有機ハロゲン化合物による環境汚染 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 2,3,7,8-TCDD 75 congeners 135 congeners 75 congeners 209 congeners 1,2,3,5,6,7-HxCN 3,4,5,3',4'-Co-PCB

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

PCB product use in Japan 1969-1971 KC-300 400 500 600 Ar-1242 1248 1254 1260

Homologue pattern reflects product use KC300 Japan KC400 Homologue pattern reflects product use KC500 KC600 Japan

Homologue Distribution PCB Homologue Distribution and Source Estimation

Source estimation KC300 KC500 Insulator N.C.P. capacitor Sediment A Sediment B KC400 KC600 Insulator Ship paint 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） Dioxin Emission Reduction Plan Matsumura et al, symposium of J.Env.Chem, 2003.6

Emission inventry vs Level in air 0.50 1997 0.40 1998 0.30 1999 PCDDs/PCDFs（pg-TEQ/m3) 0.20 2000 0.10 2001 0.00 8000 7000 6000 5000 4000 3000 2000 1000 Emission inventry (g-TEQ/year） Matsumura et al, symposium of J.Env.Chem, 2003.6

Matsumura et al, symposium of J.Env.Chem, 2003.6 Time trend of Co-PCBs（TEQ） Matsumura et al, symposium of J.Env.Chem, 2003.6

Time trend of Co-PCBs（TEQ）

PCB 使用量(t) PCB 濃度(ng/m3)

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

Ambient air ( ng/m ) ( pg/m ) 3 ) ( pg/m 3 ) 0.01 0.1 1 10 100 1000 1970 1975 1980 1985 1990 1995 2000 2005 Time trend of PCBs concentration in ambient air (ng/m 3 3 ) Time trend of PCBs concentration in ambient air (pg/m )

Low volume air sampler

Time trend of PCB levels in breast milk

Time trend of breast milk levels µg / g-fat µg g-fat 0.3 0.2 0.1 PCB 60 40 20 60 40 20 pg TEQ/g-fat pg TEQ/g-fat Dioxins Year (1973-2000) Year (1973-2000) Konishi et al. (2003) Konishi et al (2003) Organohalogen compds

Development of congener specific analysis for PCBs using HT8-PCB

Congener number number of isomer of 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

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

PCB product 13C-PeCB GC/MS-SIM chromatogram of PeCB (HT8-PCB) 20 22 24 26 28 30 32 34 36 38 Retention Time (min) 400000 800000 Intensity P5CB Calculated Retention Time #104 #96 #103 #100 #94 #102 #93 #98 #95 #88 #91 #121 #92 #84 #89 #90 #101 #113 #99 #112 #119 #83 #108 #86 #117 #97 #125 #116 #87 #115 #111 #85 #120 #110 #82 #124 #109 #107 #123 #106 #118 #114 #122 #105 #127 #126 50000 13C-P5CB PCB product 13C-PeCB Matsumura et al, J. Env. Chem. (2002)

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 #70 PCB product #66 25-25 25-34 25-23 #52 #44 245-4 23-34 #74 #56 #60 245-4 mother milk #74 24-34 #66 234-4 #60 Isomer profiles of TeCB

Isomer profiles of PeCB 245-25 236-34 #101 PCB product 236-25 #110 #118 #95 245-24 #105 #99 245-34 mother milk #118 245-24 #99 234-34 #105 Isomer profiles of PeCB

Isomer profiles of HxCB #153 236-245 PCB product 245-245 #149 234-245 #138 #153 mother milk 245-245 234-245 #138 Isomer profiles of HxCB

Isomer profiles of HpCB #180 PCB product 245-2345 245-2356 #187 234-2345 #170 #180 breast milk 245-2345 245-2356 #187 234-2345 #170 Isomer profiles of HpCB

Congener profiles of PCBs in human samples (pooled blood)

Hirai et al, (2003) Organohalogen compounds #28 Tri-CBs ＃28 24-4 ＃31 Tetra-CBs ＃74 #74 245-4 ＃80 Penta-CBs #99 245-34 ＃118 #118 ＃99 245-24 Hexa-CBs ＃153 #153 245-234 245-245 #138 ＃163/ ＃164 ＃138 Hepta-CBs #187 ＃187 245-2345 ＃180 #180 245-2356 ＃170 Chromatogram of PCB in human blood （3~7Cl） Hirai et al, (2003) Organohalogen compounds

Hirai et al, (2003) Organohalogen compounds Levels of the predominant PCB congeners in human blood (n=24) Congeners Mean ± 2S.D. Existence Ratio* (BZ#) (ng /g-lipid) (%) #153 28.0 22.3 #180 14.9 16.6 11.8 #138 10.4 9.2 8.3 #187 8.5 6.6 #118 6.9 5.9 5.5 #163,164 6.4 6.2 5.1 #99 4.7 4.2 3.8 #74 4.6 2.6 3.6 #146 4.1 3.7 3.3 #170 3.0 #156 2.8 2.3 Sum 75.6 * Mean is compare to total PCBs level cumulative (%) 22.3 34.1 42.4 49.0 54.5 59.6 63.4 67.0 70.3 73.3 75.6 245-245 245-2345 245-234 245-2356 245-34 245-24 245-4 245-235 2345-234 2345-34 Hirai et al, (2003) Organohalogen compounds

PCB congeners predominant in human samples 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-) 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) 0.1-10ng/m3 0.1-10ng/L Air Water Sediment Biota 0.1-800ng/g-wet 0.05-800ng/g-dry PCB levels in air, water, sediment and biota (2002, 環境省)

Homologue profiles of PCBs in human samples

PCBの同族体分布

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

Air Human blood Water Breast milk Bird 5 10 15 20 25 30 35 40 45 50 abundance(%) Air Human blood Water Breast milk Bird

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

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

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

(stack gas) #47 TrCB 24-24 #68 #51 TeCB 24-35 24-26

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 1982 ng/day 2001 PCB congener profiles in food sample (Konishi et al )

Congener profiles of PCB in human sample

PCB congener composition in human breast milk #153 #138 #118 #74 #99 #180 1973 #187 PCB congener composition in human breast milk #153 #138 2000 #180 #118 #187 #74 #99 PCB congener composition in human breast milk

PCB congener composition in salmon #153 #138 #118 #101 Salmon #66 #180 #187 PCB congener composition in salmon #153 #138 Breast milk #180 #118 #187 #74 #99 PCB congener composition in human breast milk

PCB product human #74　　<　 #66 #74 > #66 245-4 24-34 245-4 24-34 #99 < #101 #99 > #101 245-24 245-25 245-24 245-25 #146 < #149 #146 > #149 245-235 245-236 245-235 245-236

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

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

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

CB-105 4-OH-CB-107 CB-118

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

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

Chromatogram of PCB-OH by methylation (Sakiyama et al. J.Env.Chem.) Fish (Sea Bass) OH-TrCB OH-TeCB 4-OH-CB-107 ? OH-PeCB Sediment OH-TrCB OH-TeCB OH-PeCB Chromatogram of PCB-OH by methylation (Sakiyama et al. J.Env.Chem.)

PCB metabolite MeSO2-PCB

4-MeSO2-CB-149 Chiral metabolite

various PCB waste capacitor reactor stabilizer transformer waste sludge waste sludge (solid) activated carbon waste cloth soil adsorbent PCT PCB waste sludge（outdoor） solidified concrete ＋asphalt pavement

Sealant containing PCB - material that is used for sealing of building - sealant of polysulfide polymer made during 1968-1972 contains PCB glass window glass window sealant of building joint department in floor joint department in building

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

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 :

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 (P7CB, Port Island in June,2001) #180 #174 #170 KC300-600 Intensity Sea Water Mussel Isomer distribution (P7CB, 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)