1. Polybrominated Diphenyl Ether Trends in the Great Lakes Ecosystem A new persistent contaminant of concern? Frederick Luckey New York State Department of Environmental Conservation Division of Water, 625 Broadway, Albany, NY 12233-3508 Fjluckey@gw.dec.state.ny.us PBDE Trends in Lake Ontario Lake Trout Dept. of Fisheries & Oceans, Canadian Centre for Inland Waters Alaee, M., Luross, J.M., Sergeant, D.B., Muir, D.C.G. Whittle, D.M.,and Solomon, K.R. 1999. Distribution of polybrominated diphenyl ethers in the Canadian environment. Organohalogen Compounds 40:347-350. Bromine Science and Environmental Forum – www.bsef.com de Boer, J., de Boer, K. and Boon J. P. Handbook Environmental Chemistry (Passivirta, J., ed.), Springer- Verlag, 2000, ch 4; 61-95. Luckey, F.J., Fowler, B. and Litten, S. Establishing baseline levels of polybrominated diphenyl ethers in Lake Ontario surface waters. In Proc. 2 nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden. Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2 ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000. Manchester-Neesvig, J.B., Valters K. and Sonzogni, W.C. 2001. Comparison of polybrominated Diophenyl Ethers (PBDEs) and Polychlorinated Biphenyls (PCBs) in Lake Michigan Salmonids. Environ. Sci. Technol., 35, pp.1072-1077. Moisey, J., Simon, M. Wakeford, B., Weseloh, D.V. and Norstrum, R.J. 2001. Spatial and temporal trends of polybrominated diphenyl ethers in Great Lakes herring gulls, 1981 to 2000. In Proc. 2 nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden. Meironyte, D., Noren, K., and Bergman Ake. 1999. Analysis of Polybrominated Diphenyl Ethers in Swedish human milk. A time trend study, 1972-1997. J. of Toxicology and Environmental Health, Part A, 58:329- 341. pp. 329-341. Noren, K. and Meironyte, D. Chemosphere, 2000, 40, 1111-1123. Ryan, J. J. and Patry, B. Organohalogen Compounds, 2000, 47, 57-60. Ryan, J.J. and B. Patry, Body burdens and exposure from food for polybrominated diphenyl ethers (BDEs) in Canada 3rd Annual Workshop on Brominated Flame Retardants in the Environment, 2001, Burlington, Ontario, Canada 209. Sjodin, A., Jakobsson, E., Kiergaard, A., Marsh, G. and Sellstrom, U. 1998. Gas chromatographic identification and quantification of polybrominated diphenyl ethers in a commercial product, Bromkal 70- 5DE. J. of Chromatography A. 822, pp.83-89. World Health Organization. 1994. Environmental Health Criteria 162: Brominated Diphenyl Ethers, WHO: Geneva, Switzerland. PBDE Structure 4’ 2’ O 3’ 5’ 2 4 3 66’ 5 C 12 H 10-n Br n O Polybrominated diphenyl ethers (PBDEs) have been used for more than two decades as an effective flame retardant in a wide range of electrical applications, building materials, textiles, foams and plastics to reduce loss of life and property due to fire. Unfortunately it is now clear that PBDEs have joined the ranks of global persistent organic contaminants found in tissues of fish and wildlife even in remote corners of the earth. The purpose of this poster paper is simply to highlight some of the initial work, completed and underway, that will help us better understand the behavior of PBDEs in the Great Lakes environment. Introduction Ng/g Lipid 209 congeners / 8 homolog groups like PCBs PBDE congeners identified by the same IUPAC numbering system used for PCBs (e.g., BDE-47) bioaccumulative (K ows 5 to 6) can form brominated dioxins and furans when burned used in manufacture of additive brominated flame retardants widely used in plastics, polymers, foams, electrical equipment, textiles, TVs, computers, furniture and building materials. additive flame retardants do not bond well to polymers and other materials. PBDE flame retardant mixtures are classified by their degree of bromination: penta bromodiphenyl ether (BDE) (five bromines); octa- BDE (eight bromines); and deca-BDE (ten bromines). No current US Federal environmental criteria / standards No EPA approved analytical methods Some studies indicate that PBDE levels exponentially increasing in wildlife & human tissues. PBDE Background AmericasEuropeAsiaTotal Deca-BDE24,3007,50023,00054,800 Octa-BDE1,3754502,0003,825 Penta-BDE8,290210--8,500 1999 PBDE Global Demand Estimates (Tons) Bromine Science & Environmental Forum PBDE Trends in Gull Eggs from Eastern Lake Ontario Canadian National Wildlife Research Center & Canadian Wildlife Service 2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in: Great Lakes Trout & Gulls Baltic Salmon Arctic Ringed Seals Faroe Island Pilot Whales Human Breast Milk 2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest Preliminary results indicate BDE-47 & BDE-99 are dominant In Lake Ontario surface water. Dominant PBDE Congeners in Biota BDE -47 & BDE-99 together makeup ~70% of the Commercial flame retardant formulation “Bromkal 70-5DE” leading some to speculate that use of this product may be one source of these congeners. References 1999 PBDE Conc. in Lake Ontario Surface Waters New York State Dept. of Environmental. Conservation Ng/g Lipid PBDE trends in North American Breast Milk Data compiled by Environment Canada PBDE Lab / Field Contamination Issues Considering that PBDEs are widely used in many materials and there are no controls on its use, researchers need to take extra precautions to prevent field or lab contamination of environmental samples. In one instance PBDE lab method blank levels dramatically increased following the installation of new lab air ducts. It was discovered that the ducting material contained percent levels of brominated flame retardants levels. Method blank levels decreased after the ducts were replaced with PBDE-free ducts. Canadian Milk Bank Samples collected in New York State Samples collected in Austin & Denver Data sources: Canadian Milk Bank and New York state data: Ryan & Patry, Health Canada; Denver Colo. & Austin, Tex. Data: Papke Data complied by Mehran Alaee, Environment Canada Figure adapted from ES&T 02/01/02 Environmental News p. 50. Large volume sample, XAD resin. Cartridge glass fiber filter, HRGC/MS EPA Method 1668A Six-year old lake trout, HRGC/MS Adapted from: Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2 ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000. Adapted from: Moisey, J., Simon, M. Wakeford, B., Weseloh, D.V. and Norstrum, R.J. 2001. Spatial and temporal trends of polybrominated diphenyl ethers in Great Lakes herring gulls, 1981 to 2000. In Proc. 2 nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden.