Iron carbonates in the Earth’s lower mantle: reality or imagination?

Abstract:

Carbonates play a fundamental role in the recycling of carbon inside our planet due to their presence in oceanic slabs that sink through the Earth’s interior. Through this process, iron carbonates are potential stable carbon-bearing minerals in the deep mantle in part due to spin crossover of ferrous iron. Our goal is to identify which minerals may be the dominant carriers of carbon into the deep mantle at the relevant conditions of fO₂, P and T. All experiments were performed using synthetic FeCO₃ and MgFeCO₃ single crystals in laser heated diamond anvil cells up to 100 GPa and 3000 K in order to simulate the conditions prevailing in the Earth’s lower mantle. Transformation and decomposition products of the original carbonates were characterized at different synchrotron facilities by means of single-crystal XRD, synchrotron Mössbauer source spectroscopy and XANES techniques. At deep lower mantle conditions, we observed the transformation of FeCO₃ to two new HP-carbonate structures, monoclinic Fe₂²⁺Fe₂³⁺C₄O₁₃ and trigonal Fe₄³⁺(CO₄)₃, both characterized by the presence of CO₄ tetrahedra with different degrees of polymerization. At shallower depths in the lower mantle where temperatures are lower following the geotherm, Fe-carbonates decompose to different Fe-oxides instead of new HP-carbonates. However, at slab temperatures several hundred degrees lower than the surrounding mantle, carbonates could be stabilized until reaching conditions that trigger their transformation to HP-structures. We postulate that Fe-rich carbonates could exist in regions down to the core-mantle boundary in the proximity of subducting slabs, i.e., a “cold” environment with relatively high fO₂.