Thermodynamic constraints on carbonate stability and carbon volatility during subduction
Abstract The breakdown of carbonate minerals at high pressure is frequently cited as an important mechanism that leads to carbon release from subducted rocks. However, carbonate minerals in the subducting slab are predicted to be stable to depths that are greater than arc-generating magma depths of approximately 150 km, implying that breakdown of carbonate phases in dehydrated MORB may not be a major contributor to arc volcano carbon budgets. To account for this discrepancy, previous studies have suggested that addition of H2O-rich fluids promotes the breakdown of carbonate-rich lithologies, thus generating volatile C species that could be incorporated into arc magmas. Here, we explore the feasibility of H2O-mediated decarbonation with a simple thermodynamic model. We calculate equilibrium mineral assemblages and accompanying fluid H2O/CO2 ratios for typical subducted lithologies, assuming a range of subduction zone geotherms, and explore the implications of addition of external fluids that are generated from deserpentinization of ultramafic lithologies at various stages. Results suggest that the liberation of C along volcanic arcs is facilitated by either the breakdown of carbonate minerals due to thermodynamically favorable conditions in hotter subduction systems, or by the breakdown of carbonate minerals during periods of higher fluid productivity associated with deserpentinization at appropriate depths along colder subduction geotherms. A comparison of C fluxes measured at volcanic arcs shows that colder subduction zones generate higher C fluxes, implying that the depth at which deserpentinization reactions occur strongly controls the availability of aqueous fluids for slab decarbonation, and that fluid availability represents the dominant control on carbon volatility during subduction.