Many per- and polyfluoroalkyl substances (PFAS) are surface-active and adsorb at fluid-fluid interfaces. The interfacial adsorption controls PFAS transport in multiple environmental systems, including leaching through soils, accumulation in aerosols, and treatment methods such as foam fractionation. Most PFAS contamination sites comprise mixtures of PFAS as well as hydrocarbon surfactants, which complicates their adsorption behaviors. We present a mathematical model for predicting interfacial tension and adsorption at fluid-fluid interfaces for multicomponent PFAS and hydrocarbon surfactants. The model is derived from simplifying a prior advanced thermodynamic-based model and applies to nonionic and ionic mixtures of the same charge sign with swamping electrolytes. The only required model inputs are the single-component Szyszkowski parameters obtained for the individual components. We validate the model using literature interfacial tension data of air-water and NAPL (non-aqueous phase liquid)-water interfaces covering a wide range of multicomponent PFAS and hydrocarbon surfactants. Application of the model to representative porewater PFAS concentrations in the vadose zone suggests competitive adsorption can significantly reduce PFAS retention (up to 7 times) at some highly contaminated sites. The multicomponent model can be readily incorporated into transport models to simulate the migration of mixtures of PFAS and/or hydrocarbon surfactants in the environment.
Keywords: PFAS; air−water interfacial adsorption; competitive adsorption; hydrocarbon surfactants; leaching; surfactant mixture; thermodynamics.