Should We Not Further Study the Impact of Microbial Activity on Snow and Polar Atmospheric Chemistry?

Since 1999, atmospheric and snow chemists have shown that snow is a very active photochemical reactor that releases reactive gaseous species to the atmosphere including nitrogen oxides, hydrocarbons, aldehydes, halocarbons, carboxylic acids and mercury. Snow photochemistry therefore affects the formation of ozone, a potent greenhouse gas, and of aerosols, which affect the radiative budget of the planet and, therefore, its climate. In parallel, microbiologists have investigated microbes in snow, identified and quantified species, and sometimes discussed their nutrient supplies and metabolism, implicitly acknowledging that microbes could modify snow chemical composition. However, it is only in the past 10 years that a small number of studies have revealed that microbial activity in cold snow (< 0 °C, in the absence of significant amounts of liquid water) could lead to the release of nitrogen oxides, halocarbons, and mercury into the atmosphere. I argue here that microbes may have a significant effect on snow and atmospheric composition, especially during the polar night when photochemistry is shut off. Collaborative studies between microbiologists and snow and atmospheric chemists are needed to investigate this little-explored field.

Dynamic recycling of gaseous elemental mercury in the boundary layer of the Antarctic Plateau

Gaseous elemental mercury (Hg0) was investigated in the troposphere and in the interstitial air extracted from the snow at Dome Concordia station (alt. 3320 m) on the Antarctic Plateau during January 2009. Measurements and modeling studies showed evidence of a very dynamic and daily cycling of Hg0 inside the mixing layer with a range of values from 0.2 ng m−3 up to 2.3 ng m−3. During low solar irradiation periods, fast Hg0 oxidation processes in a confined layer were suspected. Unexpectedly high Hg0 concentrations for such a remote place were measured under higher solar irradiation due to snow photochemistry. We suggest that a daily cycling of reemission/oxidation occurs during summer within the mixing layer at Dome Concordia. Hg0 concentrations showed a negative correlation with ozone mixing ratios, which contrasts with atmospheric mercury depletion events observed during the Arctic spring. Unlike previous Antarctic studies, we think that atmospheric Hg0 removal may not be the result of advection processes. The daily and dramatic Hg0 losses could be a consequence of surface or snow induced oxidation pathways. It remains however unclear whether halogens are involved. The cycling of other oxidants should be investigated together with Hg species in order to clarify the complex reactivity on the Antarctic plateau.

Snow physics as relevant to snow photochemistry

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.

An overview of snow photochemistry: evidence, mechanisms and impacts

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 NOx 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.

Snow physics as relevant to snow photochemistry

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 the 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, optical properties, thermal conductivity, permeability and gas diffusivity. Inasmuch as possible, equations to parameterize these properties as a function 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.

An overview of snow photochemistry: evidence, mechanisms and impacts

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 NOx 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.