Sn(II) chloride speciation and equilibrium Sn isotope fractionation under hydrothermal conditions: A first principles study

Knowledge of Sn(II) speciation in aqueous and gaseous phases and the corresponding isotope effects are critical for understanding the transport and deposition of Sn in various geological and cosmochemical processes. In this study, we use first principles method to investigate the speciation of stannous (Sn(II)) chloride in fluids under hydrothermal and supercritical conditions. The results show that SnCl3−, SnCl2(H2O) and SnCl(H2O)2+ are stable in hydrothermal solutions at temperatures of up to 300 °C, with SnCl3− being the dominant species, whereas SnCl2 and SnCl2(H2O) are the stable species in vapor phases. Notably, SnCl2 is found to be stable under supercritical conditions. The reduced partition function ratios (β factors) for the stable Sn(II) species and three major Sn minerals (cassiterite, megawite, and romarchite) are also calculated by first principles methods. The calculation results show that under equilibrium, heavy Sn isotopes are preferentially partitioned into stannic (Sn(IV)) species, and gaseous species enrich heavy Sn isotopes relative to aqueous species. Based on the equilibrium Sn isotope fractionation factors derived in this study, we use a transport-precipitation model to evaluate the Sn isotope response to cassiterite precipitation in hydrothermal fluids. The modeling results show that significant Sn isotope variability could be produced during cassiterite precipitation, with temperature and Sn speciation being the primary controlling factors. Furthermore, by comparing the Sn isotope variability in natural cassiterite and those derived from the model, we argue that Sn should occur predominantly as Sn(IV) species in hydrothermal fluids during cassiterite precipitation in tin mineralizing systems.