Structures and Properties of As(OH)3 Adsorption Complexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study

Reactive mineral water interfaces exert control on the bioavailability of contaminant arsenic Species in natural aqueous systems. However, the ability to accurately predict As surface complexation is limited by the lack of molecular-level understanding of As water mineral interactions. In the present study, we report the structures and properties of the adsorption complexes of arsenous acid (As(OH)(3)) on hydrated mackinawite (FeS) surfaces, obtained from density functional theory (DFT) calculations. The fundamental aspects of the adsorption, including the registries of the adsorption complexes, adsorption energies, and structural parameters are presented. The FeS surfaces are shown to be stabilized by hydration, as is, perhaps to be expected-because the adsorbed water molecules stabilize the low-coordinated surface atoms. As(OH)(3) adsorbs weakly at the water FeS (001) interface through a network ofhydrogen-bonded interactions with water molecules on the surface, with the lowest-energy structure calculated to be an As up outer-sphere complex. Compared to the water FeS(001) interface, stronger adsorption was calculated for As(OH)(3) on the water FeS(011) and water FeS(111) interfaces, characterized by strong hybridization between the S-p and O-p states of As(OH)(3) and the surface Fe-d states. The As(OH)(3) molecule displayed a variety of chemisorption geometries on the water FeS(011) and water FeS(111) interfaces, where the most stable configuration at the water FeS(011) interface is a bidentate Fe AsO Fe complex, but on the water FeS(111) interface, a monodentate Fe-O-Fe complex was found. Detailed information regarding the adsorption mechanisms has been obtained via projected density of states (PDOS) and electron density difference iso-surface analyses and vibrational frequency assignments of the adsorbed As(OH)3 molecule.