Modeling the Influence of Coastal Site Characteristics on <scp>PFAS</scp> in Situ Remediation

The potential performance of a hypothetical colloidal-activated carbon (CAC) in situ remedy for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in groundwater in coastal zones was evaluated using estimated hydrogeologic and geochemical parameters for a coastal site in the United States. With these parameters, a reactive transport model (ISR-MT3DMS) was used to assess the effects of tidal fluctuations and near-shore geochemistry on CAC performance. The average near-shore ionic strength of 84 mM at the site was conservatively estimated to result in an increase in the adsorption of PFOA to CAC by about 50% relative to non-coastal sites with ionic strength <10 mM. The modeling also confirmed the hypothesis that tidally induced groundwater flow reversals near the shore would result in the accumulation of PFOA at the downgradient edge of the CAC zone. Slow desorption of PFOA from this downgradient CAC boundary may sustain downgradient plume concentrations above a strict cleanup criterion (e.g., USEPA MCL of 0.004 μg/L), for decades; however, there was still a large PFOA mass flux reduction (>99.9%) achieved after several decades at the shore. CAC longevity was substantially greater for PFOS with a similar source concentration; however, the higher PFOS distribution coefficient (K_d) in soil downgradient from the CAC zone resulted in substantially longer flushing times. It is recommended that short-term remedial action objectives for CAC remedies at coastal sites be based on mass flux reduction targets over a period of several decades, given the demonstrated challenges in trying to achieve very low cleanup criteria downgradient of a CAC zone in the short term.