title: Electrochemical and XAFS studies of effects of carbonate on the oxidation of arsenite.
abstract: Measurements of electrochemical (EC) arsenite oxidation demonstrated thatthe arsenite oxidation current increased in the presence of carbonate while the potential of the onset of EC arsenite oxidation exhibited a strong shift toward less positive values. Examination of pH and total carbonate concentration effects on the EC arsenite oxidation parameters showed that they were affected solely by the concentration of carbonate ion CO3(2-), which appeared to form relatively weak mono- and dicarbonate complexes with arsenite. The EC activity of these complexes was determined to be almost an order of magnitude higher than that of free arsenite. However, X-ray absorption fine-structure (XAFS) measurements did not show any changes in the properties of the As(III) inner complexation shell associated with the presence of the bound carbonate ions. It was accordingly concluded that the strength of bonds between the bound carbonate and As(III) is close to that for As(III)-OH- interactions. The acceleration of the oxidation of carbonate-As(III) complexes was hypothesized to be associated with an additional pathway of the formation of As(IV) intermediates, in which the carbonate group present in the As(III) inner shell provides an electron to form a bound carbonate radical and also a good leaving group for facile cleavage from the transient As(IV) species.
authors.affiliation: Department of Civil and Environmental Engineering, University of Washington, Seattle 98195-2700, USA.
authors.forename: Jaeshin
authors.initials: J
authors.lastname: Kim
authors.forename: Gregory V
authors.initials: GV
authors.lastname: Korshin
authors.forename: Anatoly I
authors.initials: AI
authors.lastname: Frenkel
authors.forename: Alexander B
authors.initials: AB
authors.lastname: Velichenko
mesh_terms: D018053:Arsenites / Q000032:analysis / Q000737:chemistry*; D002254:Carbonates / Q000032:analysis / Q000737:chemistry*; D004563:Electrochemistry / Q000379:methods; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D013052:Spectrometry, X-Ray Emission / Q000379:methods; D014873:Water Pollutants / Q000032:analysis
chemical_list: D018053:Arsenites; D002254:Carbonates; D014873:Water Pollutants; C015001:arsenite