A systematic investigation of single solute, binary and ternary PFAS transport in water-saturated soil using batch and 1-dimensional column studies: Focus on mixture effects

Abstract

This study aimed to investigate the transport and release of per- and polyfluoroalkyl substances (PFAS), as single solutes and binary and ternary mixtures, and associated competitive sorption effects in water-saturated soil. Batch sorption isotherm and desorption, and one-dimensional miscible displacement studies were conducted. For the batch study, the mixtures exhibited extensive sorption isotherm nonlinearity at aqueous concentrations exceeding 20 µg/L. At and above this threshold, competitive effects significantly decreased PFAS sorption, mostly affecting perfluorooctanoic acid (PFOA) and perfluorohexane sulfonate (PFHxS). Importantly, mixture effects exacerbated isotherm nonlinearity and may increase the leaching of PFAS in subsurface soil and groundwater. Further, up to 100% desorption occurred for single solutes and mixtures, indicating that the studied PFAS were weakly sorbed. For the column study, at influent concentrations (21 – 27 µg/L, depending on PFAS) near the threshold, PFOA and PFHxS breakthrough curves (BTC) generally exhibited equilibrium (nonlinear) transport, whereas perfluorooctane sulfonate (PFOS) exhibited nonequilibrium transport, with minimal or no mixture effects. Nonequilibrium transport of PFOS was driven by rate-limited sorption, especially as flow interruption tests confirmed the absence of physical nonequilibrium. The sorption distribution coefficients (Kd) from moment and frontal analyses, and 2-site modelling of the BTC, were consistent with the batch-derived Kd, although comparatively smaller. Such discrepancies may limit the applicability of batch-derived Kd values for predictive transport modelling purposes. Overall, understanding mixture impacts may aid effective predictive modelling of PFAS transport and leaching, especially in aqueous film forming foam (AFFF)-source zone areas associated with elevated PFAS concentrations. At low or environmental PFAS concentrations, mixture effects can be expected to be play a minor role in influencing PFAS transport.