Uranyl adsorption and speciation at the fused silica/water interface studied by resonantly enhanced second harmonic...

We report the first use of resonantly enhanced second harmonic generation (SHG) to study uranyl adsorption at a buried mineral oxide/water interface. Uranyl adsorption is studied in real-time, under flow conditions, and in the presence of environmentally relevant screening electrolyte concentrations. The in situ SHG spectrum of surface-bound uranyl reveals a well-defined resonance at 306 nm. By monitoring the SHG response at 306 nm, adsorption isotherms were collected for uranyl species at the fused silica/water interface at pH 7, and in the presence of aqueous carbonate. The measured adsorption free energies determined by the Langmuir isotherm are consistent with physisorption via hydrogen bonding. The speciation of the surface-active uranyl species at pH 7 was elucidated via a free energy versus interfacial potential analysis, which reveals that the uranyl adsorbates are either neutral or univalent cationic species. Complementary surface charge density data, obtained using the Eisenthal chi(3) technique, reveal that the charge on the ionic uranyl species adsorbing under the experimental conditions are positive. It is proposed that a mixture of neutral and univalent, cationic uranyl species is surface active at pH 7 and in the presence of carbonate ions. Insofar as the experimental conditions model those found in natural groundwater systems, the results of this work are valuable to the prediction and assessment of uranium pollution transport in groundwater and soils. Our thermodynamic results can also serve as important benchmarks for computer simulations of U(VI) transport in heterogeneous geochemical environments.