Although perfluorocarboxylates (PFCAs) have been detected in a number of environmental matrices, there are very few reports on concentrations in precipitation. In this study PFCAs, fluorotelomercarboxylates (FTCAs), and fluorotelomer-unsaturated carboxylates (FTUCAs), were determined in wet only precipitation samples from nine sites in North America. The analytical method involved derivatization of the carboxylates and measurement of the 2,4-difluoroanilide by GC-MS. Samples from three remote sites in Canada had low concentrations of perfluorooctanoate (PFOA) (<0.1-6.1 ng/L). Significantly higher concentrations of PFOA were found at 4 northeastern United States and 2 southern urban Canadian sites, with Delaware having the highest levels (85 ng/L PFOA, with a range of 0.6-89 ng/L) and a maximum flux of 13 000 ng/m2. 8:2- and 10:2 FTCAs and FTUCAs were detected at all 4 U.S. sites and 2 urban Canadian sites (<0.07-8.6 ng/L), most frequently at the Delaware site. Longer chained PFCAs (deca-, undeca-, and dodeca-perfluorocarboxylates) were detected (<0.07-5.2 ng/L) at 2 urban Ontario sites but not determined in other samples. Air mass back trajectory results for 3 U.S. sites indicate highly populated urban areas in the New York to Washington corridor as the main sources of PFOA, although low PFOA levels associated with air masses coming off the Atlantic Ocean imply multiple sources.

Perfluoroethylcyclohexanesulfonate (PFECHS) is a cyclic perfluorinated acid (PFA) mainly used as an erosion inhibitor in aircraft hydraulic fluids. It is expected to be as recalcitrant to environmental degradation as aliphatic PFAs including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). For the first time, PFECHS is reported in top predator fish (

We report here on the spatial distribution of C(4), C(6), and C(8) perfluoroalkyl sulfonates, C(6)-C(14) perfluoroalkyl carboxylates, and perfluorooctanesulfonamide in the Atlantic and Arctic Oceans, including previously unstudied coastal waters of North and South America, and the Canadian Arctic Archipelago. Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were typically the dominant perfluoroalkyl acids (PFAAs) in Atlantic water. In the midnorthwest Atlantic/Gulf Stream, sum PFAA concentrations (∑PFAAs) were low (77-190 pg/L) but increased rapidly upon crossing into U.S. coastal water (up to 5800 pg/L near Rhode Island). ∑PFAAs in the northeast Atlantic were highest north of the Canary Islands (280-980 pg/L) and decreased with latitude. In the South Atlantic, concentrations increased near Rio de la Plata (Argentina/Uruguay; 350-540 pg/L ∑PFAAs), possibly attributable to insecticides containing N-ethyl perfluorooctanesulfonamide, or proximity to Montevideo and Buenos Aires. In all other southern hemisphere locations, ∑PFAAs were <210 pg/L. PFOA/PFOS ratios were typically ≥1 in the northern hemisphere, ∼1 near the equator, and ≤1 in the southern hemisphere. In the Canadian Arctic, ∑PFAAs ranged from 40 to 250 pg/L, with perfluoroheptanoate, PFOA, and PFOS among the PFAAs detected at the highest concentrations. PFOA/PFOS ratios (typically ≫1) decreased from Baffin Bay to the Amundsen Gulf, possibly attributable to increased atmospheric inputs. These data help validate global emissions models and contribute to understanding of long-range transport pathways and sources of PFAAs to remote regions.

Per- and polyfluorinated alkyl substances (PFASs) enter Arctic lakes through long-range atmospheric transport and local contamination, but their behavior in aquatic food webs at high latitudes is poorly understood. This study compared the concentrations of perfluorocarboxylates, perfluorosulfonates, and fluorotelomer sulfonates (FTS) in biotic and abiotic samples from six high Arctic lakes near Resolute Bay, Nunavut, Canada. Two of these lakes are known to be locally contaminated by a small airport and Arctic char (Salvelinus alpinus) from these lakes had over 100 times higher total [PFAS] when compared to fish from neighboring lakes. Perfluorononanoate (PFOA) and perfluorooctanesulfonate (PFOS) dominated in char, benthic chironomids (their main prey), and sediments, while pelagic zooplankton and water were dominated by lower chain acids and perfluorodecanesulfonate (PFDS). This study also provides the first measures of perfluoroethylcyclohexanesulfonate (PFECHS) and FTS compounds in water, sediment, juvenile char, and benthic invertebrates from lakes in the high Arctic. Negative relationships between [PFAS] and δ(15)N values (indicative of trophic position) within these food webs indicated no biomagnification. Overall, these results suggest that habitat use and local sources of contamination, but not trophic level, are important determinants of [PFAS] in biota from freshwater food webs in the Canadian Arctic.