1. Environmental Occurrence POPs in Environmental and Human samples Takeshi NAKANO (Hyogo Pref. Inst. of Env. Sci.) ntakeshi @ elis.pref.hyogo.jp

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

3. PCB issue in Japan

4. PCB in Japan ca 60,000t National Project in 1985-1989 Decomposition in Takasago, Hyogo pref. Liquid-PCB 5,500t 90% of PCB still remain in Environment

5. TEQ Level of technical PCB

6. PCB concentration and TEQ value KC300 KC400 KC500 KC600 ２ｘ１０ －５ 0.7 ｘ１０ －５ ６ｘ１０ －５ ３ｘ１０ －５ 0.7 ｘ１０ 7 pg-TEQ/g 2 ｘ１０ 7 6 ｘ１０ 7 3 ｘ１０ 7

7. PCB 90% of PCB still remain in Environment Transformer (Japan Railway, Power company ) Carbon free Paper (Non Carbon Paper) Sealant PCB (old building during 1968-72) Fluorescent lamp stabilizer (old type) etc

8. PCB Homologue Distribution and Source Estimation

9. Source estimation KC ３０ ０ KC ４０ ０ KC ５０ ０ KC ６０ ０ Sediment A Sediment B Ship paint N.C.P. Insulator capacitor

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

11. KC ４ 00 KC ５ 00 KC ６ 00 Isomer distribution and Source estimation

12. PCB contamination in Sea sediment PCB contamination in Sea sediment

13. 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 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

14. Vertical distribution of PCB in sea sediment

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

16. Horizontal distribution of PCB in sea sediment

18. 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 Independent area western and eastern part

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

20. 海域底質の粒度分布を考慮しない場合 Hig h Lo w Hig h 濃度の単調減少 Inmost part 鳴門 Osaka Bay coast Central part : High channel Horizontal distribution in sea sediment Harima nada Before normalization by particle size distribution

21. 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 Horizontal distribution in sea sediment

22. 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 Horizontal distribution in sea sediment Osaka bay Around Kobe port PCB concentration and Distance from source

23. PCB congener profile in Environmental and Human samples

24. Isomer distribution （ TeCB ） 141516171819 Retention Time (min) 0 68784 Intensity 01Sed-55 141516171819 1000 20656 Intensity Portisland7/19-6L 141516171819 952 14512 Intensity MM-44 141516171819 0 41200 Intensity o-neck-fat #74 (2,4,4',5-) PCB product sediment sea water human milk adipose tissue

25. Isomer distribution （ PeCB ） #99 (2,2’,4,4',5-) 16171819202122 Retention Time (min) 0 33272 Intensity 01Sed-55 16171819202122 984 8520 Intensity Portisland7/19-6L 16171819202122 0 22336 Intensity MM-44 16171819202122 992 19448 Intensity o-neck-fat #118 (2,3’,4,4',5- ) PCB product sediment sea water human milk adipose tissue

26. Isomer distribution （ HxCB ） #153 (2,2',4,4',5,5'-) 18192021222324 992 5128 Intensity Portisland7/19-6L 18192021222324 0 47792 Intensity MM-44 18192021222324 0 162432 Intensity o-neck-fat #138(2,2',3,4,4',5'-) PCB product sediment sea water human milk adipose tissue

27. Isomer distribution （ HpCB ） #187 23.023.524.024.525.025.5 984 2080 Intensity Portisland7/19-6L 20.020.521.021.522.022.523.023.524.024.525.025.5 Retention Time (min) 944 16312 Intensity MM-44 20.020.521.021.522.022.523.023.524.024.525.025.5 Retention Time (min) 0 42888 Intensity o-neck-fat #180 #170 PCB product sediment sea water human milk adipose tissue

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

29. CYP1A,CYP2 A CYP2B 4-OH 3-OH

30. Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl HO #153 (2,4,5,2',4',5') guinea pig (CYP2B18) dog (CYP2B11) human (CYP2B6) rat, hamster > PCB #153 代謝 イヌ モルモッ ト > ヒト ラット ハムス ター サル

31. POPs in Human Breast Milk

32. POPs in Human Breast Milk ng/g-fat

33. PCBs in Human Breast Milk ng/g-fat

34. PCB in Water and Mussel

35. Polychlorinated biphenyl(PCB) is well-known environmental pollutants. In Japan, approximately 58,000t of PCB was produced and imported from overseas by 1972. Despite of the ban and restriction of PCB usage since 1972, 90% of total products has still been untreated. PCB is transported in the environment(water, air, and ecosystem) in various forms.

36. Sampling Points Himeji Akashi Port Island Muko River Yodo River Nanko Izumiotsu Hokutan Yura Kako River Around Harima-nada and Osaka Bay, this investigation have been done once a month from May, 2001 to Aug, 2001

37. Japan Kinki Hyog o Osak a 1962-1971 PCB production World : 1,200,000t Japan : 59,000t 1962-1971 Harima-nada Osaka-Bay

38. Harima-nada Osaka-Bay PCB in sea sediment 10 ng/g-dry100 ng/g-dryLevel

39. The range of total PCBs concentration (May,2001~July,2001) average Harima-nada Osaka-Bay 1 ng/L 35 ng/g-wet Sea Water 5 ng/L 80 ng/g Mussel

40. The range of total co-PCBs concentration (May,2001~July,2001) average Harima-nadaOsaka-BayHarima-nadaOsaka-Bay Sea WaterMussel 0.06 ng/L0.3 ng/L 5 ng/g 2 ng/g-wet

41. Sea WaterMussel Fig #11/ΣDiCB ｓ in June, 2001

42. Isomer distribution (P 7 CB, Port Island in June,2001) KC300-600 Sea Water Mussel Intensity #174 #180 #170

43. Isomer distribution (O 8 CB, Port Island in June, 2001) KC300-600 Sea Water Mussel Intensity #202#201 #196 #203 #194#195 #199

44. P2CB P3CB P4CB P5CB P6CB P7CB P8CB MusselSea Water Homologue Distribution in June,2001

45. PCB #11 New Source

46. 4,4‘ -Diamino-3,3’-dichlorobiphenyl ＃ 11

47. PCN TEQ Level in Ambient Air

48. 0.00001 0.0001 0.001 0.01 0.1 1 012345678910 Atmospheric PCN (pg-TEQ/m 3 ) in Japan (JEPA)

49. TEQ contribution of PCDD/PCDF/PCB/PCN in Ambient Air

50. Atmospheric level of PCB/PCN/PCDD/PCDF Ambient air (pg/m 3 ) Ambient air (pg-TEQ/m 3 ) Total concentration TEQ concentration

51. Air ・ Rain Air Water ・ sediment β Selected PCN isomers from result of PCA 236- 23- 1234- 1237- 1267- 12346- 12367- 146- 137- 167-

52. Unintentional Formation (HCB, PCN, PCB, Dioxins) FIRE

53. 1995.1.17 5:46am Great Earthquake (Kobe)

54. 0 10 20 30 40 50 60 70 ng/L 6406889104 震災後 経過日数 ( 日 ) PCN(ng/L) ng/L after the earthquake disaster PCN (day) PCN concentration in rain water PCN in rain water after great fire

55. Annual inventory of Dioxin from Municipal Incinerator

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

57. TEQ contribution of PCDD/PCDF/PCB/PCN in environmental samples

58. Air depo sediment watersoil Contribution in TEQ value

59. Daily variation of PCB in ambient air

60. Air Sampling 1000m 3 High volume air sampler Quartz Micro Fiber for particulate Poly Urethane Foam for gas phase

63. Relation between distribution of gas and particulate-PCB with temperature (  C) and atmospheric pressure (hPa).

64. 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 HeptaHexaPentaTetraTri Di 3,4,3’-3,4,4’- 3,3’-4,4’- 3,4-/ 3,4’-3,4,3’,4’-

65. 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

66. 13 C 12 -MCDF 13 C 12 -OCDF 13 C 12 -HpCDF 13 C 12 -DiCDF 13 C 12 -TrCDF 13 C 12 -TeCDF 13 C 12 -PeCDF 13 C 12 -HxCDF 13 C 12 -MCDD 13 C 12 -OCDD 13 C 12 -HpCDD 13 C 12 -DiCDD 13 C 12 -TrCDD 13 C 12 -TeCDD 13 C 12 -PeCDD 13 C 12 -HxCDD Breakthrough from PUF plug using High volume air sampler

67. Water Sampling 100L High volume water sampler Quartz Micro Fiber for particulate Poly Urethane Foam for dissolved

71. ２３４７８－ PeCDF ３４５３ ’ ４ ’ － Co- PCB ２３７８－ TCDD １２３５６７－ HxCN ７５ １３５ ２０９

72. PCDD/PCDF Homologue Distribution and Source Estimation Water and Sediment in River and Coastal Sea

73. PCDD/DF in Water from Impurity of Pesticide in paddy soil PCDD/DF in Air from mainly combustion process in Japan

74. Homologue Distribution River water PCDD PCDF

75. PCDD PCDF River sediment Homologue Distribution

76. PCDD PCDF Incineration pattern Homologue Distribution River sediment

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

78. PCDD PCDF 燃焼系 Homologue Distribution Sea sediment

79. 0 20 40 60 80 M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6ClHp7Cl O8Cl (pg/L) 0 20 40 60 80 M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6ClHp7Cl O8Cl (pg/L) PCDF PCDD Kako river Homologue profiles of PCDD/Fs in river water Σ=20pg/L Σ=100pg/L

80. 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

81. PCDF PCDD Homologue profiles of PCDD/Fs in river water R. Lohmann et al (1999)

82. Source estimation of PCDD/DF

83. 環境大気 Ambient air

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

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

86. 塩素漂白パターンの異性体分布 (MCDF ～ TrCDF) 28- 23- 27- 37- 2- 238- 128- 237- 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)

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

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

89. § Conc. range average medium Co-PCB （ %) §Air ０～ 1.8 pg-TEQ/m 3 0.220.155.7 §deposition0.2 ～ 170 pg-TEQ/m 2 /d 21178.3 §water 0 ～ 12 pg-TEQ/L 0.360.08912 §groundwater 0 ～ 5.3 pg-TEQ/L 0.0860.007310 §sediment 0 ～ 230 pg-TEQ/g 6.80.2311 §soil 10 -3 ～ 110 pg-TEQ/g 6.22.37.7 §biota 0 ～ 11 pg-TEQ/g-wet 0.640.3270 § Conc. range average medium Co-PCB （ %) §Air ０～ 1.8 pg-TEQ/m 3 0.220.155.7 §deposition0.2 ～ 170 pg-TEQ/m 2 /d 21178.3 §water 0 ～ 12 pg-TEQ/L 0.360.08912 §groundwater 0 ～ 5.3 pg-TEQ/L 0.0860.007310 §sediment 0 ～ 230 pg-TEQ/g 6.80.2311 §soil 10 -3 ～ 110 pg-TEQ/g 6.22.37.7 §biota 0 ～ 11 pg-TEQ/g-wet 0.640.3270 Env. Level (1998 survey)

90. Dioxin monitoring in Hyogo pref. §Air 30 stations, Soil 30 stations §water 20 stations, sediment 20 stations §total 250 samples in 2000 §Air 20 stations x 4 seasons, soil 20 stations §water 42 stations, sediment 42 stations §Stack gas 44, effluent water 44 §Air 30 stations, Soil 30 stations §water 20 stations, sediment 20 stations §total 250 samples in 2000 §Air 20 stations x 4 seasons, soil 20 stations §water 42 stations, sediment 42 stations §Stack gas 44, effluent water 44