Phase equilibria in the H2O-CO2 system between 250-330 K and 0-1.7 GPa: Stability of the CO2 hydrates and H2O-ice VI at CO2 saturation

Although carbon dioxide is of interest in planetary science, few studies have been devoted so far to the H2O-CO2 system at pressures and temperatures relevant to planetary interiors, especially of the icy moons of the giant planets. In this study, new sapphire and diamond anvil cell experiments were conducted in this binary system to constrain the stability of the CO2 hydrates and H2O-ice VI at CO2 saturation in the 250-330 K and 0-1.7 GPa temperature and pressure ranges. Phases and equilibria were characterized by in situ Raman spectroscopy and optical monitoring. The equilibrium between the CO2 sI clathrate hydrate and the H2O-rich liquid phase was constrained over the entire pressure range of stability of the hydrate, up to 0.7-0.8 GPa, with results in agreement with previous studies at lower pressures. Above this pressure and below 1 GPa, our experiments confirmed the existence of the new CO2 high-pressure hydrate reported recently. Finally, the melting curve of the H2O-ice VI at CO2 saturation in the absence of CO2 hydrates was determined between 0.8 and 1.7 GPa. Using an available chemical potential model for H2O, a first assessment of the solubility of CO2 along the H2O-ice VI melting curve is given. Consistent with these new results and previous studies of the H2O-CO2 system, a P-T-X description of the binary system is proposed. The evolution with pressure of the Raman signatures of the two CO2 hydrates is detailed, and their stability is discussed in light of other clathrate hydrate-forming systems. (C) 2013 Elsevier Ltd. All rights reserved.