Per‐ and polyfluoroalkyl substances (PFAS) are emerging contaminants of critical concern. As surfactants, PFAS tend to accumulate at air‐water interfaces and may stay in the vadose zone for long times before contaminating groundwater. Yet not well understood, the extent of retention in the vadose zone has critical implications for risk management and remediation strategies. We present the first mathematical model that accounts for surfactant‐induced flow and solid‐phase and air‐water interfacial adsorption. We apply the model to simulate PFOS (a PFAS compound of primary concern) transport in the vadose zone at a model fire‐training area site impacted by aqueous film‐forming foam (AFFF). Air‐water interfacial adsorption is shown to have a significant impact—amplified by the low water content due to gravity drainage—total retardation factors range from 233 to 1,355 for the sand and 146 to 792 for the soil used in the study. The simulations illustrate it can take several decades or longer for PFOS to reach groundwater. Counterintuitively, the lower water content in the sand—due to stronger drainage and weaker capillary retention—leads to retardation factors greater than for the soil. Also, most PFOS is adsorbed at air‐water interfaces with only 1–2% in the aqueous phase. The implications include (1) fine‐texture materials could have lower retardation factors than sand due to higher retained water content, (2) soil PFAS concentrations are likely to be orders of magnitude higher than those in groundwater at source zones. Both implications are consistent with recent field observations at hundreds of AFFF‐impacted sites.

Modeling variably saturated flow in the vadose zone is of vital importance to many scientific fields and engineering applications. Richardson-Richards equation (RRE, which is conventionally known as Richards' equation) is often chosen to physically represent the fluxes in the vadose zone when the accurate characterization of the soil water dynamics is required. Being a highly nonlinear partial differential equation, RRE is often solved numerically. Although there are mature software and codes available for simulating variably saturated flow by solving RRE, the numerical solution of RRE is nevertheless computationally expensive.Moreover, sometimes the robustness and the efficiency of RRE-based models can deteriorate rapidly when certain unfavorable conditions are met. These demerits of RRE hinder its application on large-scale vadose zone hydrology problems and uncertainty quantification, both of which requires many runs of the prediction model. To address these challenges, the accuracy, convergence, and efficiency of the numerical schemes of RRE should be further improved by testing a wide variety of cases covering different initial conditions, boundary conditions, and soil types. We reviewed and highlighted several critical issues related to the numerical modeling of RRE, including spatial and temporal discretization, the different forms of RREs, iterative and noniterative schemes, benchmark solutions, and available software and codes. Based on the review, we summarize the challenges and future work for solving RRE numerically.

No abstract

No abstract