Poly- and perfluoroalkyl substances (PFASs) are a class of fluorinated chemicals that are utilized in firefighting and have been reported in groundwater and soil at several firefighter training areas. In this study, soil and groundwater samples were collected from across a former firefighter training area to examine the extent to which remedial activities have altered the composition and spatial distribution of PFASs in the subsurface. Log Koc values for perfluoroalkyl acids (PFAAs), estimated from analysis of paired samples of groundwater and aquifer solids, indicated that solid/water partitioning was not entirely consistent with predictions based on laboratory studies. Differential PFAA transport was not strongly evident in the subsurface, likely due to remediation-induced conditions. When compared to the surface soil spatial distributions, the relative concentrations of perfluorooctanesulfonate (PFOS) and PFAA precursors in groundwater strongly suggest that remedial activities altered the subsurface PFAS distribution, presumably through significant pumping of groundwater and transformation of precursors to PFAAs. Additional evidence for transformation of PFAA precursors during remediation included elevated ratios of perfluorohexanesulfonate (PFHxS) to PFOS in groundwater near oxygen sparging wells.

Ultraviolet photochemical reaction of sulfite (SO3 2–) photosensitizer generates strongly reducing hydrated electrons (eaq –; NHE = −2.9 V) that have been shown to effectively degrade individual per- and polyfluoroalkyl substances (PFASs), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). However, treatment of complex PFAS mixtures in aqueous film-forming foam (AFFF) remains largely unknown. Here, UV-sulfite was applied to a diluted AFFF to characterize eaq – reactions with 15 PFASs identified by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) targeted analysis. Results show that reactivity varies widely among PFASs, but reaction rates observed for individual PFASs in AFFF are similar to rates observed in single-solute experiments. While some structures, including long-chain perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) were readily degraded, other structures, most notably short-chain PFSAs and fluorotelomer sulfonic acids (FTSs), were more recalcitrant. This finding is consistent with results showing incomplete fluoride ion release (up to 53% of the F content in AFFF) during reactions. Furthermore, results show that selected PFSAs, PFCAs, and FTSs can form as transient intermediates or unreactive end-products via eaq – reactions with precursor structures in AFFF. These results indicate that while UV-sulfite treatment can be effective for treating PFOS and PFOA to meet health advisory levels, remediation of the wider range of PFASs in AFFF will prove more challenging.

Bench-scale experiments were performed to assess uptake of poly- and perfluoroalkyl substances (PFAS), both single compounds and mixtures, at the air–water interface. The focus was on evaluating uptake at field-relevant PFAS concentrations (<2 × 10–4 mol m–3 or 0.1 mg L–1), assessing the impacts of various PFAS mixtures, and quantifying the impacts of background NaCl concentrations. Both interfacial tension measurements and direct quantification of PFAS mass sorbed at the air–water interface in water films were used to evaluate PFAS interfacial partitioning. Results showed that a Freundlich-based model, rather than a Langmuir-based model, described perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) interfacial uptake. At lower and field-relevant PFOS and PFOA concentrations, the Langmuir-based model underpredicted interfacial uptake by up to several orders of magnitude. The interfacial partition coefficient, k aw, increased as PFAS concentrations decreased. Results also showed that the interfacial tension and interfacial uptake of PFAS mixtures were (within a factor of 2) predicted based on the single solute systems assuming ideal dilute behavior. Furthermore, the addition of NaCl at concentrations of up to 0.01 M increased PFOS uptake by less than a factor of 2 at field-relevant PFOS concentrations. The results presented herein have important implications for PFAS migration in unsaturated soils as well as for remedial technologies that rely on PFAS interfacial sorption, particularly at field-relevant PFAS concentrations.

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Abstract. A new experimental method was developed to determine air-water interfacial area as a function of capillary pressure and water saturation in unsaturated porous media. The surfactant sodium dodecyl benzene sulfonate (SDBS) was used in equilibrium column adsorption experiments to estimate air-water interfacial area for water saturations (milliliter water per milliliter void) ranging from 0.05 to 1.0 and pressures ranging from 0 to 20 cm of water. A comparison was made between columns which were equilibrated under gravity drainage versus columns equilibrated under secondary imbibition. Gravity drainage experiments showed the air-water interfacial area decreased linearly with saturation, while imbibition experiments showed a more complex nonmonotonic relation to the saturation. The interfacial area data are then compared with existing network models. IntroductionThe distribution and transport of contaminants among phases in unsaturated porous media may often be controlled