Rapid response of Arctic ringed seals to changes in perfluoroalkyl production

Temporal trends in perfluoroalkyl compounds (PFCs) were investigated in liver samples from two ringed seal (Phoca hispida) populations in the Canadian Arctic, Arviat (Western Hudson Bay) (1992, 1998, 2004, 2005) and Resolute Bay (Lancaster Sound) (1972, 1993, 2000, 2004, 2005). PFCs analyzed included C7-C15 perfluorinated carboxylates (PFCAs) and their suspected precursors, the 8:2 and 10:2 fluorotelomer saturated and unsaturated carboxylates (FTCAs, FTUCAs), C4, C6, C8, C10 sulfonates, and perfluorooctane sulfonamide (PFOSA). Liver samples were homogenized, liquid-liquid extracted with methyl tert-butyl ether, cleaned up using hexafluoropropanol, and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). C9-C15 PFCAs showed statistically significant increasing concentrations during 1992-2005 and during 1993-2005 at Arviat and Resolute Bay, respectively. Doubling times ranged from 19.4 to 15.8 years for perfluorododecanoate (PFDoA) to 10.0-7.7 years for perfluorononanoate (PFNA) at Arviat and Resolute Bay but were shorter when excluding the 2005 samples. Conversely, perfluorooctane sulfonate (PFOS) and PFOSA concentrations showed maximum concentrations during 1998 and 2000 at Arviat and Resolute Bay, with statistically significant decreases from 2000 to 2005. In the case of Arviat, two consecutive decreases were measured from 1998 to 2003 and from 2003 to 2005. PFOS disappearance half-lives for seals at Arviat and Resolute Bay were 3.2 and 4.6 years. These results indicate that the ringed seals and their food web are rapidly responding to the phase out of perfluorooctane sulfonyl fluoride based compounds by 3M in 2001. Further, the relatively short doubling times of the PFCAs and PFOS disappearance half-lives support the hypothesis of atmospheric transport as the main transport mechanism of PFCs to the arctic environment.