Metasomatic ijolite, glimmerite, silicocarbonatite, and antiskarn formation: carbonatite and silicate phase equilibria in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–O₂–CO₂

Abstract

Silicocarbonatites are carbonatite rocks containing > 20% silicate minerals. Their formation is not well understood due to low silica solubility in carbonatite melts and negligible amounts of silicate minerals on carbonatite melt cotectics at upper crustal conditions. We explore whether silicocarbonatites can be thought of as antiskarns: rocks formed by leaching of SiO2 from siliceous wall rocks by carbonatite melts, and its deposition as solid silicate minerals by reaction with chemical components already present in the carbonatite melt. Solid state thermodynamic modelling at 1-5 kbar and 500-800 degrees C predicts that calcite-dolomite-magnetite assemblages will transform to dolomite-free silicocarbonatites with an increase in silica contents. In sodic systems, the formation of aegirine and alkali amphiboles suppresses silica activity despite elevated silica contents. Therefore, dolomite remains stable, but Fe3+ is consumed, firstly from magnetite breakdown, and secondly by coupled Fe oxidation and reduction of CO2 to CO, CH4, and graphite, particularly at higher pressures. Despite a net increase in Fe3+/Fe2+, the system evolves to increasingly lower oxygen fugacity. In aluminous systems, nepheline indicates high temperatures whereas alkali feldspars form at lower temperatures. Modelling of potassic systems demonstrates stability of mostly phlogopite-rich biotites, leading to Fe2+ increase in all other carbonate and silicate phases. We find that perthites are expected in high pressures whereas two feldspars are more likely in lower pressures. Aspects of the clinopyroxene natural compositional trend (diopside to hedenbergite to aegirine) of carbonatite systems can be explained by silica contamination. Ferrous clinopyroxenes typically require low alumina and are predicted in potassic or low temperature sodic systems, primarily at mid to high pressures. Silica contamination permits the formation of silicocarbonatite-like assemblages in a way that is not limited by SiO2 solubility in carbonatite melts. Glimmerites and clinopyroxene-rich rocks (such as the ijolite series) that often occur around carbonatite rocks at the contact with silica-oversaturated wall rocks can be explained as the extreme end of silica contamination of carbonatite melts. Therefore, these clinopyroxenites and glimmerites can form solely via metasomatic processes without the presence of a silicate melt.