Interaction of nitrate, barium, strontium and cadmium ions with fused quartz/water interfaces studied by second harmonic generation.

Inorganic anions and cations are ubiquitous in environmental chemistry. Here, we use second harmonic generation to track the interaction of the environmentally important metal cations barium, strontium, and cadmium and the nitrate anion with fused quartz/water interfaces at pH 7. Using a dynamic flow system, we assess the extent of reversibility in the binding process and report the absolute number density of adsorbed cations, their charge densities, and their free energies of adsorption. We also present resonantly enhanced second harmonic generation experiments that show that nitrate is surface active and report the free energies and binding constants for the adsorption process. The second harmonic generation spectrum of surface-bound nitrate shows a new adsorption band that cuts further into the solar spectrum than nitrate in the aqueous or solid state. The results that we obtain for all four inorganic ions and the implications for tropospheric and aquatic chemistry as well as geochemistry are discussed in the context of fundamental science as well as pollutant transport models.