1. 有機ハロゲン化合物による環境汚染
兵庫県立健康環境科学研究センター
中野　武

2. 2,3,4,7,8-PeCDF
2,3,7,8-TCDD
75 congeners
135 congeners
75 congeners
209 congeners
1,2,3,5,6,7-HxCN
3,4,5,3',4'-Co-PCB

3. Trend of PCB Use in Japan
Total 58,000t
Amount of PCB use (t)

4. PCB product use in Japan KC Ar

5. Homologue pattern reflects product use
KC300
Japan
KC400
Homologue pattern
reflects product use
KC500
KC600
Japan

6. Homologue Distribution
PCB
Homologue Distribution
and
Source Estimation

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

8. To evaluate environmental risk

9. Daily variation of PCDD/Fs and PCBs in ambient air

13. Daily variation of Dioxin Concentration

14. Time trend of PCDD/F levels in ambient air

15. Time trend of PCDDs/PCDFs（TEQ） Dioxin Emission Reduction Plan
Matsumura et al, symposium of J.Env.Chem,

16. Emission inventry vs Level in air
0.50
1997
0.40
1998
0.30
1999
PCDDs/PCDFs（pg-TEQ/m3)
0.20
2000
0.10
2001
0.00
8000
7000
6000
5000
4000
3000
2000
1000
Emission inventry (g-TEQ/year）
Matsumura et al, symposium of J.Env.Chem,

17. Matsumura et al, symposium of J.Env.Chem, 2003.6
Time trend of Co-PCBs（TEQ）
Matsumura et al, symposium of J.Env.Chem,

18. Time trend of Co-PCBs（TEQ）

19. PCB 使用量(t)
PCB 濃度(ng/m3)

20. Time trend of PCB levels in ambient air (log scale)

21. Ambient air ( ng/m ) ( pg/m )3 ) (
pg/m 3 )
0.01
0.1 1 10
100
1000
1970
1975
1980
1985
1990
1995
2000
2005
Time trend of PCBs concentration in ambient air (ng/m 3 3 )
Time trend of PCBs concentration in ambient air (pg/m )

22. Low volume air sampler

23. Time trend of PCB levels in breast milk

24. Time trend of breast milk levels
µg / g-fat
µg g-fat
0.3
0.2
0.1
PCB 60 40 20 60 40 20
pg TEQ/g-fat
pg TEQ/g-fat
Dioxins
Year ( )
Year ( )
Konishi et al. (2003)
Konishi et al (2003) Organohalogen compds

25. Development of congener specific analysis for PCBs using HT8-PCB

26. Congener number number of isomer of peak mono di tri tetra penta hexa hepta octa nona deca total

27. PCB product 13C-TrCB GC/MS-SIM chromatogram of TrCB (HT8-PCB)
Matsumura et al, J. Env. Chem. (2002)

28. PCB product 13C-PeCB GC/MS-SIM chromatogram of PeCB (HT8-PCB)20 22 24 26 28 30 32 34 36 38
Retention Time (min)
400000
800000
Intensity
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
50000
13C-P5CB
PCB product
13C-PeCB
Matsumura et al, J. Env. Chem. (2002)

29. Congener profiles of PCBs in environmental samples

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

31. Congener profiles of PCBs in environmental and human samples

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

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

34. Congener profiles of PCBs in human samples (breast milk)

35. Isomer profiles of TeCB
#70
PCB product
#66
25-25
25-34
25-23
#52
#44
245-4
23-34
#74
#56
#60
245-4
mother milk
#74
24-34
#66
234-4
#60
Isomer profiles of TeCB

36. Isomer profiles of PeCB
245-25
236-34
#101
PCB product
236-25
#110
#118
#95
245-24
#105
#99
245-34
mother milk
#118
245-24
#99
234-34
#105
Isomer profiles of PeCB

37. Isomer profiles of HxCB
#153
PCB product
#149
#138
#153
mother milk
#138
Isomer profiles of HxCB

38. Isomer profiles of HpCB
#180
PCB product
#187
#170
#180
breast milk
#187
#170
Isomer profiles of HpCB

39. Congener profiles of PCBs in human samples (pooled blood)

40. Hirai et al, (2003) Organohalogen compounds
#28
Tri-CBs
＃28
24-4
＃31
Tetra-CBs
＃74
#74
245-4
＃80
Penta-CBs
#99
245-34
＃118
#118
＃99
245-24
Hexa-CBs
＃153
#153
#138
＃163/
＃164
＃138
Hepta-CBs
#187
＃187
＃180
#180
＃170
Chromatogram of PCB in human blood （3~7Cl）
Hirai et al, (2003) Organohalogen compounds

41. Hirai et al, (2003) Organohalogen compounds
Levels of the predominant PCB congeners in human blood
(n=24)
Congeners
Mean
2S.D.
Existence Ratio*
(BZ#)
(ng /g-lipid)
(%)
#153
28.0
22.3
#180
14.9
16.6
11.8
#138
10.4
9.2
8.3
#187
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
3.0
#156
2.8
2.3
Sum
75.6 *
Mean is compare to total PCBs level
cumulative
(%)
22.3
34.1
42.4
49.0
54.5
59.6
63.4
67.0
70.3
73.3
75.6
245-34
245-24
245-4
Hirai et al, (2003) Organohalogen compounds

42. PCB congeners predominant in human samples
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-)
PCB congeners predominant in human samples

43. PCB levels and Homologue profiles in Environmental samples

44. PCB levels in air, water, sediment and biota (2002, 環境省)
0.1-10ng/m3
0.1-10ng/L
Air
Water
Sediment
Biota
ng/g-wet
ng/g-dry
PCB levels in air, water, sediment and biota (2002, 環境省)

45. Homologue profiles of PCBs in human samples

46. PCBの同族体分布

47. Fish Air 魚 大気 Water 貝類 水質 Bird 底質 鳥
Shellfish
Water 貝類 水質
Sediment
Bird 底質 鳥

48. Air Human blood Water Breast milk Bird5 10 15 20 25 30 35 40 45 50
abundance(%)
Air
Human blood
Water
Breast milk
Bird

49. Congener profiles of TrCB,TeCB in human and combustion sample (A)

50. PCB congeners predominant in human samples (TrCB, TeCB)
PCB product
PCB product
Combustion
Combustion
Breast milk
Breast milk
PCB congeners predominant in human samples (TrCB, TeCB)

51. Congener profiles of TrCB,TeCB in combustion sample (B)

52. (stack gas)
#47
TrCB
24-24
#68
#51
TeCB
24-35
24-26

53. Congener profiles of PCB in human sample

54. 12 DL-PCB(TEF)+di-ortho-PCB
Predominant PCB in product
Contribution of DL-PCBs in breast milk

55. Congener profiles of PCB in food sample

56. PCB congener profiles in food sample (Konishi et al )
ng/day
1982
ng/day
2001
PCB congener profiles in food sample (Konishi et al )

57. Congener profiles of PCB in human sample

58. PCB congener composition in human breast milk
#153
#138
#118
#74
#99
#180
1973
#187
PCB congener composition in human breast milk
#153
#138
2000
#180
#118
#187
#74
#99
PCB congener composition in human breast milk

59. PCB congener composition in salmon
#153
#138
#118
#101
Salmon
#66
#180
#187
PCB congener composition in salmon
#153
#138
Breast milk
#180
#118
#187
#74
#99
PCB congener composition in human breast milk

60. PCB product human
#74　　<　 # #74 > #66
# < # #99 > #101
# < # #146 > #149

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

62. 4-OH-3,3',4',5-tetrachlorobiphenyl Thyroxine & TTR binding OH-PCB
4-OH-CB-79
Thyroxine & TTR binding OH-PCB

63. 4-OH-2,3,3',4',5-pentachlorobiphenyl Thyroxine & TTR binding OH-PCB
4-OH-CB-107
Thyroxine & TTR binding OH-PCB

64. CB-105
4-OH-CB-107
CB-118

65. CB-138
4-OH-CB-146
CB-153

66. CB-183
4-OH-CB-187
CB-187

67. Chromatogram of PCB-OH by methylation (Sakiyama et al. J.Env.Chem.)
Fish (Sea Bass)
OH-TrCB
OH-TeCB
4-OH-CB-107 ?
OH-PeCB
Sediment
OH-TrCB
OH-TeCB
OH-PeCB
Chromatogram of PCB-OH by methylation
(Sakiyama et al. J.Env.Chem.)

68. PCB metabolite
MeSO2-PCB

69. 4-MeSO2-CB-149
Chiral metabolite

70. various PCB waste capacitor reactor stabilizer transformer
waste sludge
waste sludge (solid)
activated carbon
waste cloth
soil adsorbent
PCT
PCB waste sludge（outdoor）
solidified concrete ＋asphalt pavement

71. Sealant containing PCB
- material that is used for sealing of building
- sealant of polysulfide polymer made during contains PCB
glass window
glass window
sealant of building
joint department in floor
joint department in building

72. Homologue profiles of PCB in sealant and air
Sealant （Low-Cl)
Sealant （High-Cl)
Room air
Room air

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

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

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

76. Isomer distribution (P7CB, Port Island in June,2001)
#180
#174
#170 KC
Intensity
Sea Water
Mussel
Isomer distribution (P7CB, Port Island in June,2001)

77. 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)