Perfluorinated Compounds in Surface Waters from Northern China: Comparison to Level of Industrialization Tieyu Wang Research Center for Eco-environmental Sciences, Chinese Academy of Sciences Nov. 13-17, 2011 Perfluorinated Compounds (PFCs) • Compounds with C-F bond. C-F bond is the strongest of known covalent bonds. • Perfluorinated compounds (PFCs) are fully fluorinated, and are all anthropogenic. • However, Total production of carboxylated and sulfonated PFCs is unknown. • Relatively large amounts of PFCs are manufactured and used in China, especially by the textile, leather and paper industries. Perfluorinated Compounds (PFCs) • PFOS was listed as a POPs under the Stockholm Convention in 2009, but with many exemptions. • Recently, Annual production of PFOS-containing chemicals has grown rapidly in China, due to domestic and oversea demands. • PFOS and PFOA have received a great deal of attention, which are the terminal degradation products of several precursors, • and they have been frequently detected in environment with higher concentrations. Applications of PFCs Adhesives: Wetting agents Antifogging: Glass surfaces Antistatic agents: Microchip manufacture Cleaners for hard surfaces: Floor Polishes Coatings: Paint additives, waxes Cosmetics: Hair-conditioning Electronics: Insulators, microchips Electroplating: Chromium, copper and nickel Fire-Fighting Foams: Formulated to float on flammable liquids Herbicides and Insecticides: Wetting agents Leather: Provide water and oil repellency Paper: Oil and water repellency Textiles: Polyester etc. to impart soil, oil and water repellency. Major use is in carpeting. Production and Survey in China PFCs in Water of China Rivers of China Groundwater Tap water Sample Locations Level of Industrialization Guanting Reservoir, limited development Hohhot, Inner Mongolia, grassland and agriculture, lower development Shanxi, Fenhe River, fossil fuel, coal, extensive industrial Guanting<Hohhot<Shanxi Tianjin, Haihe <Tianjin<Liaoning River, fossil oil Liaoning, chemical and smelt industry, heavy industrial and high-tech industrial A integrated index: included GDP per capita, non-agricultural product, non-agricultural employment, degree of urbanization, informationization and foreign trade Sample collection Guanting Lake, Yanghe River and Guishui River Dahei River, Xiaohei River and Shilawusu River Fenhe River and Yellow River Haihe River system Liaohe River system, Daling River Why Monitoring? to determine concentrations, distribution, and transportation of PFCs in aquatic systems in Northern China To establish baseline environmental concentrations for identifying sources and potential risks To provide information for future effectiveness of control measures PFCs in Water from Northern China PFCs in Water from Guanting Concentrations of PFOA and PFOS were 0.55 to 2.3 ng/l and <LOQ to 0.52 ng/l in Guanting area. PFCs in Water from Hohhot Concentrations of PFOA and PFOS were 0.80 to 1.8 ng/l and <LOQ to 1.1 ng/l in Hohhot. PFCs in Water from Shanxi Concentrations of PFOA and PFOS were 0.43 to 15 ng/l and < LOQ to 5.7 ng/l in Shanxi. The higher concentrations of PFCs were found at downstream of the rivers , indicating an increasing concentration from upstream to downstream. PFCs in Water from Tianjin Concentrations of PFOA and PFOS were 3.0 to 12 ng/l and 0.09 to 11 ng/l in Tianjin. T05 from the Haihe River, near a sewage treatment plant PFCs in Water from Liaoning Concentrations of PFOA and PFOS were 2.6 to 82 ng/l and <LOQ to 31 ng/l in Liaoning. PFCs in Water from Northern China Locat Samp Guanting 7 Hohhot 8 Shanxi 9 Tianjin 8 Liaoning 10 PFOS 0.16±0.08 0.32±0.12 0.93±0.64 2.6±1.2 4.7±3.0 PFOA 1.2±0.23 6.8±1.1 27±10 1.2±0.12 2.7±1.5 PFHpA 0.06±0.04 0.04±0.02 0.32±0.12 0.87±0.26 PFNA 0.02±0.01 0.02±0.02 nd 5.9±3.3 1.1±0.61 0.14±0.13 PFDA 0.10±0.03 0.07±0.02 0.07±0.01 1.1±0.51 0.68±0.56 PFDoA 0.11±0.04 0.21±0.01 0.06±0.02 0.10±0.02 0.03±0.02 PFHxS 0.03±0.03 0.02±0.01 0.78±0.63 0.01±0.01 0.90±0.28 ∑PFCs 1.7±0.36 1.8±0.15 4.8±1.8 13±2.7 39±12 Comparison with Other Studies in China Location Guanting Hohhot Shanxi Tianjin Liaoning PFOS nd-0.52 nd-1.1 nd-5.7 0.10-11 nd-31 PFOA 0.55-2.3 0.80-1.8 0.43-15 3.0-12 2.6-82 Reference Coastal area of China 0.02-9.68 0.24-15.3 Yamashita et al., 2005 Beijing Dongguan Chongqing Yichang Wuhan Nanjing Shanghai Pearl River Delta Hong Kong 1.75-4.09 0.90-99 nd-0.35 0.29-0.61 2.3-5.3 0.33-0.38 0.62-14 0.02-12 0.09-3.1 5.51-7.85 0.85-4.4 nd-35 4.1-4.9 2.8-5.6 2.1-2.4 22-260 0.24-16 0.73-5.5 Zhao et al., 2007 So et al., 2007 So et al., 2007 So et al., 2007 Jin et al.,2006 So et al., 2007 So et al., 2007 So et al., 2004 So et al., 2004 Present study Comparison with Studies in Adjacent Countries China Location Guanting Hohhot Shanxi Tianjin Liaoning PFOS nd-0.52 nd-1.1 nd-5.7 0.10-11 nd-31 PFOA 0.55-2.3 0.80-1.8 0.43-15 3.0-12 2.6-82 Tokyo Bay 12.7-25.4 154-192 South Korea India Survey of Japan Yodo River basin Coastal of Korea Korea coast Cooum River 0.89-5.73 0.4-123 0.04-730 4.11-450 0.04-3.91 0.97-21.5 4.2-2600 0.24-320 2.95-68.6 0.04-23.1 Thailand Chao Phraya River 0.7-17.9 0.7-64.3 Japan Reference Present study Yamashita et al., 2004 Saito et al., 2004 Lein et al., 2008 So et al., 2004 Naile et al., 2010 Yeung et al., 2009 Kunacheva et al., 2009 General Conclusions Concentrations of PFCs in waters from Guanting and Hohhot were 3- to 20- fold less than those from Tianjin and Liaoning, which is consistent with little contribution of PFCs from agricultural and non-industrial activities. Concentrations of both PFOA and PFOS in waters from all regions were less than suggested allowable concentrations. However, the relatively greater concentrations of PFCs in Tianjin and Liaoning suggest that further studies are needed. PFCs in Estuarine and Coast of North Bohai Sea Heavy polluted areas, North Bohai Bay, especially Liaoning Province Sample Collection and Treatment Type Amount Water 36 Sediment 35 Soil 31 Biota 25 FB 12 PFCs in Water from North Bohai Bay PFCs in Sediment from North Bohai Bay PFCs in Soil from North Bohai Bay PFCs in Biota from North Bohai Bay Potential Ecological Risk to Aquatic Animals General Conclusions Significant concentrations of PFCs were found in water (mean: 18.4 ng/l) and biological samples (fish: 265 ng/g dw). While concentrations of PFCs in soils and sediments were less. The predominately detected compound was PFOS, with a maximum of 30.9 ng/l in water and 791 ng/g dw in fish. PFCs were significantly greater in Liaohe River system, which suggests point sources in this urbanized and industrialized region. PFOS concentrations in water and biota were both less than the reported threshold concentrations. Acknowledgements Dr. John Giesy, Professor and Canada Research Chair from University of Saskatchewan for assistance in sample analyzing. Dr. Jong Seong Khim of Korea University for collecting sample in 2008. Dr. Kannan K., Professor of State University of New York at Albany for collecting sample in 2006. Special thanks give to KC Wong Education Foundation for supporting my travel and expense of this conference. Funding from the National Basic Research Program of China. Dr. Tieyu Wang Environmental Management and Policy Group State Key Lab of Urban and Regional Ecology Research Center for Eco-Environmental Sciences, CAS Tel:86-10-62849466; E-mail:wangty@rcees.ac.cn