March 10 (Mon) 2008, Bangkok Dr. Shigeo FUJII , Professor Graduate School of Global Environmental Studies, Kyoto University Today’s Contents 1. 1. Introduction (POPs Problem) Introduction (POPs Problem) 2. 2. Perfluorinated Perfluorinated Compounds (PFCs) Compounds (PFCs) 3. 3. World Distribution World Distribution 4. 4. Their Sources and Effects of WTPs Their Sources and Effects of WTPs 5. 5. Countermeasures and Future Countermeasures and Future 1 Shigeo Fujii, JST-Bangkok, March 10 2008
POPs Problem Introduction (POPs problem) Perfluorinated compounds (PFCs) World distribution Their sources and effects of WTPs Countermeasures and future Persistent Organic Pollutants (POPs): Chemical substances that persist in the environment, bioaccumulate through the food web, and pose a risk of causing adverse effects to human health and the environment. < UNEP> http:/ / www.chem.unep.ch/ pops/ Three Key Properties: > Persistency : never be reduced naturally (in biological and photolysis processes) > Bioaccumulation : low concentration in discharge � high concentration in organisms > Risk : effects caused after long term contact (Toxicity recognition after a long period of usage) 2 Shigeo Fujii, JST-Bangkok, March 10 2008
POPs Contamination Type 1: Hazardous material Discharge Type 2: Organic Pollution Polluters = Victims Type 3: Eutrophication Merits vs . Risk Type 4: POPs Contamination Sources: Every place (manufacturers, users, consumers) Pollutants: POPs (Persistent organic pollutants) I nfluences: Increase of long-term risk to the public (sterility, feminization, endocrine disruption, cancer) Range: world-wide (including arctic circle) Measures: Ban of manufacture and use 3 Shigeo Fujii, JST-Bangkok, March 10 2008
Stockholm Convention on Persistent Organic Pollutants (POPs) 2001 May: Adoption 2004 May: Enforcement (ratification in 50 parties) Ratification: 128 parties A global treaty to protect human health and the environment from persistent organic pollutants (POPs). To outlaw nine* of the "dirty dozen" chemicals $ , To limit the use of DDT to malaria control, To reduce unintentional production of Dioxins and Furans. Parties to the convention have agreed to a process by which persistent toxic compounds can be reviewed and added to the convention, if they meet certain criteria for persistence and transboundary threat. * Aldrin, Endrin, Heptachior, HCB, Dieldrin, Chlodane, PCB, Toxaphenes, Mirex $ nine* + DDT + Dioxins and Furans; All of them are Chlorinated Cyclic Hydrocarbons 4 Shigeo Fujii, JST-Bangkok, March 10 2008
History of pollutants detected in the food-chain 60 ’ s Rachel Carson (Silent Spring) C l C l DDT (Dichloro-diphenyl-trichloro-ethane, Insecticide ) C l C l PCB 70 ’ s Soren Jensen C l (Poly-chlorinated biphenyls, ( C l ) m ( C l ) n Insultation oil ) O Dioxin 80 ’ s Chistoffer Rappe O (Poly-chlorinated dibenzo-dioxins, ( C l ) m ( C l ) n Defoliant (Viet Nam War), Incineration by-products) PBDE 90 ’ s Koidu Noren (Poly-brominated diphenyl-ehters, O Fire proofing agents ) ( B r ) m ( B r ) n PFOS 00 ’ s 3M, John Giesy (Perfluoro-octane sulfonate, C F - ( C F ) - C F S O 3 2 6 2 4 Water repellent ) 5 Shigeo Fujii, JST-Bangkok, March 10 2008
Introduction (POPs problem) Perfluorinated Perfluorinated compounds (PFCs) World distribution Compounds(PFCs) Their sources and effects of WTPs Countermeasures and future Synthesized fully fluorinated compound, CF 3 (CF 2 ) n - widely used in industrial and commercial applications since the 1960s. Unique Characteristics: hydrophobic & hydrophilic (oleophobic) � water-repellent, non-stick materials Representative compounds - PFOS: Perfluoro-octane Sulfonate C 8 F 17 SO 3 PFOA: Perfluoro-octane Acid C 8 F 15 OO - 6 Shigeo Fujii, JST-Bangkok, March 10 2008
Applications and toxicity PFOS: surface treatment, paper protection, performance chemical e.g. Scotchgard; Carpet; Cup & plate; Fire fighting foam; PFOA: intermediate, (salts:) emulsifier and surfactant e.g. Gore-Tex; Teflon (PTFE); Soap; Shampoo Toxicity: Peroxisome proliferation, Mitochondrial toxicity, Cell membrane disruption, Cancer of liver and spleen of rodents Endocrine Disrupter: I ncrease estrogen and decrease testosterone Decrease thyroid hormone levels 7 Shigeo Fujii, JST-Bangkok, March 10 2008
Study on PFOS and PFOA Y e a r C o n t e n t 1 9 5 6 Scotchgard (PFOS contained) was invented and manufactured. 1 9 9 9 High PFOS concentration were detected in the blood of laborers 2 0 0 0 3M Co. phased out manufacture and use of PFOS 2 0 0 2 OECD issued Harzardous Assessment of PFOS and its salts 2 0 0 3 US EPA issued Harzardous Assessment of PFOA and its salts - 1 9 9 9 2 0 0 0 2 0 0 1 2 0 0 2 2 0 0 3 2 0 0 4 2 0 0 5 2 0 0 6 0 2 5 5 0 7 5 1 0 0 No of papers related PFOS/PFOA in a database (JDream II) 8 Shigeo Fujii, JST-Bangkok, March 10 2008
Range of Environmental Engineering Background Scope of Commercial and the study Industries Domestic Activities PFOS, PFOA Their effects are not well understood Adverse effects: Carcinogen, No Practical Wastewater Endocrine Disruption method Air Treatment Drink Rarely reported Others Food Drinking water Spatial distribution is Surface water not well understood Bio-accumulation (especially in Bio-magnification developing countries) 9 Shigeo Fujii, JST-Bangkok, March 10 2008
Introduction (POPs problem) Surveys in the World Perfluorinated compounds (PFCs) World distribution Their sources and effects of WTPs Countermeasures and future PFOS and PFOA are found in America, Europe and Japan, including environment (water, air, food), human health, and wild animals . Our group Target Area PFCs (Red) in Water Environment and PFCs (yellow) in animals, 2007 10 10 2008/3/24 Shigeo Fujii, JST-Bangkok, March 10 2008
Asia Calgary Kinki Chukoku Vancouver Yodo Hangzhou River North America Khunming Taiwan Shenzhen Europe Hanoi Orebro Khon Kaen Bangkok Rayong Penang Kota Kinabalu Klang River Istanbul Johor Bahru Singapore Sampling areas ( :spot samples of tap water and surface water, :systematic survey) 11 11 Shigeo Fujii, JST-Bangkok, March 10 2008
I. Reproducibility of concentrations Results of repeated sampling and analysis at different periods Concentration (ng/ L) in another sampling period 1000 Y=10X 10000 Yodo R. Yodo River Kota Kinabalu 1000 Kota Kinabalu Y=10X 100 Y= X Phong River Phong River 100 Y=X 10 Y=0.1X 10 Y=0.1X 1 1 0.1 PFOS 0.1 PFOA 0.01 0.01 0.01 0.1 1 10 100 1000 0.01 0.1 1 10 100 1000 10000 Concentration (ng/ L) in a sampling period Concentrations fluctuated within one order of magnitude � confirm concentration levels 12 Shigeo Fujii, JST-Bangkok, March 10 2008
Shigeo Fujii, JST-Bangkok, March 10 2008 Concentration (ng/ L) 1000 0.01 100 0.1 10 1 Hanoi Concentrations in environmental waters N =12 Low Low Kota Kinabalu N =21 Phong R. N =29 Orebro N =12 Medium Medium PFOS Turkey N =04 < LOQ Kinki N =15 Chao Phraya R. N =15 Shenzhen N =09 High High Yodo R. N =34 90% N =24 Singapore Concentration (ng/ L) 1000 0.01 100 N =06 Johor Barhu 0.1 10 1 Orebro Low Low PFOA Kota Kinabalu Phong R. Hanoi Medium Medium Turkey Kinki < LOQ Chao Phraya R. Johor Bahru High High 85% Shenzhen Singapore 21,000 Yodo River largely fluctuated Concentrations samples in majority of were detected PFOS (PFOA) 25% percentile Median 75% percentile Max Min 13
Tap water concentration 1000 1000 Safety levels 500 n g/L 300 n g/L recommended 100 100 PFOS PFOA by Minnesota Concentration (ng/L) Concentration (ng/L) 50 n g/L State (U.S.A.) 10 10 1 1 +25% increase in 0.1 0.1 human blood concentrations 0.01 0.01 (Harada et al. Phong River Phong R. Istanbul Vancouver Hanoi Kota Kinabalu Orebro Turkey Chao Phraya R. Hangzhou Shenzhen Yodo River Johor Bahru Orebro Kota Kinabalu Hanoi Vancouver Chao Phraya R. Johor Bahru Shenzhen Yodo River Hangzhou 2003) 14 Shigeo Fujii, JST-Bangkok, March 10 2008
Tap water vs YO : Yodo R. OR : Orebro CH : Bangkok JO : Johor Bahru surface water SH : Shenzhen IS : Istanbul KK : Kota Kinablu NE : Nevshehir PH : Khon Kean VC : Vancouver HN : Hanoi HZ : Hangzhou Tap water concentration (ng/ L) Tap water concentration (ng/ L) 100 1000 y = 0.91x Y=5X Y=5X R = 0.84 y = 0.74x HZ PFOS PFOA R = 0.47 SH 100 10 Y=(1 /5)X JO YO Y=(1 /5)X NE CH CH 10 YO HZ 1 IS TR 1 SH OR PH PH OR JO 0.1 VC NE VC 0.1 KK KK HN HN 0.01 0.01 0.01 0.1 1 10 100 0.01 0.1 1 10 100 1000 Surface water concentration (ng/ L) Surface water concentration (ng/ L) � Concentrations in tap waters ~ in environmental waters: SI MI LAR! � Concentrations in tap waters ~ in environmental waters: SI MI LAR! Water sources? 15 Shigeo Fujii, JST-Bangkok, March 10 2008
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