title: Inner-sphere adsorption geometry of Se(IV) at the hematite (100)-water interface.
abstract: The 3-dimensional structure of adsorption complexes on mineral surfaces provides insight into the fundamental mechanisms controlling sorption processes. This is important to the development of a general understanding of the behavior of contaminants such as selenite in the environment. The adsorption of selenite (SeO3(2-)) on the hematite (100) surface was studied using X-ray standing wave (XSW) measurements. Inner-sphere bidentate surface complexes bridging between adjacent singly-coordinated oxygen sites were identified as the primary adsorption site. The lack of binding to doubly-coordinated oxygen sites that were also exposed on the surface was likely due to differences in the reactivity or exchange kinetics of these sites or cation-cation repulsion, although the latter appears to be a secondary effect based on past observations. While these bridging bidentate geometries are similar to those inferred in past spectroscopic studies, the Se-Fe distances are such that these species might be misidentified as edge-sharing complexes if studied by EXAFS spectroscopy, highlighting the need for a fundamental understanding of mineral surface structure.
authors.affiliation: Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA. catalano@anl.gov
authors.forename: Jeffrey G
authors.initials: JG
authors.lastname: Catalano
authors.forename: Zhan
authors.initials: Z
authors.lastname: Zhang
authors.forename: Paul
authors.initials: P
authors.lastname: Fenter
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Bedzyk