Uranium(IV) Interaction with Aqueous/Solid Interfaces Studied by Nonlinear Optics

Abstract

Second harmonic generation (SHG) was used to study U(VI) interactions with a buried mineral oxide/water interface using pH 4 uranyl solutions that contained carbonate and environmentally relevant electrolyte concentrations. The results of this work are of value as benchmarks for geochemical transport models of uranium pollution resulting from acid mine drainage and nuclear waste storage. Additionally, the binding contants, adsorption free energies, absolute adsorbate number densities, and interfacial charge densities of Al(III), Sc(III), Y(III), La(III), and Gd(III) interacting with fused silica/water interfaces held at pH 4 were determined using second harmonic generation and the Eisenthal χ(3) technique. By quantifying the exponential sensitivity of the surface coverage of the adsorbed ions to their charge state directly at the fused silica/water interface, we provide benchmarks for theory calculations describing the interactions of metal ions with oxide interfaces in geochemistry and hope to improve the prediction of trivalent metal ion transport through groundwater environments.