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 semiquantitation approach. Total PFAS concentrations determined by semiquantitation 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.

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.

Natural source zone depletion (NSZD) has emerged as a practical alternative for restoration of light non‐aqueous phase liquid (LNAPL) sites that are in the later stages of their remediation lifecycle. Due to significant research, the NSZD conceptual model has evolved dramatically in recent years, and methanogenesis is now accepted as a dominant attenuation process (e.g., Lundegard and Johnson ; Ng et al. ). Most of the methane is generated within the pore space adjacent to LNAPL (Ng et al. ) from where it migrates through the unsaturated zone (e.g., Amos and Mayer ), where it is oxidized. While great progress has been made, there are still some important gaps in our understanding of NSZD. NSZD measurements provide little insight on which constituents are actually degrading; it is unclear which rate‐limiting factors that can be manipulated to increase NSZD rates; and how longevity of the bulk LNAPL and its key constituents can be predicted. Various threads of literature were pursued to shed light on some of the questions listed above. Several processes that may influence NSZD or its measurement were identified: temperature, inhibition from acetate buildup, protozoa predation, presence of electron acceptors, inhibition from volatile hydrocarbons, alkalinity/pH, and the availability of nutrients can all affect methanogenesis rates, while factors such as moisture content and soil type can influence its measurement. The methanogenic process appears to have a sequenced utilization of the constituents or chemical classes present in the LNAPL due to varying thermodynamic feasibility, biodegradability, and effects of inhibition, but the bulk NSZD rate appears to remain quasi‐zero order. A simplified version of the reactive transport model presented by Ng et al. has the potential to be a useful tool for predicting the longevity of key LNAPL constituents or chemical fractions, and of bulk LNAPL, but more work is needed to obtain key input parameters such as chemical classes and their biodegradation rates and any potential inhibitions.

Quantifying the overall progress in remediation of contaminated groundwater has been a significant challenge. We utilized the GeoTracker database to evaluate the progress in groundwater remediation from 2001 to 2011 at over 12,000 sites in California with contaminated groundwater. This paper presents an analysis of analytical results from over 2.1 million groundwater samples representing at least $100 million in laboratory analytical costs. Overall, the evaluation of monitoring data shows a large decrease in groundwater concentrations of gasoline constituents. For benzene, half of the sites showed a decrease in concentration of 85% or more. For methyl tert-butyl ether (MTBE), this decrease was 96% and for TBE, 87%. At remediation sites in California, the median source attenuation rate was 0.18/year for benzene and 0.36/year for MTBE, corresponding to half-lives of 3.9 and 1.9 years, respectively. Attenuation rates were positive (i.e., decreasing concentration) for benzene at 76% of sites and for MTBE at 85% of sites. An evaluation of sites with active remediation technologies suggests differences in technology effectiveness. The median attenuation rates for benzene and MTBE are higher at sites with soil vapor extraction or air sparging compared with sites without these technologies. In contrast, there was little difference in attenuation rates at sites with or without soil excavation, dual phase extraction, or in situ enhanced biodegradation. The evaluation of remediation technologies, however, did not evaluate whether specific systems were well designed or implemented and did not control for potential differences in other site factors, such as soil type.