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Production of gas phase NO₂ and halogens from the photochemical oxidation of aqueous mixtures of sea salt and nitrate ions at room temperature.

Nitrate and halide ions coexist in a number of environmental systems, including sea salt particles, the Arctic snowpack, and alkaline dry lakes. However, little is known about potential synergisms between halide and nitrate ions. The effect of sea salt on NO(3)(-) photochemistry at 311 nm was investigated at 298 K using thin films of deliquesced NaNO(3)-synthetic sea salt mixtures. Gas phase NO(2), NO, and halogen products were measured as a function of photolysis time using NO(y) chemiluminescence and atmospheric pressure ionization mass spectrometry (API-MS). The production of NO(2) increases with the halide-to-nitrate ratio, and is similar to that for mixtures of NaCl with NaNO(3). Gas phase halogen production also increased with the halide-to-nitrate ratio, consistent with NO(3)(-) photolysis yielding OH which oxidizes halide ions in the film. Yields of gas phase halogens and NO were strongly dependent on the acidity of the solution, while that of NO(2) was not. An additional halogen formation mechanism in the dark involving molecular HNO(3) is proposed that may be important in other systems such as reactions on surfaces. These studies show that the yield of Br(2) relative to NO(2) during photolysis of halide-nitrate mixtures could be as high as 35% under some atmospheric conditions.