PARENT SESSION

1H a - Perfluorinated Substances
Hall 6
8:30 AM - 12:30 PM, Wednesday, 30 April 2003
Chair: de Voogt, P.¹, ¹
Co-chair: Purdy, R.², ²

(WE6/7) Identification of long-chain perfluorinated acids in animals from the North American Arctic.

Martin, Jonathan¹, Mabury, Scott¹, Smithwick, Marla², Sonne-Hansen, Christian³, Gamberg, Mary⁴, Braune, Birgit⁵, Muir, Derek⁶, ¹ University of Toronto, Toronto, Ontario, Canada² University of Guelph, Guelph, Ontario, Canada³ National Environmental Research Institute, Roskilde, Denmark⁴ ., Whitehorse, Yukon⁵ Canadian Wildlife Service, Ottawa, Ontario, Canada⁶ National Water Research Institute, Burlington, Ontario, Canada

ABSTRACT- Reports on the global detection of perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), and perfluorooctanoate (PFOA) in arctic mammals prompted us to investigate for the occurrence of longer chain-length perfluorinated acids (PFAs) in similar samples. Samples were collected by native subsistence hunters in Alaska and the Canadian Arctic, and included liver of polar bear, beluga whale, ringed seal, arctic fox, mink, loons, fulmars, guillemots, and several fishes. By applying existing methods for the extraction, concentration, and liquid chromatographic analysis of PFAs, we simply extended the electrospray tandem mass-spectrometry method (ESI/MS/MS) to monitor for longer chain-length PFAs. In addition to PFOS, PFHxS, and PFOA, long-chain PFAs detected in liver samples included perfluoroalkyl carboxylates in the homologous series ranging from perfluorononanoate (PFNA) to perfluorotetradecanoate (PFTA). Detection was confirmed for many PFAs, according to strict European Union criteria, by comparing the retention time and ratio of multiple MS/MS transitions to authentic standards. Quantitation was performed relative to a surrogate standard, perfluoroheptanoate, spiked into the matrix before extraction. Long-chain PFA concentrations in liver ranged from <1.0 to approximately 100 ng/g (wet weight), and were highest for PFNA, generally decreasing in concentration with increasing chain-length. Concentrations of long-chain PFAs were usually less than for PFOS, however, in some animals (e.g. mink) the mean concentration of PFNA exceeded PFOS, despite having a lower bioaccumulation potential. The source of long-chain PFAs to the arctic is not known, but strong statistical associations between individual PFA homologue concentrations within each organism indicated that the source is probably common to all homologues.

Key words: Arctic, perfluorinated acids , tandem mass-spectrometry, contaminants