Elevated levels of per- and polyfluoroalkyl substances (PFAS) in freshwater benthic macroinvertebrates from the Hudson River Watershed.

Per- and polyfluoroalkyl substances (PFAS) are contaminants of global concern due to their persistence and associated negative health effects. Considerable attention has been given to monitoring PFAS in the aquatic environment, however, few investigations have done so using freshwater benthic macroinvertebrates (BMIs). As these bottom-dwelling animals are known to bioconcentrate exogenous pollutants to a high degree, studying their PFAS levels may provide a more integrated view of PFAS contamination in the aquatic environment. In this study, BMIs, sediment, and surface water were collected from two streams in the Hudson River Watershed (one historically-impacted by PFAS) and analyzed for 44 PFAS using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Orbitrap high-resolution mass spectrometry (HRMS) was used to confirm the identities of quantitated analytes. Across all matrices, 17 analytes were detected with PFOA dominating in surface water and PFOS in sediment/BMIs. PFOS bioaccumulation factors (BAFs) were approximately one order of magnitude higher than those of PFOA and ranged from 857 to 5151 L kg-1 across different BMI taxa. While PFAS concentrations in surface water and sediment were not excessively high, elevated levels were still measured in most BMI taxa. This observation suggests that the extent of PFAS contamination in a local system may be severely underestimated if only surface water and sediment are used for monitoring. Moreover, these findings have relevance for human exposure assessment considering BMIs are the primary food source of many fish.

Legacy and Emerging Per- and Polyfluoroalkyl Substances: Analytical Techniques, Environmental Fate, and Health Effects.

Due to their unique chemical properties, per- and polyfluoroalkyl substances (PFAS) have been used extensively as industrial surfactants and processing aids. While several types of PFAS have been voluntarily phased out by their manufacturers, these chemicals continue to be of ecological and public health concern due to their persistence in the environment and their presence in living organisms. Moreover, while the compounds referred to as "legacy" PFAS remain in the environment, alternative compounds have emerged as replacements for their legacy predecessors and are now detected in numerous matrices. In this review, we discuss the historical uses of PFAS, recent advances in analytical techniques for analysis of these compounds, and the fate of PFAS in the environment. In addition, we evaluate current biomonitoring studies of human exposure to legacy and emerging PFAS and examine the associations of PFAS exposure with human health impacts, including cancer- and non-cancer-related outcomes. Special focus is given to short-chain perfluoroalkyl acids (PFAAs) and ether-substituted, polyfluoroalkyl alternatives including hexafluoropropylene oxide dimer acid (HFPO-DA; tradename GenX), 4,8-dioxa-3H-perfluorononanoic acid (DONA), and 6:2 chlorinated polyfluoroethersulfonic acid (6:2 Cl-PFESA; tradename F-53B).

Enhanced Sensitivity for the Analysis of Perfluoroethercarboxylic Acids Using LC-ESI-MS/MS: Effects of Probe Position, Mobile Phase Additive, and Capillary Voltage.

Perfluoroethercarboxylic acids (PFECAs) have recently emerged as replacements for toxic per- and polyfluorinated alkyl substances (PFAS) including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Compared with other PFAS, many PFECAs including hexafluoropropylene oxide dimer acid (HFPO-DA, trade name GenX) exhibit poor sensitivity during analysis using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) and are therefore often difficult to quantify. This study examined changes in ESI probe position, mobile phase additive, and capillary voltage with the goal of enhancing PFECA sensitivity. In addition, the relative contributions of existing mechanistic theories for PFAS ionization during ESI are discussed. Results indicated that the LC-ESI-MS/MS sensitivity for 9 PFECAs can be improved significantly by altering the ESI probe position. At the optimal probe position, lowering the capillary voltage from 2.0 to 0.5 kV universally enhanced the LC-ESI-MS/MS sensitivity for PFAS analysis. For most analytes, the use of ammonium bicarbonate rather than ammonium acetate as a mobile phase additive also enhanced the analytical response. These effects have not been previously reported and suggest that many laboratories may be conducting analyses of PFECAs under suboptimal conditions. Using the strategies outlined in this study, PFECAs can be more easily incorporated into comprehensive methods for PFAS analysis. Here, we describe analytical parameters that enhance the sensitivity for some PFECAs by up to 36-fold while maintaining high sensitivity for legacy PFAS. This work not only highlights solutions to mitigate inadequate PFECA sensitivity but also provides insight into the mechanisms underlying PFAS ionization efficiency during LC-ESI-MS/MS.