ABSTRACT
The atomistic level understanding of iron speciation and the probable oxidative behavior of iron (Feaq2+ â Fesurf3+) in clay minerals are fundamental for environmental geochemistry of redox reactions. Thermodynamic analyses of wet chemistry data suggest that iron adsorbs on the edge surfaces of clay minerals at distinct structural sites commonly referred as strong and weak sites (with high and low affinity, respectively). In this study, we applied ab initio molecular dynamics simulation to investigate the structure and the stability of the edge surfaces of trans- and cis-vacant montmorillonites. These structures were further used to evaluate the surface complexation energy and to calculate reference ab initio X-ray absorption spectra (XAS) for distinct inner-sphere complexes of iron. The combination of ab initio simulations and XAS allowed us to reveal the Fe-complexation mechanism and to quantify the Fe partitioning between the high and low affinity sites as a function of the oxidation state and loadings. Although iron is mostly present in the Fe3+ form, Fe2+ increasingly co-adsorbs at increasing loadings. Ab initio structure relaxations of several different clay structures with substituted Fe2+/Fe3+ in the bulk or at the surface site showed that the oxidative sorption of ferrous iron is an energetically favored process at several edge surfaces of the Fe-bearing montmorillonite.
Subject(s)
Bentonite , Iron , Adsorption , Clay , Oxidation-Reduction , X-Ray Absorption SpectroscopyABSTRACT
Fe-bearing clay minerals are abundant in argillaceous rocks as their redox-active structural iron may control the sorption mechanism of redox sensitive elements on the surface of clay minerals. The extent and efficiency of the redox reactions depend on the oxidation state (Fe2+/Fe3+ ratio) and structural distribution of the substituting cations in the TOT-layer of clay minerals. Even smectites with similar structure originating from different locations might have a distinct arrangement of isomorphic substitutions (e.g., individual iron or Fe-Fe pairs). In this study, the proportion of different iron distribution in Milos-, Wyoming-, and Texas-montmorillonite was determined by combining X-ray absorption spectroscopy (XAS) with ab initio calculations. The relaxed atomic structures of the smectite models with different arrangement of individual Fe atoms and Fe-Fe/Fe-Mg clusters served as the basis for the calculations of the XAS spectra. The combination of simulation results and measured Fe K-edge XAS spectra of Wyoming-, Milos- and Texas-montmorillonites suggested that iron is present as Fe3+ in the octahedral sheet. Fe3+ in Texas-montmorillonite has a tendency to form clusters, while no definitive statement about clustering or avoidance of Fe-Fe and Fe-Mg pairs can be made for Milos- and Wyoming-montmorillonite.
Subject(s)
Aluminum Silicates , Iron , Silicates , Texas , Wyoming , X-Ray Absorption SpectroscopyABSTRACT
Iron occurs in clay minerals in both ferric and ferrous forms. Depending on its oxidation state and the environmental conditions, it can participate in redox reactions and influence the sorption processes at surfaces of clay minerals. Knowing the oxidation state and the preferential structural position of Fe2+ and Fe3+ is essential for the detailed understanding of the mechanism and kinetics of such processes. In this study, molecular dynamics (MD) calculations based on density functional theory (DFT+U) were applied to simulate the incorporated Fe in bulk montmorillonite and to explain the measured Fe K-edge X-ray absorption fine structure (XAFS) spectra. The analysis of the experimental data and simulation results suggested that iron in montmorillonite is preferentially incorporated as Fe3+ into the octahedral layer. The simulations showed that there is no preferential occupation of cis- or trans-sites by Fe2+ and Fe3+ in bulk montmorillonite. A very good agreement between the ab initio simulated and the measured XAFS spectra demonstrate the robustness of the employed simulation approach.
