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.

Table 2. Atmospheric Mixing Ratios of Organoiodines in the MBL a mixing ratio/pptv species region mean range ref CH 3 I coastal Spitzbergen, Norway 1.04 <0.004À2.12 Schall and Heumann Mace Head, Ireland (spring) 0.43 0.12À1.47 Carpenter et al. 78 Mace Head, Ireland (summer) 3.4 1.9À8.7 Bassford et al. 293 Mace Head, Ireland (summer) 3.78 1.3À12.0 Carpenter et al. 80 Cape Grim, Australia 2.6 1.0À7.3 Carpenter et al. 80 Cape Grim, Australia 1.2 Krummel et al. 294 Cape Grim, Australia 0.53 0.14À0.9 Yokouchi et al. 50

Increasing tropospheric ozone levels over the past 150 years have led to a significant climate perturbation; the prediction of future trends in tropospheric ozone will require a full understanding of both its precursor emissions and its destruction processes. A large proportion of tropospheric ozone loss occurs in the tropical marine boundary layer and is thought to be driven primarily by high ozone photolysis rates in the presence of high concentrations of water vapour. A further reduction in the tropospheric ozone burden through bromine and iodine emitted from open-ocean marine sources has been postulated by numerical models, but thus far has not been verified by observations. Here we report eight months of spectroscopic measurements at the Cape Verde Observatory indicative of the ubiquitous daytime presence of bromine monoxide and iodine monoxide in the tropical marine boundary layer. A year-round data set of co-located in situ surface trace gas measurements made in conjunction with low-level aircraft observations shows that the mean daily observed ozone loss is approximately 50 per cent greater than that simulated by a global chemistry model using a classical photochemistry scheme that excludes halogen chemistry. We perform box model calculations that indicate that the observed halogen concentrations induce the extra ozone loss required for the models to match observations. Our results show that halogen chemistry has a significant and extensive influence on photochemical ozone loss in the tropical Atlantic Ocean boundary layer. The omission of halogen sources and their chemistry in atmospheric models may lead to significant errors in calculations of global ozone budgets, tropospheric oxidizing capacity and methane oxidation rates, both historically and in the future.

During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br⁻) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes

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