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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
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23478-PeCDF 2378-TCDD 75 135 75 209 123567-HxCN 3453’4’-Co-PCB
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PCB production World : 1,200,000t Japan : 59,000t
Harima-nada Osaka-Bay Japan Osaka Hyogo Kinki
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Map of enclosed coastal sea
Osaka Bay Harima nada Map of enclosed coastal sea
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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
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Vertical distribution
of PCB in sea sediment
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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
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Horizontal distribution
of PCB in sea sediment
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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
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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
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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
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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
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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
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Source estimation of PCB in samples
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Source estimation KC300 KC500 Insulator N.C.P. capacitor Sediment B Sediment A KC400 KC600 Insulator Ship paint capacitor
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Isomer distribution and Source estimation
Sediment A Water A KC300
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Isomer distribution and Source estimation
KC400 KC500 KC600
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Co-PCB isomer distribution and PCA
KC-300 KC-400 KC-600 KC-500 KC-600
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Co-PCB isomer ratio in environmental sample
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Co-PCB isomer ratio and Source
KC-300 flyash KC-400 Sediment A KC-500 Sediment B KC-600
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Isomer specific analysis
of PCB using GC/MS
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MCB,DiCB 5%PhMeSilicone TrCB TeCB PeCB HxCB HpCB
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Air KC-300 KC-400 KC-500 KC-600
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23478-PeCDF 2378-TCDD 75 135 75 209 123567-HxCN 3453’4’-Co-PCB
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Isomer distribution (H7CB, Port Island in June,2001)
#180 #174 #170 KC Intensity Sea Water Mussel Isomer distribution (H7CB, Port Island in June,2001)
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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)
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Isomer distribution of PCB in samples
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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-)
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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-)
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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'-)
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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
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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-)
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新たなPCBの起源
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50 KC 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'-)
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#11 4,4‘-Diamino-3,3’-dichlorobiphenyl
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Isomer distribution of PCN in samples
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PCN isomer distribution
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Contribution in TEQ value of PCDD/PCDF/PCB PCN in samples
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PCB concentration and TEQ value
KC300 KC400 KC500 KC600 0.7x10-5 2x10-5 6x10-5 3x10-5
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Ambient air Contribution in TEQ value TEQ value Total conc.
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Contribution in TEQ value
0% 20% 40% 60% 80% 100% 大気 底質 土壌 PCB PCDF PCDD Air depo sediment water soil
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Source estimation of PCDD/F in samples
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Hyogo pref Emission (g-TEQ/year) Japan Emision (g-TEQ/year)
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Homologue Distribution
River water PCDF PCDD
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Homologue Distribution
River sediment PCDF PCDD
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Homologue Distribution
River sediment Incineration pattern PCDF PCDD
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Homologue Distribution
River sediment Homologue Distribution PCP CNP Pesticide pattern PCP Pesticide pattern Incineration pattern CNP PCDD PCDF
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Homologue Distribution
Sea sediment 燃焼系 PCDD PCDF
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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, F (PCP): OCDF, F, F, F,12468-F
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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-, , , ) Pesticide(PCP) : OCDD, HpCDD( ) 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, N, (PCN product)1248-N
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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
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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)
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Precursor of PCDD/DF formation
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Precursor of PCDD/DF formation
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Authentic standard H2 ; H3 H9 H8 H6 NMR 1,4,7-TrCDF
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環境大気 Ambient air
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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)
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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)
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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)
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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)
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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)
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MCDD-TrCDD
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Map of Osaka-Bay (http://www.jhd.go.jp/)
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