Zinc adsorption on clays inferred from atomistic simulations and EXAFS spectroscopy.

Clay minerals are efficient sinks for heavy metals in the geosphere. Knowing the uptake mechanism of these elements on clays can help to protect the natural environment from industrial pollution. In this study ab initio molecular dynamics (MD) calculations were applied to simulate the uptake of Zn on the edge surfaces of montmorillonite, a dioctahedral clay, and to explain the measured K-edge extended X-ray absorption fine structure (EXAFS) spectra of adsorbed Zn. These experiments were carried out using a high ionic strength Na background electrolyte that enables one to block cation exchange processes and to restrict the Zn uptake to the sorption complexation at the edge sites of clay. The analysis of the experimental data and simulation results suggest that structurally incorporated Zn preferentially substitutes for Al(III) in the trans-symmetric sites of the octahedral layer. At low loading, Zn is incorporated into the outermost trans-octahedra on (010) and (110) edges. At medium loading, Zn forms mono- and bidentate inner-sphere surface complexes attached to the octahedral layer of (010) and (110) edge sites. The maximal site density of inner-sphere sorption sites inferred from molecular simulations agrees well with site capacities of surface complexation sites derived from macroscopic studies and modeling.