In order to understand and predict the geochemical conditions in Antarctic meltwater ponds during winter, the geochemical extremes in Bratina Island meltwater ponds over a seasonal cycle were determined and compositional variation related to key physical, chemical and biological processes. A high resolution record of vertical temperature gradients in Skua Pond during freezing, winter and thaw, highlighted a significant seasonal temperature variation (10.3˚C to -41.8˚C) driven by air temperatures and the release of latent heat of fusion. A conceptual model of freeze-thaw involved heterogeneous melting, and explained how the presence of an ice plug near the base of the pond supports the strong chemical stratification observed, which can persist throughout summer. The geochemistry of Bratina Island meltwater ponds was shown to be catchment specific with correlation between geochemical parameters within ponds, but not between ponds. Basal brines that develop during freezing were nearer in composition to the brines preserved during summer, than to those present immediately post-melting. This is due to mineral precipitation during winter removing selected dissolved ions. Therefore winter brine predictions should be based on mid-late summer conditions, and allow for existing geochemical stratification. Nutrient concentrations were vertically stratified, by the same physical processes controlling major ion concentrations. However, the relatively low nutrient concentrations meant that biological processes exerted little influence over winter brine geochemistry. FREZCHEM62 modeled winter brine compositions were consistent with those of brines present during progressive freezing. Predicted mineral precipitation was also consistent with the presence of halite (NaCl), mirabilite (Na₂SO₄.10H₂O), thenardite (Na₂SO₄), magnesite (MgCO₃), gypsum (CaSO₄), sodium carbonate (NaCO₃) and calcite (CaCO₃) in pond sediments. FREZCHEM62 can therefore be used with confidence to predict winter conditions, as long as a reliable initial bulk pond water composition is calculated, and limitations, such as the over-prediction of carbonate mineral formation, are borne in mind.

Understanding the physics of water evaporation from saline porous media is important in many processes such as soil salinity, terrestrial ecosystem functioning, vegetation and crop production, biological activities in vadose zone, and CO2 sequestration. Precipitation of salt is one of the possible outcomes of the evaporation process from saline porous media which may either enhance or interrupt the desired process depending on the localization and pattern of the precipitated salt. In the present study X-ray micro tomography was used to study the 3D dynamics and patterns of salt deposition in drying porous media under different boundary conditions and the effects of salt concentration, particle size distribution and shape of grains on the precipitation patterns and dynamics at pore-scale have been investigated. Evaporation process from porous media involves preferential invasion of large pores on the surface while the fine pores remain saturated serving as the evaporation sites to supply the evaporative demand. This results in increasing salt concentration in fine pores during evaporation. Precipitation starts when salt concentration exceeds the solubility limit in the preferential evaporation sites. At the early stages, the precipitation rate increases with time until all evaporation sites at the surface reach the solubility limit and turn into the precipitation sites. This is followed by a constant rate of precipitation proportional to the evaporation rate. We show that the formation of salt crust at the surface does not immediately interrupt the evaporation process due to the porous nature of the precipitated salt investigated using the scanning electron microscopy. Also, our results confirmed the formation of discrete efflorescence at the surface of porous media due to the presence of pores with different sizes. Distribution of these fine pores on the surface directly influences the patterns of salt precipitation and thickness of the salt crust such that in the media with more fine pores, precipitated salt forms a thinner crust as the solute transferred to the surface is distributed among more evaporation sites. In contrast, in the media with fewer evaporation sites at the surface the salt crust will be more discrete but thicker. A simple equation is also proposed to estimate the evolution if the thickness of the salt crust on the surface of porous media. Our results provide new insights regarding the physics of salt precipitation and its complex dynamics in porous media during evaporation.