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

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

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

Vertical distribution of PCB in sea sediment

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

Horizontal distribution of PCB in sea sediment

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

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

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

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

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

Source estimation of PCB in samples

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

Isomer distribution and Source estimation Sediment A Water A KC300

Isomer distribution and Source estimation KC４00 KC５00 KC６00

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

Co-PCB isomer ratio in environmental sample

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

Isomer specific analysis of PCB using GC/MS

MCB,DiCB 5%PhMeSilicone TrCB TeCB PeCB HxCB HpCB

Air KC-300 KC-400 KC-500 KC-600

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

Isomer distribution (H7CB, Port Island in June,2001) #180 #174 #170 KC300-600 Intensity Sea Water Mussel Isomer distribution (H7CB, Port Island in June,2001)

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

Isomer distribution of PCB in samples

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-)

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-)

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'-)

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

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-)

新たなPCBの起源

50 KC300-600 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'-)

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

Isomer distribution of PCN in samples

PCN isomer distribution

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

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

Ambient air Contribution in TEQ value TEQ value Total conc.

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

Source estimation of PCDD/F in samples

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

Homologue Distribution River water PCDF PCDD

Homologue Distribution River sediment PCDF PCDD

Homologue Distribution River sediment Incineration pattern PCDF PCDD

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

Homologue Distribution Sea sediment 燃焼系 PCDD PCDF

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, 23468-F (PCP): OCDF, 1234689-F,1234678-F, 124689-F,12468-F

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

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

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)

Precursor of PCDD/DF formation

Precursor of PCDD/DF formation

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

環境大気 Ambient air

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)

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)

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)

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)

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)

MCDD-TrCDD

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