Sean M. Hurt, Aaron S. Wolf

MgCO3 is one of the most important components of mantle-derived carbonatite melts, and yet also one of the most difficult to study experimentally. Attempts to constrain its thermodynamic properties are hampered by decarbonation, which occurs at only ~500 °C, far below its metastable 1 bar melting temperature. Molecular dynamic simulations, however, can predict the thermodynamic properties of the MgCO¬3 liquid component in spite of experimental challenges. Using the recently developed empirical potential model for high-pressure alkaline-earth carbonate liquids (Hurt and Wolf 2018), we simulate melts in the MgCO3-CaCO3-SrCO3-BaCO3 system from 773 to 2373 K up to 20 GPa. At 1 bar, MgCO3 liquid assumes a novel topology characterized by a 4-fold coordination of the metal cation (Mg) with both the carbonate molecule and oxygen ion; this is distinct from the other alkaline-earth carbonate liquids in which the metal cation is in ~6- and ~8-fold coordination with carbonate and oxygen. With increasing pressure, MgCO3 liquid structure becomes progressively more like that of (Ca, Sr, Ba)CO3 liquids with Mg2+ approaching 6-fold coordination with carbonate groups. The novel network topology of MgCO3 liquid results in a melt that is significantly more buoyant and compressible than other alkaline-earth carbonate liquids. Simulations of mixed MgCO3-bearing melts show that metal cation coordination with O and C is independent of bulk composition. Mixed simulation also reveal that molar volume, compressibility, enthalpy and heat capacity do not mix ideally with (Ca, Sr, Ba)CO3 liquids at 1 bar, a consequence of preferential metal-cation ordering in MgCO3-bearing mixtures. As pressure increases, however, mixing progressively approaches ideality with respect to molar volume, becoming nearly ideal by 12 GPa. The model is further applied to mantle-derived primary carbonatite melts with compositions, temperatures and pressures determined by published phase equilibrium experiments. The voluminous structure of liquid MgCO3 results in a buoyant melt that inhibits a density crossover with the surrounding mantle. Assuming FeCO3 liquid also adopts the same anomalous high-volume structure as MgCO3, we predict that even the most Fe-rich ferrocarbonatites would remain buoyant and be barred from sinking or stagnating in the mantle.