RESUMO
Detection and monitoring of per- and polyfluoroalkyl substances (PFAS) in aquatic environments has become an increasingly higher priority of regulatory agencies as public concern for human intake of these chemicals continues to grow. While many methods utilize active sampling strategies ("grab samples") for precise PFAS quantitation, here we evaluate the efficacy of low-cost passive sampling devices (Solid Phase Adsorption Toxin Tracking, or SPATTs) for spatial and temporal PFAS assessment of aquatic systems. For this study, passive samplers were initially deployed in North Carolina along the Cape Fear River during the summer and fall of 2016 and 2017. These were originally intended for the detection of microcystins and monitoring potentially harmful algal blooms, though this period also coincided with occurrences of PFAS discharge from a local fluorochemical manufacturer into the river. Additional samplers were then deployed in 2022 to evaluate changes in PFAS fingerprint and abundances. Assessment of PFAS showed legacy compounds were observed across almost all sampling sites over all 3 years (PFHxS, PFOS, PFHxA, etc.), while emerging replacement PFAS (e.g., Nafion byproducts) were predominantly localized downstream from the manufacturer. Furthermore, samplers deployed downstream from the manufacturer in 2022 noted sharp decreases in observed signal for replacement PFAS in comparison to samplers deployed in 2016 and 2017, indicating mitigation and remediation efforts in the area were able to reduce localized fluorochemical contamination.
RESUMO
Per- and polyfluoroalkyl substances (PFAS) are a class of thousands of man-made chemicals that are persistent and highly stable in the environment. The diverse structures of PFAS give them different chemical properties that influence their solubility in different environmental matrices and biological tissues. PFAS in drinking water have been extensively studied, but information on their presence in fish and other exposure routes is limited. To address this, a non-targeted analysis using liquid chromatography, ion mobility spectrometry, and mass spectrometry (LC-IMS-MS) was performed to evaluate PFAS in fish fillets from in central North Carolina and compare with PFAS data from previously published water. A total of 22 different PFAS were detected in the fillets, including only 4 of the PFAS reported in water. Both more PFAS types and higher concentrations were observed in fish caught near a known PFAS point-source compared to those from a reservoir used for drinking water and recreation. Median fillet PFOS levels were 54 ppb in fish closest to the point source and 14-20 ppb in fish from the reservoir. Thus, future PFAS monitoring should include both targeted and non-targeted analyses of both water and fish to increase understanding of human exposure risks and ecosystem impacts. SYNOPSIS: Fish fillet samples were collected from five sites in North Carolina. PFAS were detected in all samples and differences in analytes and abundances were observed at the different sites. GRAPHICAL ABSTRACT: For use in table of contents only.
RESUMO
Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative chemicals that can be toxic at very low levels. Many of these compounds have unusual chemical properties that can have a large impact on analytical methods intended to quantitate them. When analyzing environmental samples, concentrating extraction eluents can greatly increase the sensitivity of PFAS extraction and analysis workflows. However, data on PFAS stability when evaporated under vacuum drying conditions are lacking. In this study two common sample preparation methods were replicated (methanol or methanolic ammonium hydroxide) to determine if PFAS material would undergo any observable loss during vacuum evaporation. Standards containing 49 different analytes from 7 different PFAS classes were evaporated to dryness under vacuum either with or without heat and reconstituted using one of two methods. It was found that recovery of some classes (e.g. PFSA, PFESA, FTS) was not greatly impacted by evaporation conditions or reconstitution method. Some analytes such as the very long chain PFCAs were not affected by evaporation conditions but saw drastic differences in recovery depending on the reconstitution method. Others analytes, for example PFSAms, experienced significant loss during evaporation that could not be mitigated by the chosen reconstitution method. This difference could be due to the number of fluorines present on the compound which correlated with a compound's hydrophobicity. Due to these findings, it is recommend that researchers consider PFAS class, chain length, and fluorine number when designing concentration and reconstitution protocols for PFAS to ensure conditions are optimal for the specific analytes of interest.
