Air-water interfacial collapse and rate-limited solid desorption control Perfluoroalkyl acid leaching from the vadose zone.

Some Per- and polyfluoroalkyl substances (PFAS) are strongly retained in the vadose zone due to their sorption to both soils and air-water interfaces. While significant research has been dedicated to understanding equilibrium behavior for these multi-phase retention processes, leaching and desorption from aqueous film-forming foam (AFFF) impacted soils under field relevant conditions can exhibit significant deviations from equilibrium. Herein, laboratory column studies using field collected AFFF-impacted soils were employed to examine the leaching of perfluoroalkyl acids (PFAAs) under simulated rainfall conditions. The HYDRUS 1-D model was calibrated to estimate the unsaturated hydraulic properties of the soil in a layered system using multiple boundary condtions. Forward simulations of equilibrium PFAS partitioning using the HYDRUS model and simplified mass balance calculations showed good agreement with the net PFAS mass flux out of the column. However, neither were able to predict the PFAS concentrations in the leached porewater. To better understand the mechanisms controlling the leaching behavior, the HYDRUS 1-D two-site leaching model incorporating solid phase rate limitation and equilibrium air-water interfacial partitioning was employed. Three variations of the novel model incorporating different forms of equilibrium air-water interfacial partitioning were considered using built-in numerical inversion. Results of numerical inversion show that a combination of air-water interfacial collapse and rate-limited desorption from soils can better predict the unique leaching behavior exhibited by PFAAs in AFFF-impacted soils. A sensitivity analysis of the initial conditions and rate-limited desorption terms was conducted to assess the agreement of the model with measured data. The models demonstrated herein show that, under some circumstances, laboratory equilibrium partitioning data can provide a reasonable estimation of total mass leaching, but fail to account for the significant rate-limited, non-Fickian transport which affect PFAA leaching to groundwater in unsaturated soils.