Simulating PFAS transport influenced by rate-limited multi-process retention

The transport of per- and poly-fluoroalkyl substances (PFAS) in the vadose zone is complicated by the fact that multiple mass-transfer processes can contribute to their retention and retardation. In addition, PFAS transport at some sites can be further complicated by the presence of organic immiscible liquids (OIL). Mass-transfer processes are inherently rate limited and, therefore, have the potential to cause nonideal transport of PFAS. The objectives of this research were to: (1) develop a solute-transport model that explicitly accounts for multiple retention processes, including adsorption at air-water and OIL-water interfaces, adsorption by the solid phase, and diffusive mass-transfer between advective and non-advective domains, and (2) apply the model to measured transport data to delineate which processes are rate limited and contribute to observed nonideal transport. Breakthrough curves for transport of two PFAS and one hydrocarbon surfactant in sand obtained from prior miscible-displacement experiments exhibited nonideal transport. The multiprocess model effectively simulated the measured transport data. The results of the analyses indicate that adsorption at the air-water and OIL-water interface can generally be treated as effectively instantaneous for transport in porous media. The rate limitations associated with solid-phase adsorption and diffusive mass transfer between advective and nonadvective domains were of greater significance. (C) 2019 Elsevier Ltd. All rights reserved.