Perfluorinated acids (PFAs) are ubiquitously found in water and biota, including remote regions such as the High Arctic. Under environmental conditions, PFAs exist mainly as anions and are not expected to be subject to long-range atmospheric transport in the gas phase. Fluorinated telomer alcohols (FTOHs) are volatile and can be atmospherically oxidized to form perfluorocarboxylic acids. Analogously, fluorosulfamido alcohols can be oxidized to form perfluorooctane sulfonate (PFOS). High Arctic ice caps experience contamination solely from atmospheric sources. By examining concentrations of PFAs in ice cap samples, it is possible to determine atmospheric fluxes to the Arctic. Ice samples were collected from high Arctic ice caps in the spring of 2005 and 2006. Samples were concentrated using solid-phase extraction and analyzed by LC-MS-MS. PFAs were observed in all samples, dating from 1996 to 2005. Concentrations were in the low-mid pg L(-1) range and exhibited seasonality, with maximum concentrations in the spring-summer. The presence of perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA) on the ice cap was indicative of atmospheric oxidation as a source. Ratios of PFAs to sodium concentrations were highly variable, signifying PFA concentrations on the ice cap were unrelated to marine chemistry. Fluxes of the PFAs were estimated to the area north of 65 degrees N for the 2005 season, which ranged from 114 to 587 kg year(-1) for perfluorooctanoic acid (PFOA), 73 to 860 kg year(-1) for perfluorononanoic acid (PFNA), 16 to 84 kg year(-1) for PFDA, 26 to 62 kg year(-1) for PFUnA, and 18 to 48 kg year(-1) for PFOS. The PFOA and PFNA fluxes agreed with FTOH modeling estimations. A decrease in PFOS concentrations through time was observed, suggesting a fast response to changes in production. These data suggest that atmospheric oxidation of volatile precursors is a primary source of PFAs to the Arctic.
Perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) have been hypothesized to reach remote locations such as the Canadian Arctic either indirectly as volatile precursor chemicals that undergo atmospheric transport and subsequent degradation, or directly via oceanic and atmospheric transport of the PFSAs and PFCAs themselves. Water, sediment, and air samples were collected from three Arctic lakes (Amituk, Char, and Resolute) on Cornwallis Island, Nunavut, Canada. Samples were analyzed for PFSAs and PFCAs, precursor chemicals including the fluorotelomer alcohols (FTOHs) and polyfluorinated sulfonamides (FSAs), and precursor degradation products such as the fluorotelomer unsaturated carboxylates (FTUCAs). PFSAs and PFCAs were detected in water and sediment of all three Arctic lakes (concentrations ranged from nondetect to 69 ng/L and nondetect to 85 ng/g dry weight, respectively). FTOHs and FSAs were observed in air samples (mean concentrations ranged from 2.8 to 29 pg/m3), and confirm that volatile precursors are reaching Arctic latitudes. The observation of degradation products, including FTUCAs observed in sediment and atmospheric particles, and N-ethyl perfluorooctanesulfonamide (NEtFOSA) and perfluorooctanesulfonamide (PFOSA) in air samples, indicate that degradation of the FTOHs and FSAs is occurring in the Arctic environment. PFSAs and PFCAs were also observed on atmospheric particles (mean concentrations ranged from < 0.1 to 5.9 pg/m3). In addition, results of this study also indicate that local perfluoroalkyl contamination of Resolute Lake, which is located downstream of an airport wastewater input, has occurred.
Sources of human exposure to perfluorinated carboxylic acids (PFCAs) are not well-characterized. Polyfluoroalkyl phosphoric acids (PAPs) are fluorinated surfactants used in human food contact paper products. PAPs can migrate into food and food simulants, and their bioavailability and biotransformation into PFCAs has been demonstrated using a rat model. To characterize human exposure to PAP materials, we analyzed pooled human sera samples collected in 2004 and 2005 (n = 10) and 2008 (n = 10) from the midwestern United States for the 4:2 through 10:2 PAP diesters (diPAPs). The 2004 and 2005 sera samples contained 4.5 microg/L total diPAPs, with the 6:2 diPAP dominating the congener profile at 1.9 +/- 0.4 microg/L DiPAP concentrations observed in the 2004 and 2005 human sera samples were similar to those of the C8 to C11 PFCAs (0.13 +/- 0.01 to 4.2 +/- 0.3 microg/L) monitored in the same samples. 6:2 diPAP was also consistently observed in the 2008 human sera samples at a mean concentration of 0.63 +/- 0.13 microg/L As diPAPs have been shown to degrade to PFCAs in vivo, our observation of diPAPs in human sera may be a direct connection between the legacy of human PFCA contamination and PAPs commercial applications. Wastewater treatment plant (WWTP) sludge and paper fibers were analyzed for diPAPs as a proxy for human use and potential exposure to diPAPs. DiPAPs were observed in WWTP sludge at concentrations ranging from 47 +/- 22 to 200 +/- 130 ng/g, a range similar to perfluorooctane sulfonic acid (PFOS) (100 +/- 70 ng/g) and greater than the C8 to C11 PFCAs (1.6 +/- 0.6 to 0.17 +/- 0.10 ng/g) observed in the same samples. DiPAPs were observed in paper fiber extracts at concentrations ranging from 34 +/- 30 to 2200 +/- 400 ng/g. The high diPAP concentrations in WWTP sludge suggest PAP materials may be prevalent in our daily lives.
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