Abstract. It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NO x flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Abstract. Both snow manipulation experiments and ambient measurements during the Polar Sunrise Experiment 2000 atAlert (Alert2000) indicate intensive photochemical production of nitrous acid (HONO) in the snowpack. This process constitutes a major HONO source for the overlying atmospheric boundary layer in the Arctic during the springtime, and sustained concentrations of HONO high enough that upon photolysis they became the dominant hydroxyl radical (OH) source. This implies a much greater role for OH radicals in Arctic polar sunrise chemistry than previously believed. Although the observations were made in the high Arctic, this finding has a significant implication for the boundary layer atmospheric chemistry in Antarctica during sunlit seasons and in the mid to high latitudes of the Northern Hemisphere during the winter and spring seasons when approximately 50% of the land mass may be covered by snow.

[1] A measurement intensive was carried out in Barrow, Alaska, in spring 2009 as part of the Ocean-Atmosphere-Sea-Ice-Snowpack (OASIS) program. The central focus of this campaign was the role of halogen chemistry in the Arctic. A chemical ionization mass spectrometer (CIMS) performed in situ bromine oxide (BrO) measurements. In addition, a long path-differential optical absorption spectrometer (LP-DOAS) measured the average concentration of BrO along light paths of either 7.2 or 2.1 km. A comparison of the 1 min observations from both instruments is presented in this work. The two measurements were highly correlated and agreed within their uncertainties (R 2 = 0.74, slope = 1.10, and intercept = −0.15 pptv). Better correlation was found (R 2 = 0.85, slope = 1.04, and intercept = −0.11 pptv) for BrO observations at moderate wind speeds (>3 m s −1 and <8 m s −1 ) and low nitric oxide (NO) mixing ratios (<100 pptv). The improved agreement is likely due to the elimination of periods when the spatial distribution of BrO is inhomogeneous. The detection limit obtained for the CIMS was 2.6 pptv (3s) for a 4 s integration period, and the estimated uncertainty was ∼30%. The detection limits for the LP-DOAS ranged from 0.7 to 5 pptv (3s) depending on the level of ambient light and the chosen light path, and the estimated systematic error was 10%. The agreement between the CIMS and LP-DOAS is excellent and demonstrates the capability of both instruments to selectively and accurately measure BrO with high sensitivity.

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