Monte Carlo simulations of water pollutant adsorption at parts-per-billion concentration: A study on 1,4-dioxane

1,4-dioxane is an emerging water pollutant with high production volumes and a probable human carcinogen. The incompetence of conventional treatment processes demonstrates a need for an effective remediation strategy. Crystalline nanoporous materials are cost-effective adsorbents due to their high capacity and selective separation in mixtures. This study explores the potency of all-silica zeolites. These zeolites are highly hydrophobic and can preferentially adsorb nonpolar molecules from mixtures. We investigated six zeolite frameworks (BEA, EUO, FER, IFR, MFI, MOR) using Monte Carlo simulations in the Gibbs ensemble. The simulations indicate high selectivity by FER and EUO, especially at low pressures, which we attribute to pore sizes and shapes with more affinity to 1,4-dioxane. We also demonstrate a Monte Carlo simulation workflow using gauge cells to model the adsorption of an aqueous solution of 1,4-dioxane at 0.35 ppb concentration. We quantify 1,4-dioxane and water coadsorption and observe selectivities ranging from 1.1 x 10^5 in MOR to 8.7 x 10^6 in FER. We also demonstrate that 1,4-dioxane is in the infinite dilution regime in both the aqueous and adsorbed phases at this concentration. This simulation technique can be extended to model other emerging water contaminants such as per- and polyfluoroalkyl substances (PFAS), chlorates, and others, which are also found in extremely low concentrations.