Apparent Disequilibrium of Inorganic and Organic Carbon Compounds in Serpentinizing Fluids

During serpentinization of ultramafic rocks, ferrous iron in silicates is oxidized to ferric minerals and H₂O is reduced to H₂. This process is accompanied by the reduction of inorganic carbon, as observed in experiments and natural systems. To test the extent to which stable and metastable equilibria are reached among aqueous organic compounds during serpentinization, we sampled water and dissolved gases from circumneutral surface pools and hyperalkaline seeps in the Samail ophiolite in the Sultanate of Oman and analyzed for various carbon constituents, including dissolved inorganic carbon, dissolved organic carbon, methane, carbon monoxide, formate, acetate, and other small organic acid anions. Measurements of temperature, pH, dissolved H₂, O₂, major cations, major anions, and major and trace elements were also made.

The aqueous composition of the analyzed samples was speciated based on ionic equilibrium interactions in order to obtain activities for inorganic carbon species, reduced carbon species, H₂, and O₂. The redox disequilibria among carbon species was then assessed using data and parameters for the revised HKF equations of state. This analysis demonstrates that the carbon species in this system are out of equilibrium with respect to one another in ways that cannot be compensated by altering the abundance of the other constituents within analytical uncertainties. Specifically, there is too much formate and too little methane relative to stable and metastable equilibria. This result implies the following: 1) Methane and formate equilibrated in separate parts of the system, given that no reasonable temperature, pressure, or composition changes satisfy equilibrium with their measured abundances. 2) Methane production is kinetically inhibited, as seen in experiments. 3) Microbial methane oxidation altered the abundance of methane and formate; methane oxidation to formate or carbonate is calculated to be extremely thermodynamically favorable in these fluids.