Molecular mechanisms of per- and polyfluoroalkyl substances on a modified clay: a combined experimental and molecular simulation study

Repeated application of aqueous film-forming foams (AFFF) in designated firefighting training areas has caused severe groundwater contamination by perand polyfluoroalkyl substances (PFASs). Many research efforts are currently engaged for the effective removal of these chemicals from environmental waters. In this study, we demonstrate that modified clay produced by intercalating quaternary ammonium cations in the exchangeable interlayer sites of smectite clay can effectively remove PFAS pollutants in real ground-water via strong adsorption. The performance of the modified clay (with removal efficiencies 95 similar to 99%) is superior to those of granular activated carbon or hard-wood biochar and comparable to an ion exchange resin. Removal efficiency is not impacted by potential organic co-contaminants (e.g., diesel, BTEX, TCE, and 1,4 dioxane) or water chemistry (Ca2+ and Na+) at environmentally relevant concentrations. Furthermore, piecewise isotherms are identified to represent the uptake of PFASs by the modified clay. Based on molecular dynamics simulations, the anionic PFASs first occupy the highly polarized bare interlayer edge sites leading to a linear isotherm and then the interlayer surface sites resulting in a Langmuir isotherm. The ionic interactions between the cationic intercalant (N+) and the terminal oxygen atoms of carboxylate or sulfonate groups of PFASs play a dominant role in adsorption, and the lateral interaction in particular fluorophilic attraction among PFASs accelerate the adsorption. The strength of these interactions is quantified using Density Functional Theory calculations. Simulation results match reasonably well with the experimentally determined basal spacing and Fourier transform infrared spectroscopy of the modified clay loaded with PFASs. Overall, the combined experimental and molecular simulation studies elucidate the adsorption mechanism of PFASs on the modified clay and provide critical information to guide the use of modified clays for PFAS water treatment in the field. (C) 2020 Elsevier Ltd. All rights reserved.