Anastasia Nickerson

Per- and polyfluoroalkyl substances (PFASs) are frequently found at high concentrations in the subsurface of aqueous film forming foam (AFFF)-impacted sites. Geochemical parameters affect the release of PFASs from source area soils into groundwater but have not been extensively studied for soils that have been historically impacted with AFFF. This study investigated the effects of pH and salt concentrations on release of anionic and zwitterionic PFASs from AFFF-impacted soils in flow-through saturated columns. High pH (10) columns with elevated sodium concentrations had higher cumulative masses eluted of several PFASs compared to pH 3 and pH 7 columns with lower sodium concentrations, likely caused by changes to soil organic matter surface charge. Four PFASs (e.g. 4:2 fluorotelomer sulfonate, perfluorobutane sulfonamido acetic acid) eluted significantly earlier in both pH 3 and pH 10/high NaCl columns compared to pH 7 columns. The results of this study suggest that shifts in pH for soils located at AFFF-impacted sites – particularly raising the pH – may mobilize sorbed PFASs, specifically longer-chain and zwitterionic compounds that are typically strongly sorbed to soil.

Poly- and perfluorinated alkyl substances (PFASs) frequently co-occur with fuel-derived contaminants because of the use of aqueous film-forming foam (AFFF). Biosparging is a common remediation technology that injects oxygen into the saturated zone to encourage aerobic biodegradation, thereby altering aquifer redox conditions and potentially facilitating the biotransformation of polyfluorinated substances. Between 136 and 280 pore volumes of nitrogen-sparged or oxygen-sparged artificial groundwater amended with toluene were pumped through four saturated, AFFF-impacted soil columns to assess impacts on PFAS release and transformation. Column effluents and soils were analyzed for PFASs by high-resolution mass spectrometry. Significantly higher concentrations of five PFASs eluted from O₂-sparged columns compared to N₂-sparged columns shortly after sparging was initiated. The mass fractions eluted of many zwitterionic, sulfonamide-based PFASs were higher in both sets of columns than unaltered, non-biostimulated columns. Mass balance calculations suggested the transformation of sulfonamide-based precursors to perfluorinated sulfonamides (i.e., perfluorohexanesulfonamide) in oxygen- and nitrogen-sparged columns: recoveries of perfluorinated sulfonamides were 158–235% for C3–C6 homologs but recoveries of several prominent sulfonamide-based zwitterions were low. For example, the recovery of n-carboxyethyldimethyl-ammoniopropyl perfluorohexanesulfonamide was 9–13%. These results suggest biosparging can enhance the transformation and release of PFASs in saturated soils, which has important implications for site characterization and remediation.

Per- and polyfluoroalkyl substances (PFASs) are highly mobile in the saturated subsurface, yet aqueous film-forming foam (AFFF)-impacted source zones appear to be long lasting PFAS reservoirs. This study examined the release of over one hundred anionic and zwitterionic PFASs from two AFFF-impacted surface soils under saturated conditions with packed soil columns. Perfluoroalkyl acids (PFAAs) were released more rapidly than their polyfluorinated precursors, while anionic PFASs that were present in partially uncharged states were released more slowly than PFASs that were present entirely as anions, as were zwitterionic PFASs with terminal cationic functional groups when compared with analogous zwitterions with only anionic terminal groups. Nonideal transport was observed in both per- and polyfluorinated classes, as soil column effluent concentrations of slowly released PFASs increased by up to 107-fold with sustained artificial groundwater flow. A flow-interruption experiment suggested the influence of rate-limited desorption on diverse PFAS classes, including PFAAs with as few as four perfluorinated carbons. These results suggest that during infiltration the slow, rate-limited desorption of anionic and zwitterionic PFAA precursors may result in these compounds comprising an increasingly large fraction of the remaining PFASs in AFFF-impacted surface soils.

Soil and groundwater from an aqueous film-forming foam (AFFF)-impacted site were sampled at high resolution (n = 105 for soil, n = 58 for groundwater) and analyzed for an extensive list of anionic, zwitterionic, and cationic poly- and perfluoroalkyl substances (PFASs). Spatial trends for perfluoroalkyl acids and many precursors enabled a better understanding of PFAS composition, transport, and transformation. All PFASs without analytical standards were semi-quantified. Summed PFAS and individual PFAS concentrations were often higher at depth than near the surface in soil and groundwater. Zwitterionic and cationic compounds composed a majority of the total PFAS mass (up to 97%) in firefighter training area (FTA) soil. Composition of PFAS class, chain length, and structural isomers changed with depth and distance from the FTA, suggesting in situ transformation and differential transport. The percentage of branched perfluorooctane sulfonate increased with depth, consistent with differential isomeric transport. However, linear perfluorooctanoic acid (PFOA) was enriched, suggesting fluorotelomer precursor transformation to linear PFOA. Perfluorohexane sulfonamide, a potential transformation product of sulfonamide-based PFASs, was present at high concentrations (maximum 448 ng/g in soil, 3.4 mg/L in groundwater). Precursor compounds may create long-term sources of perfluoroalkyl acids, although many pathways remain unknown; precursor analysis is critical for PFAS fate and transport understanding.

Transport of poly- and perfluoroalkyl substances (PFAS) at aqueous film-forming foam (AFFF)-impacted sites is limited by various processes that can retain PFAS mass within the source area. This study used concentration data obtained via a high-resolution sampling and analytical protocol to estimate the PFAS mass distribution in source and downgradient areas of a former firefighter training area. The total PFAS mass present at the site was approximately 222 kg, with 106 kg as perfluoroalkyl acids (PFAAs) and 116 kg as polyfluorinated precursors. Zwitterionic and cationic PFAS represented 83% of the total precursor mass and were found primarily in the source and up/side-gradient areas (75%), likely due to preferential hydrophobic partitioning, electrostatic interactions, and diffusion into lower-permeability soils. Based on the release history and the high percentage of total PFAS mass represented by precursors (primarily electrochemical fluorination-derived compounds), the estimated conversion rate of precursors to PFAAs was less than 2% annually. Eighty-two percent of the total PFAS mass was encountered in lower-permeability soils, which limited the potential for advection and transformation. This contributed to a 99% decrease in the mass discharge rate at the far-downgradient plume (0.048 kg/yr compared to the near-source area (3.6 kg/yr)). The results provide field-scale evidence of the importance of these PFAS retention processes at sites where AFFF has been released.

Poly- and perfluoroalkyl substances (PFASs) derived from aqueous film-forming foam (AFFF) are increasingly recognized as groundwater contaminants, though the composition and distribution of AFFF-derived PFASs associated with soils and subsurface sediments remain largely unknown. This is particularly true for zwitterionic and cationic PFASs, which may be incompletely extracted from subsurface solids by analytical methods developed for anionic PFASs. Therefore, a method involving sequential basic and acidic methanol extractions was developed and evaluated for recovery of anionic, cationic, and zwitterionic PFASs from field-collected, AFFF-impacted soils. The method was validated by spike recovery experiments with equilibrated soil-water-AFFF and analytical standards. To determine the relative importance of PFASs lacking commercially available analytical standards, their concentrations were estimated by a novel semi-quantitation approach. Total PFAS concentrations determined by semi-quantitation were compared with concentrations determined by the total oxidizable precursor assay. Finally, the described method was applied to two soil cores from former fire-training areas in which cations and zwitterions were found to contribute up to 97% of the total PFAS mass. This result demonstrates the need for extraction and analysis methods, such as the ones presented here, that are capable of quantifying cationic and zwitterionic PFASs in AFFF-impacted source zone soils.