title: Structures and Properties of As(OH)3Adsorption Complexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study.
abstract: 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)3adsorbs weakly at the water-FeS(001) interface through a network of hydrogen-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)3on the water-FeS(011) and water-FeS(111) interfaces, characterized by strong hybridization between the S-p and O-p states of As(OH)3and the surface Fe-d states. The As(OH)3molecule 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)3molecule.
authors.affiliation: Department of Earth Sciences, Utrecht University , Princetonplein 9, 3584 CC, Utrecht, The Netherlands.
authors.forename: Nelson Y
authors.initials: NY
authors.lastname: Dzade
authors.affiliation: School of Chemistry, Cardiff University , Main Building, Park Place, Cardiff CF10 1DF, United Kingdom.
authors.forename: Alberto
authors.initials: A
authors.lastname: Roldan
authors.affiliation: Department of Earth Sciences, Utrecht University , Princetonplein 9, 3584 CC, Utrecht, The Netherlands.|School of Chemistry, Cardiff University , Main Building, Park Place, Cardiff CF10 1DF, United Kingdom.
authors.forename: Nora H
authors.initials: NH
authors.lastname: de Leeuw
mesh_terms: D000327:Adsorption; D001151:Arsenic; D008903:Minerals / Q000737:chemistry*; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D008903:Minerals; D014867:Water; D001151:Arsenic