No abstract

Human exposure to perfluorinated compounds is a worldwide phenomenon; however, routes of human exposure to these compounds have not been well-characterized. Fifty-four solid food composite samples collected as part of the Canadian Total Diet Study (TDS) were analyzed for perfluorocarboxylates and perfluorooctanesulfonate (PFOS) using a methanol extraction liquid chromatography tandem mass spectrometry method. Foods analyzed included fish and seafood, meat, poultry, frozen entrées, fast food, and microwave popcorn collected from 1992 to 2004 and prepared as for consumption. Nine composites contained detectable levels of perfluorinated compounds-four meat-containing, three fish and shellfish, one fast food, and one microwave popcorn. PFOS and perfluorooctanoate (PFOA) were detected the most frequently; concentrations ranged from 0.5 to 4.5 ng/g. The average dietary intake of total perfluorocarboxylates and PFOS for Canadians was estimated to be 250 ng/day, using results from the 2004 TDS composites. A comparison with intakes of perfluorocarboxylates and PFOS via other routes (air, water, dust, treated carpeting, and apparel) suggested that diet is an important source of these compounds. There was a substantial margin of exposure between the toxicological points of reference and the magnitude of dietary intake of perfluorinated compounds for Canadians >/= 12 years old.

An eastern Arctic marine food web was analyzed for perfluorooctanesulfonate (PFOS, C8F17SO3-), perfluorooctanoate (PFOA, C7F15COO-), perfluorooctane sulfonamide (PFOSA, C8F17SO2NH2), and N-ethylperfluorooctane sulfonamide (N-EtPFOSA, C8F17SO2NHCH2CH3) to examine the extent of bioaccumulation. PFOS was detected in all species analyzed, and mean concentrations ranged from 0.28 +/- 0.09 ng/g (arithmetic mean +/- 1 standard error, wet wt, whole body) in clams (Mya truncata) to 20.2 +/- 3.9 ng/g (wet wt, liver) in glaucous gulls (Larus hyperboreus). PFOA was detected in approximately 40% of the samples analyzed at concentrations generally smaller than those found for PFOS; the greatest concentrations were observed in zooplankton (2.6 +/- 0.3 ng/g, wet wt). N-EtPFOSA was detected in all species except redfish with mean concentrations ranging from 0.39 +/- 0.07 ng/g (wet wt) in mixed zooplankton to 92.8 +/- 41.9 ng/g (wet wt) in Arctic cod (Boreogadus saida). This is the first report of N-EtPFOSA in Arctic biota. PFOSA was only detected in livers of beluga (Delphinapterus leucas) (20.9 +/- 7.9 ng/g, wet wt) and narwhal (Monodon monoceros) (6.2 +/- 2.3 ng/g, wet wt), suggesting that N-EtPFOSA and other PFOSA-type precursors are likely present but are being biotransformed to PFOSA. A positive linear relationship was found between PFOS concentrations (wet wt) and trophic level (TL), based on delta15N values, (r2 = 0.51, p < 0.0001) resulting in a trophic magnification factor of 3.1. TL-corrected biomagnification factor estimates for PFOS ranged from 0.4 to 9. Both results indicate that PFOS biomagnifies in the Arctic marine food web when liver concentrations of PFOS are used for seabirds and marine mammals. However, transformation of N-EtPFOSA and PFOSA and potential other perfluorinated compounds to PFOS may contribute to PFOS levels in marine mammals and may inflate estimated biomagnification values. None of the other fluorinated compounds (N-EtPFOSA, PFOSA, and PFOA) were found to have a significant relationship with TL, but BMF(TL) values of these compounds were often >1, suggesting potential for these compounds to biomagnify. The presence of perfluorinated compounds in seabirds and mammals provides evidence that trophic transfer is an important exposure route of these chemicals to Arctic biota.

Rainbow trout (Onchorhynchus mykiss) liver microsomes were incubated with N-ethyl perfluorooctanesulfonamide [N-EtPFOSA, C8F17SO2NH(C2H5)], to examine the possibility of in vitro biotransformation to perfluorooctane sulfonate (PFOS, C8F17SO3-) and perfluorooctanoate (PFOA, C7F15COO-). Incubations were performed by exposing trout liver microsomes to N-EtPFOSA at 8 degrees C in the dark. Reaction mixtures were analyzed after incubation periods of 0, 2, 4, 8, 16, and 30 h for N-EtPFOSA, PFOS, PFOA, and perfluorooctanesulfonamide (PFOSA, C8F17SO2NH2), a suspected intermediate. Amounts of PFOS and PFOSA were found to increase with incubation time, but only background levels of PFOA were detected. Three possible reaction pathways are proposed for the conversion of N-EtPFOSA to PFOS: (i) direct conversion of N-EtPFOSA to PFOS by deethylamination accompanied by conversion of the sulfone group to sulfonate, (ii) deethylation of N-EtPFOSA to PFOSA, followed by deamination to form PFOS, and (iii) direct hydrolysis of N-EtPFOSA. These findings represent the first report indicating a possible biotransformation of a perfluorosulfonamide to PFOS in fish and may help to explain the detection of PFOS, which is relatively involatile, and thus not likely to undergo atmospheric transport, in biota from remote regions.