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.

The presence of snow greatly perturbs the composition of near-surface polar air, and the higher concentrations of hydroxyl radicals (OH) observed result in a greater oxidative capacity of the lower atmosphere. Emissions of nitrogen oxides, nitrous acid, light aldehydes, acetone, and molecular halogens have also been detected. Photolysis of nitrate ions contained in the snow appears to play an important role in creating these perturbations. OH formed in the snowpack can oxidize organic matter and halide ions in the snow, producing carbonyl compounds and halogens that are released to the atmosphere or incorporated into snow crystals. These reactions modify the composition of the snow, of the interstitial air, and of the overlying atmosphere. Reconstructing the composition of past atmospheres from ice-core analyses may therefore require complex corrections and modeling for reactive species.

Abstract. Even though the specific surface area (SSA) and the snow area index (SAI) of snow are crucial variables to determine the chemical and climatic impact of the snow cover, few data are available on the subject. We propose here a novel method to measure snow SSA and SAI. It is based on the measurement of the hemispherical infrared reflectance of snow samples using the DUFISSS instrument (DUal Frequency Integrating Sphere for Snow SSA measurement). DUFISSS uses the 1310 or 1550 nm radiation of laser diodes, an integrating sphere 15 cm in diameter, and InGaAs photodiodes. For SSA<60 m 2 kg −1 , we use the 1310 nm radiation, reflectance is between 15 and 50% and the accuracy of SSA determination is 10%. For SSA>60 m 2 kg −1 , snow is usually of low density (typically 30 to 100 kg m −3 ), resulting in insufficient optical depth and 1310 nm radiation reaches the bottom of the sample, causing artifacts. The 1550 nm radiation is therefore used for SSA>60 m 2 kg −1 . Reflectance is then in the range 5 to 12% and the accuracy on SSA is 12%. We propose empirical equations to determine SSA from reflectance at both wavelengths, with that for 1310 nm taking into account the snow density. DUFISSS has been used to measure the SSA of snow and the SAI of snowpacks in polar and Alpine regions.

International audienceThe comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the δ 15N of nitrate mostly deriving from anthropogenically emitted NO x is found to be significantly different (from 0 to 6‰) from nitrate sampled in locations influenced by natural NO x sources (−4 ± 2)‰. The effects on δ 15N(NO3 −) of different NO x sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (Δ17O = δ 17O − 0.52 × δ 18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NO x sinks. Different Δ17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low δ 15N values (down to −40‰) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NO x from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores

Abstract. Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

The equilibrium solubility of HCl in ice I h has been measured as a function of temperature and HCl partial pressure, between -8 and -35°C by doping large ice single crystals with gaseous HCl for several weeks. Results indicate that the solubility of HCl in ice is very low, much less than found in many previous studies. Its temperature and HCl partial pressure dependences are found to be X HCl ) 6.13 × 10 -10 e 2806.5/T (P HCl ) 1/2.73 where X HCl is the solubility in mole fraction, P HCl is the HCl partial pressure in Pa, and T is the temperature in kelvin. The diffusion coefficient of HCl in ice is also found to be very low, about 10 -12 cm 2 /s at -15°C. Extrapolations of these data yield the solidus in the temperature-composition phase diagram. The determination of the solid phase composition in equilibrium with a given gas phase composition allows the calculation of the partial enthalpy of sublimation of HCl from ice, ∆h HCl s ) 63.7 ( 7.6 kJ/mol, and of the activity of HCl in ice. Possible mechanisms of HCl incorporation in ice are discussed. Atmospheric implications concerning ozone depletion and the understanding of snow composition are examined.

Abstract. Snow on the ground is a complex multiphase photochemical reactor that dramatically modifies the chemical composition of the overlying atmosphere. A quantitative description of the emissions of reactive gases by snow requires knowledge of snow physical properties. This overview details our current understanding of how those physical properties relevant to snow photochemistry vary during snow metamorphism. Properties discussed are density, specific surface area, thermal conductivity, permeability, gas diffusivity and optical properties. Inasmuch as possible, equations to parameterize these properties as functions of climatic variables are proposed, based on field measurements, laboratory experiments and theory. The potential of remote sensing methods to obtain information on some snow physical variables such as grain size, liquid water content and snow depth are discussed. The possibilities for and difficulties of building a snow photochemistry model by adapting current snow physics models are explored. Elaborate snow physics models already exist, and including variables of particular interest to snow photochemistry such as light fluxes and specific surface area appears possible. On the other hand, understanding the nature and location of reactive molecules in snow seems to be the greatest difficulty modelers will have to face for lack of experimental data, and progress on this aspect will require the detailed study of natural snow samples.

[1] To help quantify exchanges between the atmosphere and the snow cover, we have measured the specific surface area (SSA) of 176 snow samples taken from the seasonal snowpack in the Alps, Svalbard, and the Canadian high Arctic around Alert. A volumetric method was used, and the adsorption isotherm of CH 4 on snow at 77 K was recorded. The data were analyzed by the Brunauer-Emmett-Teller method to yield SSA and ÁQ CH4 , the mean heat of adsorption of the first CH 4 monolayer. SSA values obtained were between 100 and 1580 cm 2 /g. The reproducibility of the method is estimated at 6%, and the accuracy is estimated at 12%. We propose that ÁQ CH4 = 2240 ± 200 J/mol should be used as a criterion of reliability of the measurement. The method is described in detail to promote its use. Aged snow samples have lower SSA than fresh ones. The lowest values were found for faceted crystals and depth hoar, and the highest values were found for fresh rimed dendritic snow. A method that field investigators can use to estimate SSA from a visual examination of the snow and from a density measurement is suggested. Snow samples are classified into 14 types based on snow age and crystal shapes. Within each type, a density versus SSA correlation is determined. Our data indicate that, depending on snow type, SSA can then be estimated within 25 to 40% at the 1s confidence level with the method proposed. Preliminary data suggest that SSA spatial variability of a given snow layer is low (<5%), but metamorphism can increase it.