Evaluating air-water and NAPL-water interfacial adsorption and retention of Perfluorocarboxylic acids within the Vadose zone.

The release and transport of linear perfluorocarboxylic acids (PFCA) within the vadose-zone beneath per- and polyfluoroalkyl substance (PFAS)- and non-aqueous phase liquid (NAPL)-contaminated source areas is influenced by multi-phase interfacial retention phenomena. Conceptually, interfacial adsorption results in retardation of PFCA velocities in subsurface multiphase systems. However, site hydrochemical factors influencing interfacial adsorption are not yet fully elucidated. Herein, air-water and NAPL-water interfacial tension isotherms were prepared for six homologous PFCAs of environmental significance for deionized water and five synthetic groundwaters of increasing ionic strength. The isotherms were successfully modeled by the Langmuir-Szyskowski equation and parameters used to fit the measured data are provided. Concentration-dependent interfacial adsorption coefficients and retardation factors are also provided for each PFCA and ionic strength condition and are evaluated to assess their significance. Simplifying relationships for predicting interfacial adsorption based on PFCA chain length were found to be less appropriate for natural groundwaters that contain a mixture of dissolved divalent and monovalent ions. Air-water interfacial (AWI) adsorption increased in a threshold manner with ionic strength from 0 to 6 mM, whereafter further adsorption was marginal. PFCA retention within water-unsaturated porous media is shown to depend on a number of inter-related factors and conditions that complicate the use of retardation factors within analytical models typically used for predicting transport rates under field conditions. Numerical simulation is thus necessary to model fundamental fate and transport processes. Mathematical relationships for incorporating interfacial adsorption in future and existing unsaturated flow and transport models are described.