PCB and PCN in Environment -Fate and Source- Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci.) pref.hyogo.jp

Dr. Imagawa / Dioxin symposium in Kyoto (1994) Sudden Death of Dr. Imagawa on 19th Feb It is truly a shame to lose him at such a young age, and I thank for his help to my study

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

DD/DF/PCB Levels in Air Chemosphere (1986) Daily Variation of DD/DF/PCB Atmospheric Environment(1990) PCN in Combustion Process Organohalogen compounds (1994) PCB in Water Environment IWPRC(1990)

:46am Great Earthquake

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

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 before 1972) Fluorescent

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

PCN TEQ Level in Ambient Air

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

PCN Profiles in Ambient air

Homologue distribution of PCN in Ambient air Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 7 Cl 8

Homologue distribution of PCN in Ambient air Kobe On the mountain Industrial site

Homologue distribution in Ambient air Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 7 Cl 8 PUF M1CB D2CB Tr3CB Te4CB P5CB Hx6CBHp7CB O8CB N9CB D10CB PCN (vapor+particle) PCB(gas phase)

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

PCN Profiles in Ambient Air. (Kobe)

PCN congener distribution in ambient air. PCN # MCN 1,2 PeCN DiCN 3-12 HxCN TrCN HpCN 73,74 TeCN OCN 75 HxCNPeCNTeCNTrCNDiCN

PCN isomer distribution Air Water Technical Air Depo Rain Sediment Landfill

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

TEQ contribution of PCDD/PCDFPCB/PCN in Ambient Air

Ambient air Contribution in TEQ value TEQ value Total conc.

Annual inventory of Dioxin from Municipal Incinerator

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

TEQ contribution of PCDD/PCDFPCB/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

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

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

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

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

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

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

MCB DiCB TrCBTeCB PeCB HxCB HpCB OCB NCB DeCB (pg/L) River water PCB Homologue profiles of PCBs in river water Σ=100pg/L

M1Cl D2Cl Tr3ClTe4Cl P5Cl Hx6Cl Hp7Cl O8Cl (pg/L) Homologue profiles of PCNs in river water PCN River water Σ=20pg/L

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

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

T.NAKANO and R.WEBER Organohalogen compounds,Vol.46, (2000) ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED DIBENZO-DIOXINS AND DIBENZOFURANS -

Precursor of PCDD/DF formation

4-MCP 3,4-DCP 2,3,8-TrCDF 1,2,8-TrCDF

Synthesis of 1,4,X-T 3 CDF isomers from chlorophenol Authentic standard (1,4,7- : NMR) 2,5-DCP 4-MCP 3-MCP 2-MCP O-O- m-m- p-p- 1,4,6-TrCDF 1,4,8-TrCDF 1,4,9-TrCDF 1,4,7-TrCDF

NMR 1,4,7-TrCDF Authentic standard H9H9 H9H9 H6H6 H6H6 H8H8 H8H8 H 2 ; H 3

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