Monte Carlo Simulations of Water Pollutant Adsorption at Parts-per-Billion Concentration: A Study on 1,4-Dioxane

1,4-dioxane, an emerging water pollutant with high production volumes, is a probable human carcinogen. The inadequacy of conventional treatment processes demonstrates the 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 potential of all-silica zeolites for the separation of 1,4-dioxane from water. These zeolites are highly hydrophobic and can preferentially adsorb nonpolar molecules from mixtures. We investigated six zeolite frameworks (BEA, EUO, FER, IFR, MFI, and 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 a greater 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 a 0.35 ppb concentration. We quantify 1,4-dioxane and water coadsorption and observe selectivities ranging from 1.1 × 10⁵ in MOR to 8.7 × 10⁶ in FER. We also demonstrate that 1,4-dioxane is in the infinite dilution regime in the aqueous phase at this concentration. This simulation technique can be extended to model other emerging water contaminants such as perfluoroalkyl and polyfluoroalkyl substances (PFAS), chlorofluorocarbons, and others, which are also found in extremely low concentrations.