Preferential Retention and Transport of Perfluorooctanesulfonic Acid in a Dolomite Aquifer

Per- and polyfluoroalkyl substances (PFAS) can represent a significant human health risk if present in aquifers used as a drinking water source. Accurate assessment of PFAS exposure risks requires an improved understanding of field-scale PFAS transport in groundwater. Activities at a former firefighter training site in University Park, Pennsylvania introduced perfluorooctanesulfonic acid (PFOS) to the underlying dolomite aquifer. Groundwater sampling from 2015 to 2018 delineated a PFOS plume with two concentration maxima located approximately 20 and approximately 220 m downgradient of the training site, separated by a zone of lower concentrations. We use a combination of analytical and numerical models, informed by independent measurements of aquifer porosity, hydraulic conductivity, and organic carbon content, to interpret the field observations. Our analysis demonstrates that preferential retention and transport resulting from simple heterogeneity in bedrock sorption, as caused by organic carbon (OC) content variability, provides a plausible explanation for plume separation. Dissolved PFOS partitions strongly to organic solids (high K_oc), so even a small OC (<1 wt%) significantly retards PFOS transport, whereas zones with little to no OC allow for transport rates that approximate those of a conservative solute. Our work highlights an important consideration for modeling the groundwater transport of PFOS, and other compounds with high K_oc. In aquifers with discrete layers of varying OC, models using a uniform site-average OC will underestimate transport distances, thereby misrepresenting exposure risks for downgradient communities.