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兵庫県立公害研究所　中野　武

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. ２３４７８－ PeCDF. ２３７８－ TCDD. ７５. １３５. ７５. ２０９. １２３５６７－ HxCN. ３４５３’４’－ Co-PCB. PCB production World : 1,200,000t Japan : 59,000t. Harima-nada Osaka-Bay. Japan. Osaka. 1962-1971. Hyogo. Kinki. 1962-1971. Osaka Bay. Harima nada.

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兵庫県立公害研究所　中野　武

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  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 productionWorld : 1,200,000t Japan : 59,000t Harima-nadaOsaka-Bay Japan Osaka 1962-1971 Hyogo Kinki 1962-1971

  4. 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. 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 Channel : fast stream sand silt silt sand Central part: slow stream Particle size in sea sediment

  11. 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. 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濃度の距離減衰 PCB concentration and Distance from source

  14. Source estimation of PCB in samples

  15. Source estimation KC３００ KC５００ Insulator N.C.P. capacitor Sediment B Sediment A KC４００ KC６００ Ship paint Insulator 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. 5%PhMeSilicone MCB,DiCB 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. #180 #174 #170 KC300-600 Intensity Sea Water Mussel Isomer distribution (H7CB, Port Island in June,2001)

  26. KC300-600 Intensity Sea Water Mussel #196#203 #195 #194 #199 #202 #201 Isomer distribution (O8CB, Port Island in June, 2001)

  27. Isomer distribution of PCB in samples

  28. HW1013+KC3-600 357936 Intensity 0 14 15 16 17 18 19 Retention Time (min) Isomer distribution（TeCB） PCB product sediment 01Sed-55 68784 Intensity 0 14 15 16 17 18 19 Retention Time (min) seawater 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 0 14 15 16 17 18 19 #74(2,4,4',5-)

  29. HW1013+KC3-600 122592 Intensity 0 16 17 18 19 20 21 22 Retention Time (min) Isomer distribution （PeCB） PCB product sediment 01Sed-55 33272 Intensity 0 16 17 18 19 20 21 22 Retention Time (min) seawater Portisland7/19-6L 8520 Intensity 984 16 17 18 19 20 21 22 human milk MM-44 22336 Intensity 0 16 17 18 19 20 21 22 adipose tissue o-neck-fat 19448 Intensity 992 16 17 18 19 20 21 22 #118(2,3’,4,4',5-) #99(2,2’,4,4',5-)

  30. HW1013+KC3-600 124328 Intensity 0 18 19 20 21 22 23 24 Retention Time (min) 01Sed-55 32392 Intensity 0 18 19 20 21 22 23 24 Retention Time (min) Isomer distribution （HxCB） PCB product sediment seawater Portisland7/19-6L 5128 Intensity 992 18 19 20 21 22 23 24 human milk MM-44 47792 Intensity 0 18 19 20 21 22 23 24 adipose tissue o-neck-fat 162432 Intensity 0 18 19 20 21 22 23 24 #153(2,2',4,4',5,5'-) #138(2,2',3,4,4',5'-)

  31. HW1013+KC3-600 74056 Intensity 0 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) 01Sed-55 8744 Intensity 960 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) 20.0 20.5 21.0 21.5 22.0 22.5 Isomer distribution （HpCB） PCB product sediment seawater 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 0 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 KC300-600 40 30 20 10 0 #11 (3,3’) 60 Sediment 50 #35 (3,3’,4) 40 30 20 10 0 50 Water 40 30 20 10 0 80 70 Rain 60 50 40 30 20 10 0 40 35 Air (gas phase) 30 25 20 15 10 5 0 #4 #11 #25 #35 #37 #15 #26 #8/#5 #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/PCBPCN in samples

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

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

  41. 100% 80% 60% 40% 20% 0% 大気 底質 土壌 Contribution in TEQ value PCB PCDF PCDD water soil Air sediment depo

  42. Source estimation of PCDD/F in samples

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

  44. River water Homologue Distribution PCDF PCDD

  45. River sediment Homologue Distribution PCDF PCDD

  46. Homologue Distribution River sediment Incineration pattern PCDF PCDD

  47. 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 patternTeCDF (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, 23468-F (PCP): OCDF, 1234689-F,1234678-F, 124689-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-, 12468-, 12368-, 12379-) Pesticide(PCP) : OCDD, HpCDD(1234678-) 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, 12367-N, (PCN product)1248-N

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