Water activities of NaClO4, Ca(ClO4)2, and Mg(ClO4)2 brines from experimental heat capacities: Water activity >0.6 below 200 K

Perchlorate salts found on Mars are extremely hygroscopic and form low eutectic temperature aqueous solutions, which could allow liquid water to exist on Mars despite cold and dry conditions. The formation, dynamics, and potential habitability of perchlorate salt solutions can be broadly understood in terms of water activity. Water activity controls condensation and evaporation of water vapor in brines, deliquescence and efflorescence of crystalline salts, and ice formation during freezing. Furthermore, water activity is a basic parameter defining the habitability of aqueous solutions. Despite the importance of water activity, its value in perchlorate solutions has only been measured at 298.15 K and at the freezing point of water. To address this lack of data, we have determined water activities in NaClO4, Ca(ClO4)(2), and Mg(ClO4)(2) solutions using experimental heat capacities measured by Differential Scanning Calorimetry. Our results include concentrations up to near-saturation and temperatures ranging from 298.15 to 178 K. We find that water activities in NaClO4 solutions increase with decreasing temperature, by as much as 0.25 a(w) from 298.15 to 178 K. Consequently, a(w) reaches similar to 0.6-0.7 even for concentrations up to 15 molal NaClO4 below 200 K. In contrast, water activities in Ca(ClO4)(2) and Mg(ClO4)(2) solutions generally decrease with decreasing temperature. The temperature dependence of water activity indicates that low-temperature NaClO4 solutions will evaporate and deliquesce at higher relative humidity, crystallize ice at higher temperature, and potentially be more habitable for life (at least in terms of water activity) compared to solutions at 298.15 K. The opposite effects occur in Ca(ClO4)(2) and Mg(ClO4)(2) solutions. (C) 2016 Elsevier Ltd. All rights reserved.