Breyite inclusions in diamond: experimental evidence for possible dual origin

Inclusions of breyite (previously known as walstromite-structured CaSiO3) in diamond are usually interpreted as retrogressed CaSiO3 perovskite trapped in the transition zone or the lower mantle. However, the thermodynamic stability field of breyite does not preclude its crystallization together with diamond under uppermantle conditions (6-10 GPa). The possibility of breyite forming in subducted sedimentary material through the reaction CaCO3 + SiO2 = CaSiO3 + C + O-2 was experimentally evaluated in the CaO-SiO2-C-O-2 +/- H2O system at 6-10 GPa, 900-1500 degrees C and oxygen fugacity 0.5-1.0 log units below the Fe-FeO (IW) buffer. One experimental series was conducted in the anhydrous subsystem and aimed at determining the melting temperature of the aragonite-coesite (or stishovite) assemblage. It was found that melting occurs at a lower temperature (similar to 1500 degrees C) than the decarbonation reaction, which indicates that breyite cannot be formed from aragonite and silica under anhydrous conditions and an oxygen fugacity above IW - 1. In the second experimental series, we investigated partial melting of an aragonite-coesite mixture under hydrous conditions at the same pressures and redox conditions. The melting temperature in the presence of water decreased strongly (to 900-1200 degrees C), and the melt had a hydrous silicate composition. The reduction of melt resulted in graphite crystallization in equilibrium with titanite-structured CaSi2O5 and breyite at similar to 1000 degrees C. The maximum pressure of possible breyite formation is limited by the reaction CaSiO3 + SiO2 = CaSi2O5 at similar to 8 GPa. Based on the experimental results, it is concluded that breyite inclusions found in natural diamond may be formed from an aragonite-coesite assemblage or carbonate melt at 6-8 GPa via reduction at high water activity.