Observations were made of water column chemistry in four Na-Cl dominated ponds on the McMurdo Ice Shelf from the end of January to early April in 2008. During that time the ponds went from ice-free to predominantly frozen, with only a small volume of residual hypoxic, saline liquid trapped at the base of each pond. Changes in the concentrations of inorganic solutes with time distinguished Na, Cl, Mg, K, SO4, As, U and Mn as ions and trace elements that behave mainly conservatively during freezing, from those which are affected by biological processes (removing HCO3) and the precipitation of mineral phases such as calcite (removing Ca and more HCO3). Dissolved Fe, Mo, Cu and Zn also show evidence of precipitation from the water column during freezing; geochemical speciation modelling predicts the formation of stable insoluble mineral phases such as Fe oxides and oxyhydroxides while conditions are oxic, and Fe-, Cu-, Mo- and Zn-sulphide minerals in the presence of H2S. Consequently, under winter conditions, residual liquid beneath the ice in such ponds is anticipated to be an anoxic Na-Cl brine with the capacity to develop high concentrations of toxic trace elements such as As and U.

The geochemistry and vertical stratification of shallow meltwater ponds at 78°S near Bratina Island (McMurdo Ice Shelf) have been determined for late winter (October) and summer (January) conditions as part of the Latitudinal Gradient Project. Of the five frozen ponds investigated in October, all were stratified with respect to conductivity, and three had highly saline basal brines beneath the ice at temperatures of −16 to −20°C. In the ice column, inclusions of saline fluid were observed in channels between ice crystals; the abundance increasing with depth and decreasing ice crystal size. In January, seven of the ten ponds investigated (including ponds sampled in October) retained conductivity stratification, whereas significant thermal stratification was observed in only three ponds (maximum ΔT = 5.5°C). Basal brines, ice and meltwaters were Na-Cl or Na-SO4 dominated. FREZCHEM52 modelling, supported by changes in ion ratios, indicated that the precipitation of mirabilite (Na2SO4.10H2O) and gypsum (CaSO4.2H2O) during progressive freezing is an important determinant in chemical evolution of the basal brine. High pH (8.8–11.2) and over-saturation with respect to dissolved oxygen (> 20 mg L−1) in summer, and the presence of sulphide ions in basal brines in winter, occurred in those ponds which experienced high biological productivity during the summer months.