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環境・生体試料中の PCB 異性体パターン 兵庫県立健康環境科学研究センター 中野 武
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2,3,4,7,8-PeCDF 3,4,5,3',4'-Co-PCB 2,3,7,8-TCDD 1,2,3,5,6,7-HxCN 75 congeners 135 congeners 209 congeners
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Trend of PCB Use in Japan Total 58,000t Amount of PCB use (t)
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PCB product use in Japan Ar-1242 1248 1254 1260 1969-1971 KC-300 400 500 600
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KC300 KC400 KC500 KC600 Japan Homologue pattern reflects product use
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PCB Homologue Distribution and Source Estimation
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Source estimation KC300 KC400 KC500 KC600 Sediment A Sediment B Ship paint N.C.P. Insulator capacitor
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To evaluate environmental risk
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Daily variation of PCDD/Fs and PCBs in ambient air
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Daily variation of Dioxin Concentration
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Time trend of PCDD/F levels in ambient air
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Time trend of PCDDs/PCDFs ( TEQ ) Matsumura et al, symposium of J.Env.Chem, 2003.6 Dioxin Emission Reduction Plan
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0.00 0.10 0.20 0.30 0.40 0.50 0 10002000300040005000600070008000 Emission inventry (g-TEQ/year ) PCDDs/PCDFs ( pg-TEQ/m3) 1997 1998 1999 2000 2001 Emission inventry vs Level in air Matsumura et al, symposium of J.Env.Chem, 2003.6
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Time trend of Co-PCBs ( TEQ )
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PCB 使用量 (t) PCB 濃度 (ng/m 3 )
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Time trend of PCB levels in ambient air (log scale)
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Time trend of PCBs concentration in ambient air (pg/m 3 ) Time trend of PCBs concentration in ambient air (ng/m 3 ) (pg/m 3 ) (ng/m 3 ) Ambient air
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Low volume air sampler
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Time trend of PCB levels in breast milk
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Time trend of breast milk levels Dioxins PCB pg TEQ / g-fat µg g-fat 60 40 20 0 Year (1973-2000) Konishi et al. (2003) Konishi et al (2003) Organohalogen compds pg TEQ/g-fat µg / g-fat Year (1973-2000) 60 40 20 0 0.3 0.2 0.1 0
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Development of congener specific analysis for PCBs using HT8-PCB
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Congener number number of isomerof peak mono 3 3 di 12 10 tri 24 23 tetra 42 39 penta 46 38 hexa 42 40 hepta 24 23 octa 12 12 nona 3 3 deca 1 1 total 209 192
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Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of TrCB (HT8-PCB) PCB product 13 C-TrCB
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Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of PeCB (HT8-PCB) 13 C-PeCB PCB product
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Congener profiles of PCBs in environmental samples
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Congener profiles of PCBs(Di-, Tri-) in environmental samples
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Congener profiles of PCBs in environmental and human samples
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Congener profiles of PCBs(Hexa-) in environmental and human samples
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Congener profiles of PCBs(Hepta-) in environmental and human samples
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Congener profiles of PCBs in human samples (breast milk)
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Isomer profiles of TeCB PCB product mother milk #74 #66 #74 #66 #70 #52 #44 #60 #56 25-25 25-23 25-34 245-4 24-34 234-4 23-34 245-4
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Isomer profiles of PeCB PCB product mother milk #118 #105 #99 #110 #101 245-24 245-34 234-34 245-25 245-24 236-34 236-25 #95
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Isomer profiles of HxCB PCB product mother milk #153 #138 #149 #138 236-245 234-245 245-245
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Isomer profiles of HpCB PCB product breast milk #180 #170 #187 234-2345 245-2345 245-2356
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Congener profiles of PCBs in human samples (pooled blood)
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# 28 # 31 # 74 # 80 # 99 # 118 # 153 # 138 # 163/ # 164 # 187 # 180 # 170 Tri-CBs Tetra-CBs Penta-CBs Hexa-CBs Hepta-CBs Chromatogram of PCB in human blood ( 3~7Cl ) Hirai et al, (2003) Organohalogen compounds #187 #180 #153 #138 #74 #99 #118 #28 245-2345 245-245 245-234 245-34 245-2356 245-4 245-24 24-4
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(n=24) CongenersMean ± 2S.D. Existence Ratio* (BZ#)(ng /g-lipid)(%) #153 28.0 ± 22.3 #18014.9 ± 16.611.8 #13810.4 ± 9.28.3 #1878.3 ± 8.56.6 #1186.9 ± 5.95.5 #163,1646.4 ± 6.25.1 #994.7 ± 4.23.8 #744.6 ± 2.63.6 #1464.1 ± 3.73.3 #1703.8 ± 4.13.0 #1562.8 ± 3.02.3 Sum75.6 * Mean is compare to total PCBs level Levels of the predominant PCB congeners in human blood Hirai et al, (2003) Organohalogen compounds 245-2345 2345-234 245-245 245-234 245-4 245-24 245-34 245-2356 245-235 2345-34 22.3 34.1 42.4 49.0 54.5 59.6 63.4 67.0 70.3 73.3 75.6 cumulative (%)
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human milk/adipose tissue #74 (2,4,4',5-) #99 (2,2',4,4',5-) #118 (2,3',4,4',5-) #153 (2,2',4,4',5,5'-) #138 (2,2',3,4,4',5'-) #187 (2,2',3,4',5,5',6-) PCB congeners predominant in human samples
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PCB levels and Homologue profiles in Environmental samples
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PCB levels in air, water, sediment and biota (2002, 環境省 ) Air Sediment Water Biota 0.1-10ng/m 3 0.1-10ng/L 0.05-800ng/g-dry 0.1-800ng/g-wet
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Homologue profiles of PCBs in human samples
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PCB の同族体分布
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Air Water Bird Fish Shellfish Sediment 大気 水質 魚 貝類 底質 鳥
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Air Water Bird 0 5 10 15 20 25 30 35 40 45 50 abundance(%) Human blood Breast milk
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Congener profiles of TrCB,TeCB in human and combustion sample (A)
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PCB congeners predominant in human samples (TrCB, TeCB) PCB product Combustion Breast milk Combustion PCB product Breast milk
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Congener profiles of TrCB,TeCB in combustion sample (B)
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(stack gas) TrCB TeCB #68 #51 #47 24-26 24-24 24-35
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Congener profiles of PCB in human sample
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12 DL-PCB(TEF)+di-ortho-PCB Predominant PCB in product Contribution of DL-PCBs in breast milk
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Congener profiles of PCB in food sample
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PCB congener profiles in food sample (Konishi et al ) 2001 1982 ng/day
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Congener profiles of PCB in human sample
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1973 2000 PCB congener composition in human breast milk #187 #180 #153 #138 #74 #99 #118 #187 #180 #153 #138 #74 #99 #118
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Salmon Breast milk PCB congener composition in human breast milk PCB congener composition in salmon #187 #180 #153#138 #66 #101 #118 #187 #180 #153 #138 #74 #99 #118
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PCB product human #74 #66 245-4 24-34 #99 #101 245-24 245-25 #146 #149 245-235 245-236
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PCB metabolite OH-PCB, (OH) 2 -PCB
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Thyroxine 4-OH-3,3',4',5-tetrachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-79
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Thyroxine 4-OH-2,3,3',4',5-pentachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-107
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CB-118 CB-105
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4-OH-CB-146 CB-138 CB-153
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4-OH-CB-187 CB-187 CB-183
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Sediment OH-TrCB OH-TeCB OH-PeCB Chromatogram of PCB-OH by methylation (Sakiyama et al. J.Env.Chem.) OH-TrCB OH-TeCB OH-PeCB Fish (Sea Bass) 4-OH-CB-107 ?
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PCB metabolite MeSO 2 -PCB
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4-MeSO 2 -CB-149 Chiral metabolite
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various PCB waste capacitorreactor waste sludge waste sludge (solid)activated carbonwaste cloth PCT transformer stabilizer PCB waste sludge ( outdoor ) solidified concrete + asphalt pavement soil adsorbent
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Sealant containing PCB - material that is used for sealing of building - sealant of polysulfide polymer made during 1968-1972 contains PCB glass window sealant of building joint department in building joint department in floor
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Homologue profiles of PCB in sealant and air Sealant ( Low-Cl) Sealant ( High-Cl) Room air
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transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc : PCB waste stock
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transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc :
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PCB waste stock transformer and capacitor : 370,000 stabilizer for Flu. lamp : 2,400,000 non carbon paper : 644,000 kg waste sludge : 117,000 kg waste : 105,000,000 kg other equipments : 33,000 waste PCB etc :
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Isomer distribution (P 7 CB, Port Island in June,2001) KC300-600 Sea Water Mussel Intensity #174 #180 #170
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Isomer distribution (O 8 CB, Port Island in June, 2001) KC300-600 Sea Water Mussel Intensity #202#201 #196 #203#194#195 #199
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