Environmental Occurrence POPs in Environmental and Human samples Takeshi NAKANO (Hyogo Pref. Inst. of Env. Sci.) elis.pref.hyogo.jp

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

PCB issue in Japan

PCB in Japan ca 60,000t National Project in Decomposition in Takasago, Hyogo pref. Liquid-PCB 5,500t 90% of PCB still remain in Environment

TEQ Level of technical PCB

PCB concentration and TEQ value KC300 KC400 KC500 KC600 ２ｘ１０ －５ 0.7 ｘ１０ －５ ６ｘ１０ －５ ３ｘ１０ －５ 0.7 ｘ１０ 7 pg-TEQ/g 2 ｘ１０ 7 6 ｘ１０ 7 3 ｘ１０ 7

PCB 90% of PCB still remain in Environment Transformer (Japan Railway, Power company ) Carbon free Paper (Non Carbon Paper) Sealant PCB (old building during ) Fluorescent lamp stabilizer (old type) etc

PCB Homologue Distribution and Source Estimation

Source estimation KC ３０ ０ KC ４０ ０ KC ５０ ０ KC ６０ ０ Sediment A Sediment B Ship paint N.C.P. Insulator capacitor

KC300 Isomer distribution and Source estimation Sediment A Water A

KC ４ 00 KC ５ 00 KC ６ 00 Isomer distribution and Source estimation

PCB contamination in Sea sediment PCB contamination in Sea sediment

海域底質中 PCB の鉛直分布 海域底質中 PCB の水平分布 PCB 汚染の時間的・経年変 化 PCB は汚染拡散の重要な指標 環境中で分解しない。：難分解性 使用期間 10 ～ 20 年の環境負荷 PCB 汚染の空間的移動 異性体 209 ： 情報量が多い 熱安定性 化学的 生物学的 PCB: important index for Pollutant dispersion Vertical distribution of PCB in sediment core Horizontal distribution of PCB in sediment Historical trend of PCB pollution Spatial migration of PCB 209 congeners : much information Stable in environment : persistent Environmental loading : years Thermal chemical biological

Vertical distribution of PCB in sea sediment

Production of N.C.P Annual production Sediment core PCB concentration Annual production and Vertical distribution in sediment

Horizontal distribution of PCB in sea sediment

海底の地形・水深 播磨灘 大阪湾 スープ皿のような地形 東半分：陸、西半分：海 Horizontal distribution in sea sediment Osaka Bay Harima nada Sea bottom and water depth like a soup dish Independent area western and eastern part Independent area western and eastern part

silt sand Channel : fast stream Central part: slow stream silt Horizontal distribution in sea sediment Particle size in sea sediment

海域底質の粒度分布を考慮しない場合 Hig h Lo w Hig h 濃度の単調減少 Inmost part 鳴門 Osaka Bay coast Central part : High channel Horizontal distribution in sea sediment Harima nada Before normalization by particle size distribution

海域底質の粒度分布を考慮した場合 海域底質中 PCB の水平分布 恒流図と濃度分布 粒径・微細粒子・比表面積で規格化 Constant flow map and PCB distribution After normalization by particle size distribution Horizontal distribution in sea sediment

海域底質の水平分布 大阪湾 PCB 濃度の距離減衰 神戸港周辺 Horizontal distribution in sea sediment Osaka bay Around Kobe port PCB concentration and Distance from source

PCB congener profile in Environmental and Human samples

Isomer distribution （ TeCB ） Retention Time (min) Intensity 01Sed Intensity Portisland7/19-6L Intensity MM Intensity o-neck-fat #74 (2,4,4',5-) PCB product sediment sea water human milk adipose tissue

Isomer distribution （ PeCB ） #99 (2,2’,4,4',5-) Retention Time (min) Intensity 01Sed Intensity Portisland7/19-6L Intensity MM Intensity o-neck-fat #118 (2,3’,4,4',5- ) PCB product sediment sea water human milk adipose tissue

Isomer distribution （ HxCB ） #153 (2,2',4,4',5,5'-) Intensity Portisland7/19-6L Intensity MM Intensity o-neck-fat #138(2,2',3,4,4',5'-) PCB product sediment sea water human milk adipose tissue

Isomer distribution （ HpCB ） # Intensity Portisland7/19-6L Retention Time (min) Intensity MM Retention Time (min) Intensity o-neck-fat #180 #170 PCB product sediment sea water human milk adipose tissue

human milk/adipose tissue #74 (2,4,4',5-) #74 (2,4,4',5-) #99 (2,2’,4,4',5-) #118 (2,3’,4,4',5-) #118 (2,3’,4,4',5-) #153 (2,2',4,4',5,5'-) #153 (2,2',4,4',5,5'-) #138 (2,2',3,4,4',5'-) #138 (2,2',3,4,4',5'-) #187 (2,2',3,4’,5,5’,6 -) #187 (2,2',3,4’,5,5’,6 -)

CYP1A,CYP2 A CYP2B 4-OH 3-OH

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl HO #153 (2,4,5,2',4',5') guinea pig (CYP2B18) dog (CYP2B11) human (CYP2B6) rat, hamster > PCB #153 代謝 イヌ モルモッ ト > ヒト ラット ハムス ター サル

POPs in Human Breast Milk

POPs in Human Breast Milk ng/g-fat

PCBs in Human Breast Milk ng/g-fat

PCB in Water and Mussel

Polychlorinated biphenyl(PCB) is well-known environmental pollutants. In Japan, approximately 58,000t of PCB was produced and imported from overseas by Despite of the ban and restriction of PCB usage since 1972, 90% of total products has still been untreated. PCB is transported in the environment(water, air, and ecosystem) in various forms.

Sampling Points Himeji Akashi Port Island Muko River Yodo River Nanko Izumiotsu Hokutan Yura Kako River Around Harima-nada and Osaka Bay, this investigation have been done once a month from May, 2001 to Aug, 2001

Japan Kinki Hyog o Osak a PCB production World : 1,200,000t Japan : 59,000t Harima-nada Osaka-Bay

Harima-nada Osaka-Bay PCB in sea sediment 10 ng/g-dry100 ng/g-dryLevel

The range of total PCBs concentration (May,2001~July,2001) average Harima-nada Osaka-Bay 1 ng/L 35 ng/g-wet Sea Water 5 ng/L 80 ng/g Mussel

The range of total co-PCBs concentration (May,2001~July,2001) average Harima-nadaOsaka-BayHarima-nadaOsaka-Bay Sea WaterMussel 0.06 ng/L0.3 ng/L 5 ng/g 2 ng/g-wet

Sea WaterMussel Fig #11/ΣDiCB ｓ in June, 2001

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

P2CB P3CB P4CB P5CB P6CB P7CB P8CB MusselSea Water Homologue Distribution in June,2001

PCB #11 New Source

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

PCN TEQ Level in Ambient Air

Atmospheric PCN (pg-TEQ/m 3 ) in Japan (JEPA)

TEQ contribution of PCDD/PCDF/PCB/PCN in Ambient Air

Atmospheric level of PCB/PCN/PCDD/PCDF Ambient air (pg/m 3 ) Ambient air (pg-TEQ/m 3 ) Total concentration TEQ concentration

Air ・ Rain Air Water ・ sediment β Selected PCN isomers from result of PCA

Unintentional Formation (HCB, PCN, PCB, Dioxins) FIRE

:46am Great Earthquake (Kobe)

ng/L 震災後 経過日数 ( 日 ) PCN(ng/L) ng/L after the earthquake disaster PCN (day) PCN concentration in rain water PCN in rain water after great fire

Annual inventory of Dioxin from Municipal Incinerator

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

TEQ contribution of PCDD/PCDF/PCB/PCN in environmental samples

Air depo sediment watersoil Contribution in TEQ value

Daily variation of PCB in ambient air

Air Sampling 1000m 3 High volume air sampler Quartz Micro Fiber for particulate Poly Urethane Foam for gas phase

Relation between distribution of gas and particulate-PCB with temperature (  C) and atmospheric pressure (hPa).

KC PUF QMF #11 #12/#13 #15#35#37#74#70#66 #80/#55 #56#77 #107#123#118#114#105#126#156#157#169#180#193#191#170#190#189 Co-PCB in air and technical PCB Gas phase particulate HeptaHexaPentaTetraTri Di 3,4,3’-3,4,4’- 3,3’-4,4’- 3,4-/ 3,4’-3,4,3’,4’-

Importance of Low chlorinated DD/DF formation mechanism PCB PCN PCDD PCDF MCDF >> TCDF Air, Water degradation mechanism Source estimation Monitoring of stack gas Monitoring of Environment on site analysis Isomer distribution Biodegradation pathway Important information

13 C 12 -MCDF 13 C 12 -OCDF 13 C 12 -HpCDF 13 C 12 -DiCDF 13 C 12 -TrCDF 13 C 12 -TeCDF 13 C 12 -PeCDF 13 C 12 -HxCDF 13 C 12 -MCDD 13 C 12 -OCDD 13 C 12 -HpCDD 13 C 12 -DiCDD 13 C 12 -TrCDD 13 C 12 -TeCDD 13 C 12 -PeCDD 13 C 12 -HxCDD Breakthrough from PUF plug using High volume air sampler

Water Sampling 100L High volume water sampler Quartz Micro Fiber for particulate Poly Urethane Foam for dissolved

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

PCDD/PCDF Homologue Distribution and Source Estimation Water and Sediment in River and Coastal Sea

PCDD/DF in Water from Impurity of Pesticide in paddy soil PCDD/DF in Air from mainly combustion process in Japan

Homologue Distribution River water PCDD PCDF

PCDD PCDF River sediment Homologue Distribution

PCDD PCDF Incineration pattern Homologue Distribution River sediment

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

PCDD PCDF 燃焼系 Homologue Distribution Sea sediment

M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6ClHp7Cl O8Cl (pg/L) M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6ClHp7Cl O8Cl (pg/L) PCDF PCDD Kako river Homologue profiles of PCDD/Fs in river water Σ=20pg/L Σ=100pg/L

Herbicide in the past in Japan CNP and 1379-TCDD (condensation of 2,4,6-TCP) PCP OCDD, HpCDD 2,4-D 2,7- and 2,8- DiCDD still using

PCDF PCDD Homologue profiles of PCDD/Fs in river water R. Lohmann et al (1999)

Source estimation of PCDD/DF

環境大気 Ambient air

環境大気の異性体分布 (MCDF ～ TrCDF) Ambient air Incineration (flyash) Isomer distribution of ambient air(MCDF-TrCDF)

環境大気の異性体分布 (MCDD ～ TrCDD) Isomer distribution of ambient air(MCDD-TrCDD) Incineration (flyash) Ambient air

塩素漂白パターンの異性体分布 (MCDF ～ TrCDF) TCDF 2378-TCDF 238-TrCDF 237-TrCDF 128-TrCDF 37-DiCDF 27-DiCDF 23-DiCDF 28-DiCDF Isomer distribution of bleaching process(MCDF-TrCDF)

塩素漂白パターンの異性体分布 (MCDF ～ TrCDF) 環境大気の異性体分布 (MCDF ～ TrCDF) Isomer distribution of ambient air(MCDF-TrCDF) Isomer distribution of bleaching process(MCDF-TrCDF) Ambient air

農薬 CNP 中の異性体分布 (MCDF ～ TrCDF) 環境大気の異性体分布 (MCDF ～ TrCDF) Isomer distribution of ambient air(MCDF-TrCDF) Isomer distribution of pesticide CNP (MCDF-TrCDF) pesticide CNP Ambient air

§ Conc. range average medium Co-PCB （ %) §Air ０～ 1.8 pg-TEQ/m §deposition0.2 ～ 170 pg-TEQ/m 2 /d §water 0 ～ 12 pg-TEQ/L §groundwater 0 ～ 5.3 pg-TEQ/L §sediment 0 ～ 230 pg-TEQ/g §soil ～ 110 pg-TEQ/g §biota 0 ～ 11 pg-TEQ/g-wet § Conc. range average medium Co-PCB （ %) §Air ０～ 1.8 pg-TEQ/m §deposition0.2 ～ 170 pg-TEQ/m 2 /d §water 0 ～ 12 pg-TEQ/L §groundwater 0 ～ 5.3 pg-TEQ/L §sediment 0 ～ 230 pg-TEQ/g §soil ～ 110 pg-TEQ/g §biota 0 ～ 11 pg-TEQ/g-wet Env. Level (1998 survey)

Dioxin monitoring in Hyogo pref. §Air 30 stations, Soil 30 stations §water 20 stations, sediment 20 stations §total 250 samples in 2000 §Air 20 stations x 4 seasons, soil 20 stations §water 42 stations, sediment 42 stations §Stack gas 44, effluent water 44 §Air 30 stations, Soil 30 stations §water 20 stations, sediment 20 stations §total 250 samples in 2000 §Air 20 stations x 4 seasons, soil 20 stations §water 42 stations, sediment 42 stations §Stack gas 44, effluent water 44