For several decades, a common processing aid in the production of fluoropolymers was the ammonium salt of perfluorooctanoic acid (PFOA). Because PFOA is persistent, bioaccumulative, and toxic, its production and use are being phased out in the United States. In 2009, the US Environmental Protection Agency stipulated conditions for the manufacture and commercial use of GenX, a PFOA replacement. While GenX is produced for commercial purposes, the acid form of GenX is also generated as a byproduct during the production of fluoromonomers. The discovery of high concentrations of GenX and related perfluoroalkyl ether acids (PFEAs) in the Cape Fear River and in finished drinking water of more than 200,000 North Carolina residents required quick action by researchers, regulators, public health officials, commercial laboratories, drinking water providers, and consulting engineers. Information about sources and toxicity of GenX as well as an analytical method for the detection of GenX and eight related PFEAs is presented. GenX/PFEA occurrence in water and GenX/PFEA removal by different drinking water treatment processes are also discussed.

Per-and polyfluoroalkyl substances (PFASs) are widely used anthropogenic chemicals. The PFAS class includes almost 5000 registered compounds, but analytical methods are lacking for most PFASs. The total oxidizable precursor (TOP) assay was developed to indirectly quantify unknown PFASs that are precursors to commonly measured perfluoroalkyl acids. To understand the behavior of recently identified per-and polyfluoroalkyl ether acids (PFEAs), including fluorinated replacements and manufacturing byproducts, we determined the fate of 15 PFEAs in the TOP assay. Ten perfluoroalkyl ether acids and a chlorinated polyfluoroalkyl ether acid (F-53B) were stable in the TOP assay and represent terminal products that are likely as persistent as historically used PFASs. Adding perfluoroalkyl ether acids and F-53B to the target analyte list for the TOP assay is recommended to capture a higher percentage of the total PFAS concentration in environmental samples. In contrast, polyfluoroalkyl ether acids with a -O-CFH-moiety were oxidized, typically to products that could not be identified by liquid chromatography and highresolution mass spectrometry. Application of the TOP assay in its proposed enhanced form revealed high levels of PFEAs, the presence of precursors that form perfluoroalkyl carboxylic acids, and the absence of precursors that form PFEAs in surface water impacted by PFAScontaining wastewater discharges.

Per-and polyfluoroalkyl substances (PFAS) are an ensemble of persistent organic pollutants of global interest because of their associations with adverse health outcomes. Currently, environmental PFAS pollution is prolific as a result of the widespread manufacturing of these compounds and their chemical persistence. In this work, we demonstrate the advantages of adding ion mobility spectrometry (IMS) separation to existing LC-MS workflows for PFAS analysis. Using a commercially available drift tube IMS-MS, we characterized PFAS species and isomeric content both in analytical standards and wastewater samples. Molecular trendlines based on intrinsic mass and structural relationships were also explored for the PFAS subclasses (e.g. PFSA, PFCA, etc.). Results from rapid IMS-MS analyses provided a link between mass and collision cross sections (CCS) for specific PFAS families and are linked to compositional differences in molecular structure. In addition, CCS values provide additional confidence of annotating prioritized features in untargeted screening studies for potential environmental pollutants. Results from this study show that the IMS separation provides novel information to support traditional LC-MS PFAS analyses and will greatly benefit the evaluation of unknown pollutants in future environmental studies.

We quantified per-and polyfluoroalkyl substance (PFAS) transport from groundwater to five tributaries of the Cape Fear River near a PFAS manufacturing facility in North Carolina (USA). Hydrologic and PFAS data were coupled to quantify PFAS fluxes from groundwater to the tributaries. Up to 29 PFAS were analyzed, including perfluoroalkyl acids and recently identified fluoroethers. Total quantified PFAS (ΣPFAS) in groundwater was 20−4773 ng/L (mean = 1863 ng/L); the range for stream water was 426−3617 ng/L (mean = 1717 ng/L). Eight PFAS constituted 98% of ΣPFAS; perfluoro-2-(perfluoromethoxy)propanoic acid (PMPA) and hexafluoropropylene oxide dimer acid (GenX) accounted for 61%. For PFAS discharge from groundwater to one tributary, values estimated from stream water measurements (18 ± 4 kg/yr) were similar to those from groundwater measurements in streambeds (22−25 ± 5 kg/yr). At baseflow, 32 ± 7 kg/yr of PFAS discharged from groundwater to the five tributaries, eventually reaching the Cape Fear River. Given the PFAS emission timeline at the site, groundwater data suggest the abundant fluoroethers moved through the subsurface to streams in ≪50 yr. Discharge of contaminated groundwater may lead to long-term contamination of surface water and impacts on downstream drinking water supplies. This work addresses a gap in the PFAS literature: quantifying PFAS mass transfer between groundwater and surface water using field data.

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