title: Insights into H(4)SiO(4) surface chemistry on ferrihydrite suspensions from ATR-IR, Diffuse Layer Modeling and the adsorption enhancing effects of carbonate.
abstract: Silicic acid (H(4)SiO(4)) adsorbs at the ferrihydrite-water interface as monomeric or oligomeric surface silicate complexes.ATR-IR spectra were used to determine the proportions of monomeric and oligomeric surface silicate as a function of pH and Si surface concentrations (Γ(Si)) for H(4)SiO(4) in ferrihydrite suspensions.At each pH the proportion of adsorbed silicate present as monomers decreased as Γ(Si) increased while at a given Γ(Si) the proportion of adsorbed silicate present as monomers was higher at higher pH. ATR-IR spectra for ferrihydrite suspensions in combination with the adsorption isotherm data were used to calibrate the Diffuse Layer Model (DLM) to describe H(4)SiO(4) adsorption as monomers and oligomers on ferrihydrite surface sites (≡FeOH). Using a set of reactions that were consistent with the ATR-IR spectra the DLM could accurately describe the H(4)SiO(4) adsorption isotherms, the distribution of surface monomeric and oligomeric silicates, and the decrease in surface potential with Γ(Si).The reactions included the formation of monomeric complexes (≡FeH((3-n))SiO(4)((-n))) and trimeric silicate complexes formed between two surface sites(≡Fe(2)H((6-n))Si(3)O(10)((-n))). This oligomer stoichiometry is consistent with previous studies suggesting the surface silicate oligomer is formed by a solution H(4)SiO(4) bridging two adjacent adsorbed monomers to form a linear trimer. This study also showed that carbonate can enhance H(4)SiO(4) adsorption between pH 9 and 11. The data were consistent with formation of an outer-sphere complex between a solution H(3)SiO(4)(-) and a protonated adsorbed carbonate species which is analogous to the mechanism by which carbonate enhances the goethite adsorption of sulfate.
authors.affiliation: Department of Chemistry, University of Auckland, Private Bag, 92019 Auckland, New Zealand. p.swedlund@auckland.ac.nz
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Swedlund
authors.forename: Rossuriati Dol
authors.initials: RD
authors.lastname: Hamid
authors.forename: Gordon M
authors.initials: GM
authors.lastname: Miskelly
mesh_terms: D000327:Adsorption; D002254:Carbonates / Q000737:chemistry*; D004058:Diffusion; D005290:Ferric Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D008958:Models, Molecular; D012824:Silicic Acid / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013499:Surface Properties; D013535:Suspensions / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D002254:Carbonates; D005290:Ferric Compounds; D013535:Suspensions; D014867:Water; D012824:Silicic Acid; C092844:ferric oxyhydroxide