High-Pressure Orthorhombic Ferromagnesite as a Potential Deep-Mantle Carbon Carrier

Knowledge of the physical and chemical properties of candidate deep-carbon carriers such as ferromagnesite [(Mg,Fe)CO₃] at high pressure and temperature of the deep mantle is necessary for our understanding of deep-carbon storage as well as the global carbon cycle of the planet. Previous studies have reported very different scenarios for the (Mg,Fe)CO₃ system at deep-mantle conditions including the chemical dissociation to (Mg,Fe)O+CO₂, the occurrence of the tetrahedrally-coordinated carbonates based on CO₄ structural units, and various high-pressure phase transitions. Here we have studied the phase stability and compressional behavior of (Mg,Fe)CO₃ carbonates up to relevant lower-mantle conditions of approximately 120 GPa and 2400 K. Our experimental results show that the rhombohedral siderite (Phase I) transforms to an orthorhombic phase (Phase II with Pmm2 space group) at approximately 50 GPa and 1400 K. The structural transition is likely driven by the spin transition of iron accompanied by a volume collapse in the Fe-rich (Mg,Fe)CO₃ phases; the spin transition stabilizes the high-pressure phase II at much lower pressure conditions than its Mg-rich counterpart. It is conceivable that the low-spin ferromagnesite phase II becomes a major deep-carbon carrier at the deeper parts of the lower mantle below 1900 km in depth.