Constraints on the distribution of CaSO4·nH2O phases on Mars and implications for their contribution to the hydrological cycle

The stability of minerals in the CaSO4·nH2O system was investigated using a Bruker D8 X-ray powder diffractometer equipped with an environmental cell interfaced to a heating stage, low-temperature chiller, and relative humidity (RH) generator. This in situ analysis procedure allowed for precise monitoring of dehydration/hydration reactions over a range of PH2O values from 4 to 15,000 Pa. The formation of bassanite from gypsum was sluggish below 323 K and is unlikely to occur under current martian conditions over a diurnal/seasonal cycle from desiccation alone. Dehydration is possible on a localized scale in association with volcanic/impact events although temperatures of dehydration and rates of reaction depend on PH2O, particle size, sample thickness and heating rate. Analysis of anhydrite rehydration at 258 K suggests that if gypsum dehydration were to occur, bassanite would be observed on the martian surface under present low PH2O conditions. In addition, a stable bassanite phase could potentially cycle between n = 0.5 and n = 0.67 as a function of relative humidity (1–80%), resulting in a small flux of H2O between the atmosphere and the regolith over a diurnal cycle. Rehydration of bassanite to gypsum occurs only under conditions of 100%RH; therefore the presence of a bassanite phase on the surface of Mars can be used to help constrain paleoclimates. Low-temperature (258 K) XRD hydration experiments of bassanite resulted in the formation of gypsum in the presence of ice, suggesting that bassanite will not be present in association with H2O ice. This behavior could simulate a potential hydration mechanism on the martian surface at higher latitudes as well as at depth in association with subsurface ice at lower latitudes.