Contribution of Nonaqueous-Phase Liquids to the Retention and Transport of Per and Polyfluoroalkyl Substances (PFAS) in Porous Media

Per and polyfluoroalkyl substances (PFAS) cocontamination with nonaqueous-phase organic liquids (NAPLs) has been observed or suspected at various sites, particularly at fire-training areas at which aqueous film-forming foams (AFFFs) were applied. The objectives of this study are to (1) delineate the relative significance of specific PFAS-NAPL processes on PFAS retention, including partitioning into the bulk NAPL phase and adsorption to the NAPL–water interface; (2) investigate the influence of NAPL properties, saturation, and mass-transfer constraints on PFAS retention; and (3) determine whether PFAS may impact NAPL distribution through mobilization or dissolution. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are used as representative PFAS, and trichloroethene (TCE) and decane are used as representative NAPLs. NAPL–water interfacial adsorption was quantified with NAPL–water interfacial-tension measurements; partitioning into NAPL was quantified with batch experiments, and retardation factors (R) in the absence and presence of residual NAPL were determined with miscible-displacement transport experiments. R values increased in the presence of residual NAPL, with adsorption to the NAPL–water interface accounting for as much as ∼77% of retention and solid-phase adsorption also significantly contributing to retention. Additionally, this study provides the first QSPR analysis focused on NAPL–water interfacial adsorption coefficients, with results consistent with those from previous air–water studies. Lastly, this initial investigation into PFAS impacts on NAPL behavior determined that PFOS/PFOA are unlikely to enhance solubilization or mobilization of NAPL under the conditions present at many AFFF legacy sites.