Spatial distribution of nitrate and nitrite anions at the liquid/vapor interface of aqueous solutions

Depth-resolved ion spatial distributions of nitrate and nitrite anions in aqueous solution have been quantitatively measured using X-ray photoemission spectroscopy on a 15 microm aqueous liquid jet containing 3 M NaNO(3), 3 M NaNO(2), or an equimolar mixture of the two. The surface region, which extends to photoelectron kinetic energies of 400-500 eV, is partially depleted in anions relative to the bulk 3 M concentration. The nitrate and nitrite solutions exhibit similar depth-dependent anion profiles. The results presented here are compared with recent molecular dynamics simulations of a NaNO(3) solution and are found to agree at high photoelectron kinetic energies. At shallower probe depths, the experiment measured a surface anion concentration less than that predicted by theory. Possible origins of the discrepancy are discussed in terms of the confined size of the simulation box and uncertainties that remain in regard to the inelastic mean free path of photoelectrons in aqueous media. The importance of our findings is discussed in relation to the observed increase in photochemical activity of nitrate-containing aerosols in the atmosphere.