Surprisingly small HONO emissions from snow surfaces at Browning Pass, Antarctica

Abstract

Measured Fluxes of nitrous acid at Browning Pass, Antarctica were very low, despite conditions that are generally understood as favorable for HONO emissions, including: acidic snow surfaces, an abundance of NO3- anions in the snow surface, and abundant UV light for NO3- photolysis. Photochemical modeling suggests noon time HONO fluxes of 5-10 nmol m(-2) h(-1); the measured fluxes, however, were close to zero throughout the campaign. The location and state of NO3- in snow is crucial to its reactivity. The analysis of soluble mineral ions in snow reveals that the NO3- ion is probably present in aged snows as NaNO3. This is peculiar to our study site, and we suggest that this may affect the photochemical reactivity of NO3-, by preventing the release of products, or providing a reactive medium for newly formed HONO. In fresh snow, the NO3- ion is probably present as dissolved or adsorbed HNO3 and yet, no HONO emissions were observed. We speculate that HONO formation from NO3- photolysis may involve electron transfer reactions of NO2 from photosensitized organics and that fresh snows at our site had insufficient concentrations of adequate organic compounds to favor this reaction.