title: Mechanisms of arsenic uptake from aqueous solution by interaction with goethite, lepidocrocite, mackinawite, and pyrite: an X-ray absorption spectroscopy study.
abstract: The mechanisms whereby As(III) and As(V) in aqueous solution (pH 5.5-6.5) interact with the surfaces of goethite, lepidocrocite, mackinawite, and pyrite have been investigated using As K-edge EXAFS and XANES spectroscopy. Arsenic species retain original oxidation states and occupy similar environments on the oxyhydroxide substrates, with first-shell coordination to four oxygens at 1.78 A for As(III) and 1.69 A for As(V). In agreement with other workers, we find that inner sphere complexes form, apparently involving bidentate (bridging) arsenate or arsenite. Interaction of As(III) and As(V) with the sulfide surfaces shows primary coordination to four oxygens (As-O: 1.69-1.76 A) with further sulfur (approximately 3.1 A) and iron (3.4-3.5 A) shells suggesting outer sphere complexation. Arsenic species were also coprecipitated with mackinawite (pH 4.0), and these samples were further studied following oxidation. At high As(III) or As(V) concentrations, arsenate or arsenite species form, probably as sorption complexes, along with poorly crystalline arsenic sulfide (the only product at low As(V) concentrations). All oxidized samples show primary coordination to four oxygens at 1.7 A, indicating As(V); these arsenates may show both outer sphere complexation with residual mackinawite and inner sphere complexation with new oxyhydroxides. These experiments help to clarify our understanding of As mobility in near-surface environments.
authors: Department of Earth Sciences and Williamson Research Centre for Molecular Environmental Science, University of Manchester, UK.
authors: Morag L
authors: ML
authors: Farquhar
authors: John M
authors: JM
authors: Charnock
authors: Francis R
authors: FR
authors: Livens
authors: David J
authors: DJ
authors: Vaughan
mesh_terms: D000327:Adsorption; D001151:Arsenic / Q000493:pharmacokinetics*; D006863:Hydrogen-Ion Concentration; D007501:Iron / Q000737:chemistry; D058085:Iron Compounds / Q000737:chemistry; D008903:Minerals; D010084:Oxidation-Reduction; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry; D014867:Water / Q000737:chemistry; D014873:Water Pollutants / Q000493:pharmacokinetics*
chemical_list: D058085:Iron Compounds; D008903:Minerals; D013440:Sulfides; D014873:Water Pollutants; D014867:Water; C094886:goethite; C011342:pyrite; D007501:Iron; D001151:Arsenic