Understanding the sorption behaviors of heavy metal ions in the interlayer and nanopore of montmorillonite: A molecular dynamics study

The molecular-scale adsorption mechanism of heavy metal ions in the interlayer and nanopore regions of montmorillonite (MMT) were investigated by molecular dynamics simulations. Three typical heavy metals (zinc, cadmium, and lead) were selected as the model ions, and two types of MMT (Arizona and Wyoming) were considered. The results showed that Cd2+ and Pb2+ can form both inner- and outer-sphere complexes on Wyoming MMT, while Zn2+ only formed outer-sphere complex due to the stronger hydration interaction of Zn2+ than Cd2+ and Pb2+. For Arizona MMT, all of the three ions only formed outer-sphere complexes on its interlayer and external basal surface in which the cations remained a fully hydrated state. The calculated diffusion coefficients of three cations in interlayer and nanopore indicated that their diffusion abilities were significantly impaired, implying that MMT adsorbents have a strong ability to fix and retard heavy metal ions. The derived results and mechanisms are instrumental to a profound understanding of the transport and retention of heavy metal elements in subsurface environments, and provide guidance for the management of heavy metal pollution. [Display omitted] •Zn2+ cannot form inner-sphere adsorption on Wyoming MMT surface.•The adsorption strength of Wyoming MMT was slightly stronger than that of Arizona.•The electrostatic force was the dominant energy for adsorption of cations.•The mobilities of cations in the interlayer and nanopore of MMT was retarded.