Enantiomer fractions of chiral Perfluorooctanesulfonate (PFOS) in human sera.

Perfluorooctane sulfonate (PFOS) is the most prominent perfluoroalkyl contaminant in humans and wildlife, but there is great uncertainty in exposure pathways, particularly with respect to the importance of PFOS-precursors (PreFOS). We explored the hypothesis that nonracemic proportions of chiral PFOS in serum are qualitative and semiquantitative biomarkers of human PreFOS exposure. A new chiral HPLC-MS/MS method was developed for alpha-perfluoromethyl branched PFOS (1m-PFOS, typically 2-3% of total PFOS) and applied to enantiomer fraction (EF) analysis in biological samples. In blood and tissues of rodents exposed subchronically to electrochemical PFOS, 1m-PFOS was racemic (EF = 0.485-0.511) and no evidence for enantioselective excretion was found in this model mammal. 1m-PFOS in serum of pregnant women, from Edmonton, was significantly nonracemic, with a mean EF (±standard deviation) of 0.432 ± 0.009, similar to pooled North American serum. In a highly exposed Edmonton family (mother, father, and 5 children) living in a house where ScotchGard had been applied repeatedly to carpet and upholstery, EFs ranged from 0.35 to 0.43, significantly more nonracemic than in pregnant women. Semiquantitative estimates of % serum 1m-PFOS coming from 1m-PreFOS biotransformation in both subpopulations were in reasonable agreement with model predictions of human exposure to PFOS from PreFOS. The data were overall suggestive that the measured nonracemic EFs were influenced by the relative extent of exposure to PreFOS. The possibility of using 1m-PFOS EFs for assessing the relative contribution of 1m-PreFOS (or PreFOS in general) in biological samples requires further application before being fully validated, but could be a powerful tool for probing general sources of PFOS in environments where the importance of PreFOS is unknown.