1. PCB and PCN in Environment -Fate and Source- Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci.) ntakeshi @ pref.hyogo.jp

2. Dr. Imagawa / Dioxin symposium in Kyoto (1994) Sudden Death of Dr. Imagawa on 19th Feb. 2001 It is truly a shame to lose him at such a young age, and I thank for his help to my study

3. ２３４７８－ PeCDF ３４５３ ’ ４ ’ － Co- PCB ２３７８－ TCDD １２３５６７－ HxCN ７５ １３５ ２０９

4. PCB issue in Japan

5. 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

6. DD/DF/PCB Levels in Air Chemosphere (1986) Daily Variation of DD/DF/PCB Atmospheric Environment(1990) PCN in Combustion Process Organohalogen compounds (1994) PCB in Water Environment IWPRC(1990)

7. 1995.1.17 5:46am Great Earthquake

8. 0 10 20 30 40 50 60 70 ng/L 6406889104 震災後 経過日数 ( 日 ) PCN(ng/L) ng/L The progress number of days after the earthquake disaster PCN (day) PCN concentration in rain water PCN in rain water after great fire

10. TEQ Level of technical PCB

11. 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

12. PCB 90% of PCB still remain in Environment Transformer (Japan Railway, Power company ) Carbon free Paper (Non Carbon Paper) Sealant PCB (old building before 1972) Fluorescent

13. PCB Homologue Distribution and Source Estimation

14. 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

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

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

17. PCN TEQ Level in Ambient Air

18. 0.00001 0.0001 0.001 0.01 0.1 1 012345678910 Atmospheric PCN (pg-TEQ/m 3 ) in Japan (JEPA)

19. PCN Profiles in Ambient air

20. Homologue distribution of PCN in Ambient air 0.000 0.100 0.200 0.300 0.400 0.500 0.600 Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 7 Cl 8

21. Homologue distribution of PCN in Ambient air Kobe On the mountain Industrial site

22. Homologue distribution in Ambient air 0.000 0.100 0.200 0.300 0.400 0.500 0.600 Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 7 Cl 8 PUF 0 10 20 30 40 50 M1CB D2CB Tr3CB Te4CB P5CB Hx6CBHp7CB O8CB N9CB D10CB PCN (vapor+particle) PCB(gas phase)

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

24. PCN Profiles in Ambient Air. (Kobe)

25. PCN congener distribution in ambient air. PCN # MCN 1,2 PeCN 49-62 DiCN 3-12 HxCN 63-72 TrCN 13-26 HpCN 73,74 TeCN 27-48 OCN 75 HxCNPeCNTeCNTrCNDiCN

26. PCN isomer distribution Air Water Technical Air Depo Rain Sediment Landfill

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

28. TEQ contribution of PCDD/PCDFPCB/PCN in Ambient Air

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

30. Annual inventory of Dioxin from Municipal Incinerator

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

32. TEQ contribution of PCDD/PCDFPCB/PCN in environmental samples

33. Air depo sediment watersoil Contribution in TEQ value

34. Daily variation of PCB in ambient air

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

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

43. 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’-

44. 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

45. 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

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

50. ２３４７８－ PeCDF ３４５３ ’ ４ ’ － Co- PCB ２３７８－ TCDD １２３５６７－ HxCN ７５ １３５ ２０９

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

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

53. 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

54. Homologue Distribution River water PCDD PCDF

55. PCDD PCDF River sediment Homologue Distribution

56. PCDD PCDF Incineration pattern Homologue Distribution River sediment

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

58. PCDD PCDF 燃焼系 Homologue Distribution Sea sediment

59. 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

60. 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

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

62. 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

63. 0 10 20 30 MCB DiCB TrCBTeCB PeCB HxCB HpCB OCB NCB DeCB (pg/L) River water PCB Homologue profiles of PCBs in river water Σ=100pg/L

64. 0 1 2 3 4 5 6 7 M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6Cl Hp7Cl O8Cl (pg/L) Homologue profiles of PCNs in river water PCN River water Σ=20pg/L

65. PCB contamination in Sea sediment PCB contamination in Sea sediment

66. 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

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

69. 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

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

71. 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

72. 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

73. 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

74. T.NAKANO and R.WEBER Organohalogen compounds,Vol.46, 558-561 (2000) ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED DIBENZO-DIOXINS AND DIBENZOFURANS -

75. Precursor of PCDD/DF formation

76. 4-MCP 3,4-DCP 2,3,8-TrCDF 1,2,8-TrCDF

77. Synthesis of 1,4,X-T 3 CDF isomers from chlorophenol Authentic standard (1,4,7- : NMR) 2,5-DCP 4-MCP 3-MCP 2-MCP O-O- m-m- p-p- 1,4,6-TrCDF 1,4,8-TrCDF 1,4,9-TrCDF 1,4,7-TrCDF

78. NMR 1,4,7-TrCDF Authentic standard H9H9 H9H9 H6H6 H6H6 H8H8 H8H8 H 2 ; H 3

79. 環境大気 Ambient air

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

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

82. 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)

83. 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

84. 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