Increasing ionic strength and valency of cations enhance sorption through hydrophobic interactions of PFAS with soil...

The effect of soluble cations on sorption in soils of a range of anionic PFAS is not well studied. We investigated the role of three common cations (Na⁺, Ca²⁺, and Mg²⁺) at varying solution concentrations on the sorption coefficients (K_d) of 18 anionic PFAS in two contrasting soils. The effective charge of the soil suspension (Zeta potential) became less negative as the concentration of these cations increased in the soil solutions. Perfluorinated compounds showed greater sorption than polyfluorinated compounds, with sulfonates of comparable chain lengths showing higher sorption than the carboxylates. We observed that the K_d values of several PFAS in the two soils were positively correlated with the concentration of cations in solution, especially in the presence of polyvalent cations (Ca²⁺and Mg²⁺). The changes in sorption with cation concentration were more prominent for long-chain PFAS, with C > 10 PFAS being completely removed from solution at higher cation concentrations. The emerging PFAS (replacement compounds GenX and ADONA) showed negligible or little sorption (K_d < 0.6 L/kg). While several mechanisms contribute towards sorption of PFAS in the presence of cations, we conclude that the primary effect of cations is through screening of negative charges on head groups of PFAS and reorientation of molecules at the interface between organic matter surfaces and soil solution as well as charge neutralisation at soil solid surface. Screening of negative charges allows for greater hydrophobic interaction between hydrophobic tails of PFAS and soil surfaces resulting in greater sorption. Increasing cation concentrations in soil solutions could thus reduce mobility of PFAS through a soil profile.