1. 環境中ダイオキシン類の
異性体分析と起源推定
兵庫県立公害研究所　中野　武

2. ２３４７８－PeCDF
２３７８－TCDD ７５
１３５ ７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB

3. PCB production World : 1,200,000t Japan : 59,000t
Harima-nada Osaka-Bay
Japan
Osaka
Hyogo
Kinki

4. Map of enclosed coastal sea
Osaka Bay
Harima nada
Map of enclosed coastal sea

5. 熱安定性
PCBは汚染拡散の重要な指標
化学的
環境中で分解しない。：難分解性
生物学的
使用期間10～20年の環境負荷
異性体 209 ： 情報量が多い
海域底質中PCBの鉛直分布
PCB汚染の時間的・経年変化
海域底質中PCBの水平分布
PCB汚染の空間的移動

6. Vertical distribution
of PCB in sea sediment

7. Annual production and Vertical distribution in sediment
Production of N.C.P
PCB concentration
Sediment core
Annual production
Annual production and Vertical distribution in sediment

8. Horizontal distribution
of PCB in sea sediment

9. Horizontal distribution in sea sediment
播磨灘
Harima nada
大阪湾
Osaka Bay
Independent area
western and eastern part
スープ皿のような地形
東半分：陸、西半分：海
like a soup dish
Sea bottom and water depth
海底の地形・水深

10. Horizontal distribution in sea sediment Particle size in sea sediment
Channel : fast stream
sand
silt
silt
sand
Central part: slow stream
Particle size in sea sediment

11. Before normalization by particle size distribution
海域底質の粒度分布を考慮しない場合
Before normalization by particle size distribution
coast
High
Inmost part
High
Low
channel
High
Harima nada
Low 鳴門
Osaka Bay
Central part : High
NAKANO (1979)
Horizontal distribution in sea sediment

12. After normalization by particle size distribution
海域底質の粒度分布を考慮した場合
After normalization by particle size distribution
Constant flow map and PCB distribution
恒流図と濃度分布
海域底質中PCBの水平分布
Horizontal distribution in sea sediment

13. Horizontal distribution in sea sediment 海域底質の水平分布
神戸港周辺
Around Kobe port
Osaka bay
大阪湾
PCB concentration and Distance from source
PCB濃度の距離減衰

14. Source estimation
of PCB in samples

15. Source estimation
KC３００
KC５００
Insulator
N.C.P.
capacitor
Sediment B
Sediment A
KC４００
KC６００
Insulator
Ship paint
capacitor

16. Isomer distribution and Source estimation
Sediment A
Water A
KC300

17. Isomer distribution and Source estimation
KC４00
KC５00
KC６00

18. Co-PCB isomer distribution and PCA
KC-300
KC-400
KC-600
KC-500
KC-600

19. Co-PCB isomer ratio in environmental sample

20. Co-PCB isomer ratio and Source
KC-300
flyash
KC-400
Sediment A
KC-500
Sediment B
KC-600

21. Isomer specific analysis
of PCB using GC/MS

22. MCB,DiCB
5%PhMeSilicone
TrCB
TeCB
PeCB
HxCB
HpCB

23. Air
KC-300
KC-400
KC-500
KC-600

24. ２３４７８－PeCDF
２３７８－TCDD ７５
１３５ ７５
２０９
１２３５６７－HxCN
３４５３’４’－Co-PCB

25. Isomer distribution (H7CB, Port Island in June,2001)
#180
#174
#170 KC
Intensity
Sea Water
Mussel
Isomer distribution (H7CB, Port Island in June,2001)

26. Isomer distribution (O8CB, Port Island in June, 2001)KC
Intensity
Sea Water
Mussel
#196　　　#203
#195
#194
#202
#201
#199
Isomer distribution (O8CB, Port Island in June, 2001)

27. Isomer distribution
of PCB in samples

28. Isomer distribution（TeCB）
PCB product 14 15 16 17 18 19
Retention Time (min)
357936
Intensity
HW1013+KC3-600
sediment
01Sed-55
68784
Intensity 14 15 16 17 18 19
Retention Time (min)
sea　water
Portisland7/19-6L
20656
Intensity
1000 14 15 16 17 18 19
human milk
MM-44
14512
Intensity
952 14 15 16 17 18 19
adipose tissue
o-neck-fat
41200
Intensity 14 15 16 17 18 19
#74　(2,4,4',5-)

29. Isomer distribution （PeCB）
PCB product 16 17 18 19 20 21 22
Retention Time (min)
122592
Intensity
HW1013+KC3-600
sediment
01Sed-55
33272
Intensity 16 17 18 19 20 21 22
Retention Time (min)
sea　water
Portisland7/19-6L
8520
Intensity
984 16 17 18 19 20 21 22
human milk
MM-44
22336
Intensity 16 17 18 19 20 21 22
adipose tissue
o-neck-fat
19448
Intensity
992 16 17 18 19 20 21 22
#99　(2,2’,4,4',5-)
#118　(2,3’,4,4',5-)

30. Isomer distribution （HxCB）
PCB product 18 19 20 21 22 23 24
Retention Time (min)
124328
Intensity
HW1013+KC3-600
sediment 18 19 20 21 22 23 24
Retention Time (min)
32392
Intensity
01Sed-55
sea　water
Portisland7/19-6L
5128
Intensity
992 18 19 20 21 22 23 24
human milk
MM-44
47792
Intensity 18 19 20 21 22 23 24
adipose tissue
o-neck-fat
162432
Intensity 18 19 20 21 22 23 24
#153 (2,2',4,4',5,5'-)
#138(2,2',3,4,4',5'-)

31. Isomer distribution （HpCB）
PCB product
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)
74056
Intensity
HW1013+KC3-600
sediment
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
Intensity
01Sed-55
sea　water
Portisland7/19-6L
2080
Intensity
984
23.0
23.5
24.0
24.5
25.0
25.5
human milk
MM-44
16312
Intensity
944
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)
adipose tissue
o-neck-fat
42888
Intensity
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)
#187
#180
#170

32. human milk/adipose tissue
#153
(2,2',4,4',5,5'-)
#74　
(2,4,4',5-)
#138
(2,2',3,4,4',5'-)
#99　(2,2’,4,4',5-)
#187
(2,2',3,4’,5,5’,6-)
#118　
(2,3’,4,4',5-)

33. 新たなPCBの起源

34. 50 KC 40 30 20 10 60
#11 (3,3’) 50
Sediment
#35 (3,3’,4) 40 30 20 10 50 40
Water 30 20 10 80 70 60
Rain 50 40 30 20 10 40 35
Air (gas phase) 30 25 20 15 10 5 #4
#8/#5
#11
#15
#26
#25
#35
#37
#12/#13
#18/#17
#16/#32
#31/#28
#33/#20
Isomer distribution of Di-TrCB in PCB product and environmental samples
#10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-),
#18(2,2',5-)/#17(2,2',4-), #16(2,2',3-)/#32(2,4',6-), #26(2,3',5-), #25(2,3',4-),
#31(2,4',5-)/#28(2,4,4'-),#33(2',3,4-)/#20(2,3,3'-),#35(3,3',4-), #37(3,4,4'-)

35. ＃11
4,4‘-Diamino-3,3’-dichlorobiphenyl

36. Isomer distribution
of PCN in samples

37. PCN isomer distribution

38. Contribution in TEQ value of PCDD/PCDF/PCB PCN in samples

39. PCB concentration and TEQ value
KC300
KC400
KC500
KC600
0.7ｘ１０－５
２ｘ１０－５
６ｘ１０－５
３ｘ１０－５

40. Ambient air
Contribution in TEQ value
TEQ value
Total conc.

41. Contribution in TEQ value0%
20%
40%
60%
80%
100% 大気 底質 土壌
PCB
PCDF
PCDD
Air
depo
sediment
water
soil

42. Source estimation
of PCDD/F in samples

43. Hyogo pref
Emission (g-TEQ/year)
Japan
Emision (g-TEQ/year)

44. Homologue Distribution
River water
PCDF
PCDD

45. Homologue Distribution
River sediment
PCDF
PCDD

46. Homologue Distribution
River sediment
Incineration pattern
PCDF
PCDD

47. Homologue Distribution
River sediment
Homologue Distribution
PCP
CNP
Pesticide pattern
PCP
Pesticide pattern
Incineration pattern
CNP
PCDD
PCDF

48. Homologue Distribution
Sea sediment
燃焼系
PCDD
PCDF

49. Incineration
Pesticide
PCDF
bleaching pattern　TeCDF (2,3,7,8-, 1,2,7,8-)
Chloralkali : 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-)
Incineration(FBI) : 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-)
Pesticide(24-D) : TeCDF (2,4,6,8‐)
(CNP) : 24-F,246-F,248-F,2468-F,12468-F, F
(PCP): OCDF, F, F, F,12468-F

50. Important Isomer for origin estimation
PCDD
Incineration(FBI) : 2,6-PeCDD(xxx68, xxx79)pattern　
Incineration(stoker : 2,3-PeCDD pattern
Pesticide(CNP) : PCDD(13-,136-,138-,137-,139-, 1368-,1379-,12479-, , , )
Pesticide(PCP) : OCDD, HpCDD( )
Pesticide(24-D) : D2CDD (2,7- , 2,8-)
PCB Incineration and PCB product(KC,AC)
#118/#77ratio、#77/#126 ratio
PCN Incineration and PCN product(HALOWAX)
(Incineration)1267-N, N, (PCN product)1248-N

51. on site analysis Monitoring of stack gas Monitoring of Environment
Importance of Low chlorinated DD/DF
Isomer distribution
formation mechanism
Bio degradation pathway
degration mechanism
Important information
origin estimation
on site analysis
Monitoring of stack gas
MCDF > TCDF
Monitoring of Environment
PCB PCN PCDD PCDF
水系、大気系

52. Organohalogen compounds, (2000)
Detail is as follows
ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED DIBENZO-DIOXINS AND DIBENZOFURANS -
T.NAKANO and R.WEBER
Organohalogen compounds, (2000)

53. Precursor of PCDD/DF formation

54. Precursor of PCDD/DF formation

55. Authentic standard
H2 ; H3 H9 H8 H6
NMR 1,4,7-TrCDF

56. 環境大気
Ambient air

57. Incineration (ｆlyash)
Ambient air
Incineration (ｆlyash)
環境大気の異性体分布(MCDF～TrCDF)
Isomer distribution of ambient air(MCDF-TrCDF)

58. Incineration (ｆlyash)
Ambient air
Incineration (ｆlyash)
環境大気の異性体分布(MCDD～TrCDD)
Isomer distribution of ambient air(MCDD-TrCDD)

59. 塩素漂白パターンの異性体分布(MCDF～TrCDF)
28- 2-
37-DiCDF
23-
27-DiCDF
27-
37-
23-DiCDF
28-DiCDF
128-TrCDF
238-
128-
237-TrCDF
238-TrCDF
237-
1278-TCDF
2378-TCDF
塩素漂白パターンの異性体分布(MCDF～TrCDF)
Isomer distribution of bleaching process(MCDF-TrCDF)

60. 塩素漂白パターンの異性体分布(MCDF～TrCDF)
238-
128- 2-
28-
237-
27-
塩素漂白パターンの異性体分布(MCDF～TrCDF)
Isomer distribution of bleaching process(MCDF-TrCDF)
Ambient air
24-
124-
Isomer distribution of ambient air(MCDF-TrCDF)
環境大気の異性体分布(MCDF～TrCDF)

61. Isomer distribution of pesticide CNP (MCDF-TrCDF)
24-
248-
246-
pesticide CNP
Ambient air
24-
124-
環境大気の異性体分布(MCDF～TrCDF)
Isomer distribution of ambient air(MCDF-TrCDF)

63. MCDD-TrCDD

64. Map of Osaka-Bay (http://www.jhd.go.jp/)