C‐O‐H‐S fluid composition and oxygen fugacity in graphitic metapelites

Abstract

Abstract C‐O‐H fluid produced by the equilibration of H2O and excess graphite must maintain the atomic H/O ratio of water, 2:1. This constraint implies that all thermodynamic properties of the fluid are uniquely determined at isobaric‐isothermal conditions. The O2, H2O and CO2 fugacities (fo2, fH2O and fCO2) of such fluids have been estimated from equations of state and fit as a function of pressure and temperature. These fugacities can be taken as characteristic for graphitic metamorphic systems in which the dominant fluid source is dehydration, e.g. pelitic lithologies. Because there are no compositional degrees of freedom for graphite‐saturated fluids produced entirely by dehydration, the variance of the dehydration process is not increased in comparison with that in non‐graphitic systems. Thus, compositional ‘buffering’of C‐O‐H fluids by dehydration equilibria, a common petrological model, requires that redox reactions, decarbonation reactions or external, H/O ± 2, fluid sources perturb the evolution of the metamorphic system. Such perturbations are not likely to be significant in metapelitic environments, but their tendency will be to increase the fO2 of the fluid phase. At high metamorphic grades, pyrite desulphidation reactions may cause a substantial reduction of fH2O and slight increases in fO2 and fCO2 relative to sulphur‐free fluid. At low metamorphic grade, sulphur solubility in H/O ± 2 fluids is so low that pyrite decomposition must occur by sulphur‐conserving reactions that cause iron depletion in silicates, a common feature of sulphidic pelites. With increasing temperature and sulphur solubility, pyrite desulphidation may be driven by dehydration reactions or infiltration of H2O‐rich fluids. The absence of magnetite and the assemblages carbonate + aluminosilicate or pyrite + pyrrhotite + ilmenite from most graphitic metapelites is consistent with an H/O = 2 model for GCOH(S) fluid. For graphitic rocks in which such a model is inapplicable, a phase diagram variable that defines the H/O ratio of GCOH(S) fluid is more useful than the conventional fO2 variable.