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. 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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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

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

Trend of PCB Use in Japan Total 58,000t Amount of PCB use (t)

PCB product use in Japan Ar KC

KC300 KC400 KC500 KC600 Japan Homologue pattern reflects product use

PCB Homologue Distribution and Source Estimation

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

To evaluate environmental risk

Daily variation of PCDD/Fs and PCBs in ambient air

Daily variation of Dioxin Concentration

Time trend of PCDD/F levels in ambient air

Time trend of PCDDs/PCDFs ( TEQ ) Matsumura et al, symposium of J.Env.Chem, Dioxin Emission Reduction Plan

Emission inventry (g-TEQ/year ) PCDDs/PCDFs ( pg-TEQ/m3) Emission inventry vs Level in air Matsumura et al, symposium of J.Env.Chem,

Time trend of Co-PCBs ( TEQ )

PCB 使用量 (t) PCB 濃度 (ng/m 3 )

Time trend of PCB levels in ambient air (log scale)

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

Low volume air sampler

Time trend of PCB levels in breast milk

Time trend of breast milk levels Dioxins PCB pg TEQ / g-fat µg g-fat Year ( ) Konishi et al. (2003) Konishi et al (2003) Organohalogen compds pg TEQ/g-fat µg / g-fat Year ( )

Development of congener specific analysis for PCBs using HT8-PCB

Congener number number of isomerof peak mono 3 3 di tri tetra penta hexa hepta octa nona 3 3 deca 1 1 total

Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of TrCB (HT8-PCB) PCB product 13 C-TrCB

Matsumura et al, J. Env. Chem. (2002) GC/MS-SIM chromatogram of PeCB (HT8-PCB) 13 C-PeCB PCB product

Congener profiles of PCBs in environmental samples

Congener profiles of PCBs(Di-, Tri-) in environmental samples

Congener profiles of PCBs in environmental and human samples

Congener profiles of PCBs(Hexa-) in environmental and human samples

Congener profiles of PCBs(Hepta-) in environmental and human samples

Congener profiles of PCBs in human samples (breast milk)

Isomer profiles of TeCB PCB product mother milk #74 #66 #74 #66 #70 #52 #44 #60 #

Isomer profiles of PeCB PCB product mother milk #118 #105 #99 #110 # #95

Isomer profiles of HxCB PCB product mother milk #153 #138 #149 #

Isomer profiles of HpCB PCB product breast milk #180 #170 #

Congener profiles of PCBs in human samples (pooled blood)

# 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 #

(n=24) CongenersMean ± 2S.D. Existence Ratio* (BZ#)(ng /g-lipid)(%) # ± 22.3 # ± # ± # ± # ± #163, ± #994.7 ± #744.6 ± # ± # ± # ± Sum75.6 * Mean is compare to total PCBs level Levels of the predominant PCB congeners in human blood Hirai et al, (2003) Organohalogen compounds cumulative (%)

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

PCB levels and Homologue profiles in Environmental samples

PCB levels in air, water, sediment and biota (2002, 環境省 ) Air Sediment Water Biota ng/m ng/L ng/g-dry ng/g-wet

Homologue profiles of PCBs in human samples

PCB の同族体分布

Air Water Bird Fish Shellfish Sediment 大気 水質 魚 貝類 底質 鳥

Air Water Bird abundance(%) Human blood Breast milk

Congener profiles of TrCB,TeCB in human and combustion sample (A)

PCB congeners predominant in human samples (TrCB, TeCB) PCB product Combustion Breast milk Combustion PCB product Breast milk

Congener profiles of TrCB,TeCB in combustion sample (B)

(stack gas) TrCB TeCB #68 #51 #

Congener profiles of PCB in human sample

12 DL-PCB(TEF)+di-ortho-PCB Predominant PCB in product Contribution of DL-PCBs in breast milk

Congener profiles of PCB in food sample

PCB congener profiles in food sample (Konishi et al ) ng/day

Congener profiles of PCB in human sample

PCB congener composition in human breast milk #187 #180 #153 #138 #74 #99 #118 #187 #180 #153 #138 #74 #99 #118

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

PCB product human #74 # #99 # #146 #

PCB metabolite OH-PCB, (OH) 2 -PCB

Thyroxine 4-OH-3,3',4',5-tetrachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-79

Thyroxine 4-OH-2,3,3',4',5-pentachlorobiphenyl Thyroxine & TTR binding OH-PCB 4-OH-CB-107

CB-118 CB-105

4-OH-CB-146 CB-138 CB-153

4-OH-CB-187 CB-187 CB-183

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 ?

PCB metabolite MeSO 2 -PCB

4-MeSO 2 -CB-149 Chiral metabolite

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

Sealant containing PCB - material that is used for sealing of building - sealant of polysulfide polymer made during contains PCB glass window sealant of building joint department in building joint department in floor

Homologue profiles of PCB in sealant and air Sealant ( Low-Cl) Sealant ( High-Cl) Room air

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

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 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 :

Isomer distribution (P 7 CB, Port Island in June,2001) KC Sea Water Mussel Intensity #174 #180 #170

Isomer distribution (O 8 CB, Port Island in June, 2001) KC Sea Water Mussel Intensity #202#201 #196 #203#194#195 #199