Influence of kinetic air-water interfacial partitioning on unsaturated transport of PFAS in sandy soils

This study investigates the impact of kinetic air-water partitioning on the transport of perfluoroalkyl substances (PFAS) within homogeneous and heterogeneous sandy vadose zones under transient unsaturated flow conditions. These experimental conditions are realistic for field behavior, where transient flow foments the continual growth and collapse of air-water interfaces (AWIs), and where layered heterogenous conditions enhance the perturbations of AWIs. Short-chain PFAS behave like conservative tracers with negligible air-water interface partitioning, whereas longer-chain PFAS demonstrate non-equilibrium retention behavior, especially in heterogeneous media. AWI partitioning kinetics were found to be important in controlling PFAS transport and mass flux, particularly during PFAS sorption to the air-water interface, which results because of the different nature and more rapid changes in AWI during drainage, wherein PFAS are moving toward the interface to achieve equilibrium, than during imbibition, where PFAS are leaving the interface to achieve equilibrium. Neglecting these kinetic AWI sorption processes can result in an underestimate of the PFAS transport velocities and mass flux reaching the water table. The presence of trapped air may also inhibit PFAS partitioning in a similar manner by causing longer diffusion paths from bulk water to a portion of the AWIs. The modified HYDRUS effectively captured the transport processes and provided an excellent match to the measured breakthrough curves. To assess relevance using realistic transient infiltration rates, simulations were conducted using precipitation data from an actual site. The results showed that accounting for kinetic AWI partitioning increases the cumulative PFOS mass flux to groundwater by a factor of 2.3 compared to equilibrium conditions, significantly impacting PFAS porewater concentrations. This difference was threefold under experimental conditions, suggesting that the importance of kinetic effects may vary significantly over the long term and under different climatic conditions or soil types, due to their strong dependence on water flux.