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Equilibrium dihedral angles in the system H2O−CO2−NaCl-calcite, and implications for fluid flow during metamorphism

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Abstract

Fluid-calcite-calcite dihedral angles have been measured for fluids in the system H2O−CO2−NaCl, between 1 and 2 kbar, and 550–750° C. It is found that the calcite-calcite-H2O dihedral angle decreases steadily with addition of NaCl from a value of about 80° (pure water) to 44° (60 wt% NaCl). The CO2−H2O system displays a well-defined minimum at \(X_{CO_2 } = 0.5\), with a dihedral angle of 50°, in contrast to those of pure CO2 and H2O which are 90° and 80° respectively. Experiments containing fluids which are immiscible at run conditions showed a bimodal distribution of dihedral angles in the CO2−H2O−NaCl system, which can be approximately correlated with the compositions of the two fluid phases. Such bimodality was only observed for immiscible fluids in the H2O−NaCl system if the quench rate exceeded about 200°C per min. This is probably due to the extremely rapid establishment of the single phase dihedral angle on quenching. The fluid phase topology in devolatilising marbles will only be a connected network for very saline brines and fluids with \(X_{CO_2 } \) close to 0.5. Fluids trapped in fluid inclusions in calcite grains in marbles may be predominantly H2O-rich or CO2-rich, and of low salinity. All other fluid compositions in the H2O−CO2−NaCl-calcite system will occupy isolated pores, the largest of which will grow at the expense of the smallest. Escape of fluid produced during devolatilisation reactions under such conditions will occur by fluid overpressuring and hydrofracture. In contrast, previous experimental studies of quartz-fluid dihedral angles between 950° and 1100° C (Watson and Brenan 1987) predict that quartz-dominated lithologies will permit pervasive flow of H2O−NaCl fluids, but not of H2O−CO2 fluids. Documented geological examples of differences in permeability and fluid flow mechanism between metamorphic argillites, psammites and limestones which support the results of the experimental studies are discussed.

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Holness, M.B., Graham, C.M. Equilibrium dihedral angles in the system H2O−CO2−NaCl-calcite, and implications for fluid flow during metamorphism. Contr. Mineral. and Petrol. 108, 368–383 (1991). https://doi.org/10.1007/BF00285944

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