Adsorption of L-aspartate to rutile (α-TiO2): Experimental and theoretical surface complexation studies

Interactions between aqueous amino acids and mineral surfaces influence many geochemical processes from biomineralization to the origin of life. However, the specific reactions involved and the attachment mechanisms are mostly unknown. We have studied the adsorption of L-aspartate on the surface of rutile (alpha-TiO2, pH(PPZC) = 5.4) in NaCl(aq) over a wide range of pH, ligand-to-solid ratio and ionic strength, using potentiometric titrations and batch adsorption experiments. The adsorption is favored below pH 6 with a maximum of 1.2 mu mol of adsorbed aspartate per m(2) of rutile at pH 4 in our experiments. The adsorption decreases at higher pH because the negatively charged aspartate molecule is repelled by the negatively charged rutile surface above pH(PPZC). At pH values of 3-5, aspartate adsorption increases with decreasing ionic strength. The adsorption of aspartate on rutile is very similar to that previously published for glutamate (Jonsson et al., 2009). An extended triple-layer model was used to provide a quantitative thermodynamic characterization of the aspartate adsorption data. Two reaction stoichiometries identical in reaction stoichiometry to those for glutamate were needed. At low surface coverages, aspartate, like glutamate, may form a bridging-bidentate surface species binding through both carboxyl groups, i.e. "lying down" on the rutile surface. At high surface coverages, the reaction stoichiometry for aspartate was interpreted differently compared to glutamate: it likely involves an outer-sphere or hydrogen bonded aspartate surface species, as opposed to a partly inner-sphere complex for glutamate. Both the proposed aspartate species are qualitatively consistent with previously published ATR-FTIR spectroscopic results for aspartate on amorphous titanium dioxide. The surface complexation model for aspartate was tested against experimental data for the potentiometric titration of aspartate in the presence of rutile. In addition, the model correctly predicted a decrease of the isoelectric point with increased aspartate concentration consistent with previously published studies of the aspartate anatase system. Prediction of the surface speciation of aspartate on rutile indicates that the relative proportions of the two complexes are a strong function of environmental conditions, which should be taken into account in considerations of geochemical systems involving the interactions of biomolecules and minerals in electrolyte solutions. (C) 2010 Elsevier Ltd. All rights reserved.