AbstractUnderstanding the retention of per‐ and polyfluoroalkyl substances (PFAS) in the vadose zone is vital to the management of impacted sites. This paper examines PFAS retention in the unsaturated zone above the water table using a mathematical model, MODFLOW‐USG‐Transport PFAS or “USGT‐PFAS.” The USGT‐PFAS model incorporates adsorption onto air‐water interfaces, providing a more comprehensive understanding of PFAS retention near the water table and release to groundwater. Modeling of a hypothetical perfluorooctane sulfonic acid (PFOS) site under various idealized site conditions illustrated that the impacts on PFOS retention from smallest to largest were water table fluctuations, low episodic recharge, constant recharge, moderate episodic recharge, constant recharge with water table fluctuations, and high episodic recharge. PFOS retention also varied by sand type, with greater retention occurring in simulations incorporating coarse sand with low capillary potential versus fine sand with high capillary potential. PFAS management strategies were also explored, including the adaptation of gas sparging, a method traditionally used for volatile organic compounds. Gas sparging can concentrate PFAS in groundwater and the vadose zone around the water table, facilitating retention or removal. Model simulations for a simplified hypothetical site demonstrated that PFAS can be substantially retained in the unsaturated zone once gas sparging results in an upward concentration of PFAS in groundwater and the unsaturated zone near the water table. Modeling can aid in understanding PFAS behavior but requires simulation of multiple interrelated processes to correctly predict PFAS fate and transport in subsurface conditions.
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