Biotransformation of PFAA Precursors by Oxygenase-Expressing Bacteria in AFFF-Impacted Groundwater and in Pure-Compound Studies with 6:2 FTS and EtFOSE.

Numerous US drinking water aquifers have been contaminated with per- and polyfluoroalkyl substances (PFAS) from fire-fighting and fire-training activities using aqueous film-forming foam (AFFF). These sites often contain other organic compounds, such as fuel hydrocarbons and methane, which may serve as primary substrates for cometabolic (i.e., nongrowth-linked) biotransformation reactions. This work investigates the abilities of AFFF site relevant bacteria (methanotrophs, propanotrophs, octane, pentane, isobutane, toluene, and ammonia oxidizers), known to express oxygenase enzymes when degrading their primary substrates, to biotransform perfluoroalkyl acid (PFAA) precursors to terminal PFAAs. Microcosms containing AFFF-impacted groundwater, 6:2 fluorotelomer sulfonate (6:2 FTS), or N-ethylperfluorooctane sulfonamidoethanol (EtFOSE) were inoculated with the aerobic cultures above and incubated for 4 and 8 weeks at 22 °C. Bottles were sacrificed, extracted, and subjected to target, nontarget, and suspect screening for PFAS. The PFAA precursors 6:2 FTS, N-sulfopropyldimethyl ammoniopropyl perfluorohexane sulfonamide (SPrAmPr-FHxSA), and EtFOSE transformed up to 99, 71, and 93%, respectively, and relevant daughter products, such as the 6:1 fluorotelomer ketone sulfonate (6:1 FTKS), were identified in quantities previously not observed, implicating oxygenase enzymes. This is the first report of a suite of site relevant PFAA precursors being transformed in AFFF-impacted groundwater by bacteria grown on substrates known to induce specific oxygenase enzymes. The data provide crucial insights into the microbial transformation of these compounds in the subsurface.

An Integrated Approach for Determination of Total Per- and Polyfluoroalkyl Substances (PFAS).

Per- and polyfluoroalkyl substances (PFAS) are difficult to analyze in environmental media due challenges such as extraction recovery and lack of analytical standards. The total oxidizable precursor (TOP) assay and suspect screening analysis coupled with semiquantitative (SQ) concentration estimates are two approaches to assess total PFAS in environmental media, but studies are needed to optimize workstreams for total PFAS analysis. This study applied two soil extraction methods, TOP assay, and SQ analysis to three aqueous film-forming foams (AFFFs) and three AFFF-impacted soils. In soils, the total PFAS estimated with results from an extraction method utilizing sequential acidic and basic solvents led to a 35% increase in precursors during TOP assay relative to results from a basic solvent only extraction in one of three soils tested, but concentrations did not increase significantly in remaining soils. Furthermore, sample-specific dilution schemes were required to overcome matrix effects caused by the acidic extraction step that influenced estimates of total PFAS by SQ analysis. The results highlight that there is not an advantage to routine application of an acid extraction step in PFAS-impacted soils. In three AFFFs, suspect screening of post-TOP samples identified eight classes of PFAS present after oxidation. Concentrations of three classes increased, suggesting they are new TOP end points. Concentrations of the remaining five classes either remained constant after TOP or exhibited slight decreases. As a result, combined TOP and SQ workstreams may yield the most representative assessment of total PFAS composition and concentration. The eight classes of PFAS present after TOP did not degrade in harsh conditions. Some are structurally similar to PFCAs and PFSAs and are known to occur in the environment, suggesting a similar degree of persistence and a need for more routine monitoring.

Enhanced Recovery of Per- and Polyfluoroalkyl Substances (PFASs) from Impacted Soils Using Heat Activated Persulfate.

Varying transport potential of cationic, zwitterionic, and anionic per- and polyfluoroalkyl substances (PFASs) may pose challenges for remediation of aqueous film forming foam (AFFF) impacted sites, particularly during groundwater extraction. Slow desorption of stronger sorbing, zwitterionic, and cationic PFASs may cause extended remediation times and rebound in aqueous PFAS concentrations. Persulfate oxidation has the potential to convert a complex mixture of PFASs into a simpler and more recoverable mixture of perfluoroalkyl acids (PFAAs). AFFF-impacted soils were treated with heat-activated persulfate in batch reactors and subjected to 7-day leaching experiments. Soil and water were analyzed using a combination of targeted and high resolution liquid chromatography mass spectrometry techniques as well as the total oxidizable precursors assay. Following oxidation, total PFAS composition showed the expected shift to a higher fraction of PFAAs, and this led to higher total PFAS leaching in pretreated reactors (108-110%) vs control reactors (62-90%). In both pretreated and control soils, precursors that remained following leaching experiments were 61-100% cationic and zwitterionic. Results suggest that persulfate pretreatment of soils has promise as an enhanced recovery technique for remediation of total PFASs in impacted soils. They also demonstrate that PFAS distribution may have been altered at sites where in situ chemical oxidation was applied to treat co-occurring contaminants of concern.

Lithium-ion battery components are at the nexus of sustainable energy and environmental release of per- and polyfluoroalkyl substances.

Lithium-ion batteries (LiBs) are used globally as a key component of clean and sustainable energy infrastructure, and emerging LiB technologies have incorporated a class of per- and polyfluoroalkyl substances (PFAS) known as bis-perfluoroalkyl sulfonimides (bis-FASIs). PFAS are recognized internationally as recalcitrant contaminants, a subset of which are known to be mobile and toxic, but little is known about environmental impacts of bis-FASIs released during LiB manufacture, use, and disposal. Here we demonstrate that environmental concentrations proximal to manufacturers, ecotoxicity, and treatability of bis-FASIs are comparable to PFAS such as perfluorooctanoic acid that are now prohibited and highly regulated worldwide, and we confirm the clean energy sector as an unrecognized and potentially growing source of international PFAS release. Results underscore that environmental impacts of clean energy infrastructure merit scrutiny to ensure that reduced CO2 emissions are not achieved at the expense of increasing global releases of persistent organic pollutants.

Per- and polyfluoroalkyl substances (PFAS) in grocery store foods: method optimization, occurrence, and exposure assessment.

Dietary exposure to per- and polyfluoroalkyl substances (PFAS) is poorly understood. Evaluating PFAS in food is complicated by the need to evaluate varied matrices and a lack of a standard, matrix-specific sample extraction methods. Prior food studies implemented universal rather than matrix-specific extraction approaches, which may yield false negatives and an underestimation of PFAS dietary exposure if methods are not suitable to all matrices. Here the objectives were to screen and optimize PFAS extraction methods for plants, tissues, and dairy; apply optimized extraction methods to a grocery store food survey; and compare estimated exposure to published reference doses (RfDs). Optimized, matrix-specific extractions generally yielded internal standard recoveries of 50-150% and matrix spike recoveries of 70-130%. The frequency of PFAS detection in grocery store foods (16 of 22 products) was higher than in previous work. PFAS were detected at concentrations of 10 ng kgdw-1 (perfluorobutane sulfonate; washed green beans and perfluorohexanoic acid; unwashed tomato) to 2680 ng kgdw-1 (perfluorohexane sulfonate; radish). Concentrations of perfluorooctanoic acid (PFOA) in carrots, lettuce, radish, and canned green beans yielded median exposure intake (EI) values of 0.016-0.240 ng per kgbw-day, which exceeded the EPA RfD (0.0015 ng per kgbw-day). Washing reduced radish PFOA concentrations below detection, but EIs at the reporting limit still exceeded the RfD. The combination of improved data quality and greater frequency of PFAS detection vs. prior studies plus EI > RfD for some PFAS suggests a need for matrix-specific extractions and analysis of PFAS in additional grocery store foods from broader geographic regions.