Experimental Determination of Sr partitioning and Ca Isotope Fractionation in the CaSO4-NaCl-H2O system

Anhydrite and gypsum are important, retrograde soluble minerals in geologic environments including mid ocean ridge hydrothermal systems and saline aquifers. Precipitation and/or dissolution of Ca-sulfate phases may control the distribution of stable Ca isotopes and Sr concentrations between fluids and minerals. Considerable research in the CaCO3-H2O system suggests that stable isotope fractionation of Ca between the dissolve pool and precipitating mineral are primarily controlled by the mineral growth rates. The partitioning of Sr appears to be growth rate dependent as well. We designed a series of hydrothermal precipitation experiments to test the idea that similar rate dependent isotope and trace metal fractionation occurs in the CaSO4-H2O system. Experiments were conducted between 110-160C using a titanium Parr mini bench top reactor. Mixtures of CaCl2, SrCl2 and Na2SO4 were dissolved in water and loaded into a Teflon lined vessel. Sealed experiments were purged with nitrogen gas for approximately 20 minutes to create a CO2-free environment. Experiments were rapidly charged to approximately 250 psi and heated to the desired run temperature. Experiment duration was between 36 and 360 hours. Completed experiments were depressurized and solid run products were recovered by filtration. Fluid samples from the beginning and end of each experiment were preserved for elemental and isotopic measurements. Preliminary results for experiments with CaSO4 supersaturation ~10 have thin needle-like crystals of mixed gypsum-bassanite-anhydrite based on SEM and XRD analysis. Sr distribution coefficients range between 0.48-0.74, greater than published equilibrium values, while D44Ca = 0.7-1.1 per mil, similar to low temperature carbonates.