The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO₂CO fluids in a mid-ocean ridge basalt (morb) has been measured at 1200°C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. High oxygen fugacities, and thus CO₂-rich fluids, were produced by using a starting material equilibrated at NNO, and Ag₂C₂O₄ as the fluid source. Low oxygen fugacities were achieved by using graphite capsules, and MgCO₃ as the fluid source. These graphite-saturated fluids have the lowest possible CO₂ CO ratio for a given pressure and temperature. Experiments were run in a rapid-quench internally heated pressure vessel. Fluid compositions were measured using a simple vacuum technique and by Raman spectroscopy of fluid inclusions. The two techniques yielded comparable results. Fourier transform micro-infrared spectroscopy was used to identify and measure concentrations of dissolved volatiles in double-polished wafers of the quenched glasses. Carbonate was the only carbon-bearing species identified. Raman spectroscopic analysis of inclusion-free areas of glass confirmed the absence of dissolved molecular CO₂, CO and carbon. The measured concentrations of dissolved CO₂ in the glasses were proportional to the fugacity of CO₂ during the experiments, calculated from the measured fluid compositions. The data were fit to the equation X_CO2 ^melt(ppm) = 0.492 fCO₂ (bar). The insolubility of CO, compared to CO₂, may be related to the fact that dissolution of CO requires reduction of another species in the melt, whereas dissolution of CO₂ does not. Due to the fact that CO will be an important component of natural CO fluids at low pressures and low oxygen fugacities, equilibrium dissolved CO₂ contents will be less than calculated assuming pure CO₂ fluids, but as the CO₂ CO ratio in a pure CO fluid at fixed pressure and temperature is a direct function of oxygen fugacity, measurement of the oxygen fugacity of quenched glasses or trapped fluids in natural samples should allow saturation concentrations to be calculated. Dissolved CO₂ contents of some morb are less than expected if they were in equilibrium with pure CO₂. These samples must, therefore, have been more reduced than average if they were fluid-saturated. Together with results from other studies of CO₂ and H₂O solubilities in basalt, the results of this study provide a comprehensive framework for modelling CO₂ solution in morb.