Impact of a Hydrocarbon Surfactant on the Retention and Transport of Perfluorooctanoic Acid in Saturated and Unsaturated Porous Media

The transport and retention behavior of perfluorooctanoic acid (PFOA) in the presence of a hydrocarbon surfactant under saturated and unsaturated conditions was investigated. Miscible-displacement transport experiments were conducted at different PFOA and sodium dodecyl sulfate (SDS) input ratios to determine the impact of SDS on PFOA adsorption at solid-water and air-water interfaces. A numerical flow and transport model was employed to simulate the experiments. The PFOA breakthrough curves for unsaturated conditions exhibited greater retardation compared to those for saturated conditions in all cases, owing to air-water interfacial adsorption. The retardation factor for PFOA with a low concentration of SDS (PFOA-SDS ratio of 10:1) was similar to that for PFOA without SDS under unsaturated conditions. Conversely, retardation was greater in the presence of higher levels of SDS (1:1 and 1:10) with retardation factors increasing from 2.4 to 2.9 and 3.6 under unsaturated conditions due to enhanced adsorption at the solid-water and air-water interfaces. The low concentration of SDS had no measurable impact on PFOA air-water interfacial adsorption coefficients (K_ia) determined from the transport experiments. The presence of SDS at the higher PFOA-SDS concentration ratios increased the surface activity of PFOA, with transport-determined K_ia values increased by 27 and 139%, respectively. The model provided very good independently predicted simulations of the measured breakthrough curves and showed that PFOA and SDS experienced various degrees of differential transport during the experiments. These results have implications for the characterization and modeling of poly-fluoroalkyl substances (PFAS) migration potential at sites wherein PFAS and hydrocarbon surfactants co-occur.