Although molten carbonates only represent, at most, a very minor phase in the Earth’s mantle, they are thought to be implied in anomalous high-conductivity zones in its upper part (70–350 km). Besides, the high electrical conductivity of these molten salts is also exploitable in fuel cells. Here, we report quantitative calculations of their properties, over a large range of thermodynamic conditions and chemical compositions, which are a requisite to develop technological devices and to provide a better understanding of a number of geochemical processes. To model molten carbonates by atomistic simulations, we have developed an optimized classical force field based on experimental data of the literature and on the liquid structure issued from ab initio molecular dynamics simulations performed by ourselves. In implementing this force field into a molecular dynamics simulation code, we have evaluated the thermodynamics (equation of state and surface tension), the microscopic liquid structure and the transport properties (diffusion coefficients, electrical conductivity, and viscosity) of molten alkali carbonates (Li2CO3, Na2CO3, K2CO3, and some of their binary and ternary mixtures) from the melting point up to the thermodynamic conditions prevailing in the Earth’s upper mantle (∼1100–2100 K, 0–15 GPa). Our results are in very good agreement with the data available in the literature. To our knowledge, a reliable molecular model for molten alkali carbonates covering such a large domain of thermodynamic conditions, chemical compositions, and physicochemical properties has never been published yet.

Atomistic simulations provide a meaningful way to determine the physicochemical properties of liquids in a consistent theoretical framework. This approach takes on a particular usefulness for the study of molten carbonates, in a context where thermodynamic and transport data are crucially needed over a large domain of temperatures and pressures (to ascertain the role of these melts in geochemical processes) but are very scarce in the literature, especially for the calcomagnesian compositions prevailing in the Earth’s mantle. Following our work on Li2CO3–Na2CO3–K2CO3 melts, we extend our force field to incorporate Ca and Mg components. The empirical interaction potentials are benchmarked on the density data available in the experimental literature [for the crystals and the K2Ca(CO3)2 melt] and on the liquid structure issued from ab initio molecular dynamics simulations. Molecular dynamics simulations are then performed to study the thermodynamics, the microscopic structure, the diffusion coefficients, the electrical conductivity, and the viscosity of molten Ca,Mg-bearing carbonates up to 2073 K and 15 GPa. Additionally, the equation of state of a Na–Ca–K mixture representative of the lavas emitted at Ol Doinyo Lengai (Tanzania) is evaluated. The overall agreement between the MD results and the existing experimental data is very satisfactory and provides evidence for the ability of the force field to accurately model any MgCO3–CaCO3–Li2CO3–Na2CO3–K2CO3 melt over a large T–P range. Moreover, it is the first report of a force field allowing us to study the transport properties of molten magnesite (MgCO3) and molten dolomite [CaMg(CO3)2].

Significance Platinum group elements (PGE) are highly valued by many industrial applications, serve as important geochemical tracers of planetary processes, and are among eagerly sought natural resources of critical trace metals. We show here that aqueous sulfur-bearing fluids play a far more important role than believed in many natural and technological processes in which PGE are involved. This role is essentially ensured by the radical sulfur ion S 3 •− that forms extremely stable and soluble complexes with both Pt II and Pt IV . By enabling enhanced dissolution, transport, and precipitation of Pt, these species may be key players in PGE transfer, fractionation, and accumulation in the Earth’s crust. They may also offer novel opportunities for optimizing ore processing and nanomaterial synthesis.

No abstract

No abstract