61 50 51 54 57 62

5 59 49 56

2 63 65 70

PeCN HxCN

11/8 3 10 9

4 14 15 16 17

6 13 22 23 18

DiCN TrCN

PCN congener distribution in ambient air.

11/8 3 10 9

4 15 16 17

6/13 22 23 18 42

0 46 41

0 58 61 50 51 54 57 62

5 59 49 56

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 39 32

0 46 31 41

/60 58 61 50 51 54 57 62

5 59 49 56

2 63 65 70

PeCN HxCN

11/8 3 10 9

4 14 15 16 17

6 13 22 23 18

DiCN TrCN

11/8 3 10 9

4 15 16 17

6/13 22 23 18 42

0 46 41

0 58 61 50 51 54 57 62

5 59 49 56

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

Measurement GC/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

３４５３’４’－ Co-PCB

２３７８－ TCDD

１２３５６７－HxCN

７５７５

１３５

２０９

Air depo sediment water soil

Contribution in TEQ value

Ambient air

1PCB PCN PCDD PCDF

pg-TEQ/m3

PCB PCN PCDD PCDF

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

6/1211/8 310

9 20/19

15 16 1725/26/1322

37/33/34

45/3628/43

30/27 39 32 35/48

463141

51 5457

6253/55 59

49 5666/67

64/6869 71/72

63 6570

020406080

11/8 3 10 9

4 15 16 17

6/13 22 23 18 42

3/34 44 47

7 39 32

0 46 31 41

0 58 61 50 51 54 57 62

5 59 49 56

2 63 65 70

Sediment

6/1211/8 3

10 920/19

15 16 1725/26/132223

4237/33/34

45/3628/43

30/27 39 32 35/4838/40

46 3141

5051 54

57 62 53/55 5949 5666/67

6971/72 63

020406080

HALOWAX

6/1211/83

10 9 20/19

15 16 1725/26/1322

37/33/34

45/3628/43

30/27 39 3235/48

38/4046

314152/60

6150 51 54

57 62 53/55

49 5666/6764/68

20406080

dry-depos i ti o n

6/1211/8 3

10 920/19

161725/26/13

18 4237/33/34

44 4745/3628/43

30/27 39 3235/48

463141

52/60 5861 50

5457 62 53/55

49 5666/6764/68

6971/72

63 6570

020406080

rain　particle

6/1211/8

310 9 20/19

15 16 1725/26/1322

2318 42

37/33/34

444745/3628/4330/27

39 3235/48

38/4046

314152/60

54 57 62 53/55 5949 56

64/6869

63 6570

020406080

5/76/1211/8

310 920/19

15 16 17

25/26/13

22 23 18 42

37/33/34

44 4745/3628/43

39 3235/4838/4046 3141

51 5457 6253/5559 49 56

64/6869

63 6570

020406080

PCN isomer distribution

Annual inventory of Dioxin from Incinerator

1. Hyogo pref 2. Japan

Hyogo pref

Emision (g-TEQ/year)

Emission (g-TEQ/year)

Homologue Distribution

十五社橋

020406080

100120140

River water

PCDD PCDF

脇田橋

0100200300400500600700800900

1000T4

River sediment

辰巳橋

0200400600800

10001200140016001800

PCDD PCDF

Incineration pattern

River sediment

脇田橋

0100200300400500600700800900

Pesticide pattern CNP

辰巳橋

0200400600800

10001200140016001800

PCDD PCDF

Incineration pattern

Homologue Distribution River sediment

Pesticide pattern

PCDD PCDF

燃焼系

神戸市東部沖

0200400600800

1000120014001600

Sea sediment

PCB concentration and TEQ value

KC300 KC400 KC500 KC600

２ｘ１０－

５0.7 ｘ１０

－５６ｘ１０－

５３ｘ１０－

Source estimation

KC ３００

KC ４００

KC ５００

KC ６００

Sediment A Sediment B

Ship paint

N.C.P.

Insulator

capacitor

環境試料中のコプラナ PCBの相対比

Isomer distribution and Source estimation

Sediment A Water A

KC ４ 00 KC ５ 00

KC ６ 00

Isomer 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-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‐)

燃焼起源農薬起源

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

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 estimation

quick cleanup methods

simultaneous analysis

analysis of low chlorinated DD/DF

origin estimation

Isomer distribution

排出源毎の特徴的分布を蓄積

Incineration

PCB （ KC ３～６００）

Pesticide

PCN （ Halowax）

Homologue distribution

２３４７８－TCDF

３４５３’４’－ Co-PCB

２３７８－ TCDD

１２３５６７－HxCN

７５７５

１３５

２０９

海域底質中 PCBの鉛直分布

海域底質中 PCBの水平分布

PCB 汚染の時間的・経年変化

PCBは汚染拡散の重要な指標

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

PCB汚染の空間的移動

異性体 209 ：情報量が多い

熱安定性

化学的

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

播磨灘大阪湾

スープ皿のような地形東半分：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

Channel : fast stream

Central part: slow stream

Particle size in sea sediment

海域底質の粒度分布を考慮しない場合

濃度の単調減少

Inmost part

鳴門 Osaka Bay

Central part : High

channel

NAKANO (1979)

Harima nada

Before normalization by particle size distribution

海域底質の粒度分布を考慮した場合

海域底質中 PCBの水平分布

恒流図と濃度分布

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

大阪湾

PCB濃度の距離減衰

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

13 1714

342628

136 16

環境大気Ambient air

環境大気

1 3 2 4 13 17 14 18 1612

, 24 37 27 23

8 2619

, 34 46 137

燃焼起源

1 3 2 4 13 17 14 18 1612

, 24 37 27 23

8 2619

, 34 46 137

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 1327

, 17 18 16 12 19 137

燃焼起源

2 1 1327

, 17 18 16 12 19 137

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)

0.000.100.200.300.400.500.600.70

1 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34

00.050.1

0.150.2

0.250.3

0.350.4

27-37-

1278-TCDF

2378-TCDF

238-TrCDF

237-TrCDF

128-TrCDF

37-DiCDF

27-DiCDF

23-DiCDF

28-DiCDF

Isomer distribution of bleaching process(MCDF-TrCDF)

塩素漂白パターンの異性体分布 (MCDF～TrCDF)

0.000.100.200.300.400.500.600.70

1 3 2 4 13 17 14 18 16 12 24 37 27 23 28 26 34

00.050.1

0.150.2

0.250.3

0.350.4

環境大気

1 3 2 4 13 17 14 18 1612

, 24 37 27 23

8 2619

, 34 46 137

238-128-

237-2-

Isomer distribution of bleaching process(MCDF-TrCDF)

Ambient air

1 3 2 4 13 17 14 18 16

24 37 27 23

34 46 137

147 178

236 267

農薬 CNP 中の異性体分布 (MCDF～ TrCDF)

環境大気

1 3 2 4 13 17 14 18 1612

, 24 37 27 23

8 2619

, 34 46 137

248- 246-

124-24-

Isomer distribution of pesticide CNP (MCDF-TrCDF)

pesticide CNP

Ambient air

Detail is as follows

T.NAKANO and R.WEBEROrganohalogen 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;

24 25 23 26 35 34 235

2345 PCP

246-P/ 245-P　=２

24 25 23 26 35 34 235

2345 PCP

246-P/ 245-P　=７

02000400060008000100001200014000

DCDD 13

27, 23, 28

14, 17 18 16 12 19

139, 237 147

246-P/ 245-P　=２

020004000600080001000012000140001600018000

DCDD 13

27, 23, 28

14, 17 18 16 12 19

139, 237 147

246-P/ 245-P　=10

MCDD-TrCDD

NMR 1,4,7-TrCDF

Authentic standard

H2 ; H3

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