Air-water interfacial adsorption coefficients for PFAS when present as a multi-component mixture

Surface tension isotherms and calculated air-water interfacial (AWI) adsorption data are presented for solution mixtures of per- and polyfluoroalkyl substances (PFAS), specifically a series of binary and one ternary mixtures of homologous linear perfluorocarboxylic acids (PFCAs) in a simulated groundwater, and two 8-component mixtures containing both PFCAs and linear perfluoroalkane sulfonates (PFSAs). In all cases, non-ideal competitive adsorption was observed that favored the most surface-active component(s) of the solution mixture. The multi-component extended Langmuir (EL) isotherm model was observed to accurately predict the competitive adsorption observed in the binary and ternary PFCA solution mixtures. However, the predictive utility of the EL model was observed to diminish when mixtures contained both PFCAs and PFSAs, which differ in their hydrophile structure, resulting in overpredictions and underpredictions of the AWI adsorption isotherms derived from measured data depending on the specific components present in the solution mixtures. Observations indicate that the individual component adsorptive affinities for the AWI can change in response to competitive preferential adsorption as their solution concentrations increase that is not being captured by the EL model. Our results demonstrate that alternative mathematical models are needed that support concentration dependent affinity coefficients for non-similar mixtures of PFAS, such that the transport of individual target PFAS components within a larger mixture of components can be accurately predicted across a wider range of solution concentration. •Non-ideal competitive air-water interfacial (AWI) adsorption observed for components of PFAS when present as a mixture.•AWI adsorption favors the more surface-active PFAS components at higher solution concentration.•Competitive preferential adsorption of more surface-active PFAS components reduces the adsorption the other components.•Discussion of the implications of these processes on PFAS transport is provided.•Interfacial adsorption models are evaluated for including these effects in unsaturated flow and transport models.