Nitrate Concentration near the Surface of Frozen Aqueous Solutions

Photolysis of nitrate plays an important role in the emission of nitrogen oxides from snow and ice, which affects the composition of the overlying atmosphere. In order to quantify these reactions, it is necessary to know how much nitrate is available for photolysis near the surfaces of snow and ice. The concentration of nitrate excluded from frozen solutions of nitric acid, sodium nitrate, and magnesium nitrate was measured with attenuated total reflection infrared spectroscopy. Liquid water and nitrate were observed at and near the bottom surface of frozen aqueous solutions during annealing from -18 to -2 °C. At -2 °C, the nitrate concentration was determined to be ∼1.0 mol/L for frozen NaNO(3) and Mg(NO(3))(2) solutions and ∼0.8 mol/L for frozen HNO(3) solutions. At lower temperatures, nitrate concentration ranged from 1.6 to 3.7 mol/L. Ideal thermodynamics overestimates nitrate concentration at colder temperatures where the brine is highly concentrated for all solutions. The nitrate concentration at ice surfaces is well described by bulk freezing point depression data close to the melting point of ice and for nitric acid at colder temperatures. Effects of temperature and counterions and implications for modeling snow chemistry are discussed.