Melting curve of compressed barium carbonate from in situ ionic conductivity measurements: Implications for the melting behavior of alkaline earth carbonates in Earth's deep carbon cycle

The whereabouts of subducted carbonates place a major constraint on the Earth's deep carbon cycle, but the fraction of carbon retained in the slab and transported into the deep mantle, compared to that released from the slab and recycled to the surface, is still under debate. Knowledge of the stability of carbonated mantle rocks is pivotal for assessing the ability of slabs to carry carbonates into the deep mantle. Determination and systematic comparison of the melting curves of alkali and alkaline earth carbonates at high pressure can help construct thermodynamic models to predict the melting behavior of complex carbonated mantle rocks. Among alkaline earth carbonates, the melting behavior of barium carbonate (BaCO3) has not been adequately understood. The reported melting point of BaCO3at 1 bar differ by nearly 800 °C and constraints on the melting curve of BaCO3 at high pressure are not available. In this study, the melting temperatures of BaCO3 were determined up to 11 GPa from in situ ionic conductivity measurements using the multi-anvil apparatus at the University of Michigan. The solid-liquid boundary at high pressure was detected on the basis of a steep rise in conductivity through the sample upon melting. The melting point of BaCO3 was found to drop from 1797 °C at 3.3 GPa to 1600 °C at 5.5 GPa and then rise with pressure to 2180 °C at 11 GPa. The observed melting depression point at 5.5 GPa corresponds to the phase transition of BaCO3 from the aragonite structure (Pmcn) to post-aragonite structure (Pmmn) at 6.3 GPa, 877 °C and 8.0 GPa, 727 °C, determined from synchrotron X-ray diffraction measurements using laser-heated DAC experiments at the Advanced Photon Source, Argonne National Laboratory. These results are also compared with ex situ falling marker experiments, and the three methods together place tight constraints on the melting curve of BaCO3 and elucidates the effect of structural phase transitions on its melting behavior.