Effects of Organic Matter, Iron (Hydr)oxides, and Iron Reductive Dissolution on Per- and Polyfluoroalkyl Substances...

Aqueous film-forming foams (AFFFs) are a major source of per- and polyfluoroalkyl substances (PFAS) contamination in groundwater and soil. Although PFAS sorption is known to depend on the properties of solid matrices, the roles of organic matter and iron (hydr)oxides remain poorly understood, especially for polyfluorinated compounds. To investigate the interplay between particulate organic matter and iron (hydr)oxides in PFAS-contaminated subsurface environments, we studied the partitioning of neutral, cationic, and anionic PFAS in AFFF to well-characterized solids using the mixed-mode solid-phase extraction (SPE) technique combined with the total oxidizable precursor (TOP) assay. Our results indicated that organic matter consistently enhanced PFAS sorption. In contrast, the effect of goethite, a representative iron-containing mineral, on PFAS sorption varied with PFAS charge. Using three different AFFFs, we found that anionic PFAS exhibited strong sorption regardless of organic matter content, while cationic and zwitterionic PFAS sorbed poorly at circumneutral pH. These trends were more pronounced for iron-coated sand, which showed higher affinity for anionic PFAS. Treatment with ascorbate, a mild reductant, released PFAS associated with iron (hydr)oxides. These findings highlight the importance of iron (hydr)oxides in the retention of anionic PFAS and could be leveraged to manage PFAS mobility through subsurface iron amendments or in situ iron (hydr)oxide formation/dissolution.