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Zhang, Z, Qin T, Pommier A, Hirschmann MM.  2019.  Carbon storage in Fe-Ni-S liquids in the deep upper mantle and its relation to diamond and Fe-Ni alloy precipitation. Earth and Planetary Science Letters. 520:164-174.   10.1016/j.epsl.2019.05.039   AbstractWebsite

To better understand the role of sulfide in C storage in the upper mantle, we construct a thermodynamic model for Fe-Ni-S-C sulfide melts and consider equilibrium between sulfide melts, mantle silicates, Fe-Ni alloy, and diamond. The sulfide melt model is based upon previous parameterization of Fe-Ni-S melts calibrated at 100 kPa, which we have extended to high pressure based on volumetric properties of end-member components. We calculate the behavior of C in the sulfide melt from empirical parameterization of experimental C solubility data. We calculate the continuous compositional evolution of Fe-Ni sulfide liquid and associated effects on carbon storage at pressure and redox conditions corresponding to mantle depths of 60 to 410 km. Equilibrium and mass balance conditions were solved for coexisting Fe-Ni-S melt and silicate minerals (olivine [(Mg,Fe,Ni)(2)SiO4], pyroxene [(Mg,Fe)SiO3]) in a mantle with 200 ppmw S. With increasing depth and decreasing oxygen fugacity ( f(02)), the calculated melt (Fe+Ni)/S atomic ratio increases from 0.8-1.5 in the shallow oxidized mantle to 2.0-10.5 in the reduced deep upper mantle (>8 GPa), with Fe-Ni alloy saturation occurring at >10 GPa. Compared to previous calculations for the reduced deep upper mantle, alloy saturation occurs at greater depth owing to the capacity of sulfide melt to dissolve metal species, thereby attenuating the rise of Fe and Ni metal activities. The corresponding carbon storage capacity in the metal-rich sulfide liquid rises from negligible below 6 GPa to 8-20 ppmw at 9 GPa, and thence increases sharply to 90-110 ppmw at the point of alloy saturation at 10-12 GPa. The combined C storage capacity of liquid and solid alloy reaches 110-170 ppmw at 14 GPa. Thus, in the deep upper mantle, all carbon in depleted sources (10-30 ppmw C) can be stored in the sulfide liquid, and alloy and sulfide liquids host a significant fraction of the C in enriched sources (30-500 ppmw C). Application of these results to the occurrences of inferred metal-rich sulfide melts in the Fe-Ni-S-C system and inclusions in diamonds from the mantle transition zone suggests that oxidization of a reduced metal-rich sulfide melt is an efficient mechanism for deep-mantle diamond precipitation, owing to the strong effect of (Fe+Ni)/S ratio on carbon solubility in Fe-Ni-S melts. This redox reaction likely occurs near the boundary between oxidized subducted slabs and the reduced ambient peridotitic mantle. (C) 2019 Elsevier B.V. All rights reserved.

Zhang, Z, Pommier A.  2017.  Electrical Investigation of Metal-Olivine Systems and Application to the Deep Interior of Mercury. Journal of Geophysical Research: Planets.   10.1002/2017JE005390   Abstract

We report electrical conductivity measurements on metal-olivine systems at about 5 and 6 GPa and up to 1,675°C in order to investigate the electrical properties of core-mantle boundary (CMB) systems. Electrical experiments were conducted in the multianvil apparatus using the impedance spectroscopy technique. The samples are composed of one metal layer (Fe, FeS, FeSi2, or Fe-Ni-S-Si) and one polycrystalline olivine layer, with the metal:olivine ratio ranging from 1:0.7 to 1:9.2. For all samples, we observe that the bulk electrical conductivity increases with temperature from 10−2.5 to 101.8 S/m, which is higher than the conductivity of polycrystalline olivine but lower than the conductivity of the pure metal phase at similar conditions. In some experiments, a conductivity jump is observed at the temperature corresponding to the melting temperature of the metallic phase. Both the metal:olivine ratio and the metal phase geometry control the electrical conductivity of the two-layer samples. By combining electrical results, textural analyses of the samples, and previous studies of the structure and composition of Mercury's interior, we propose an electrical profile of the deep interior of the planet that accounts for a layered CMB-outer core structure. The electrical model agrees with existing conductivity estimates of Mercury's lower mantle and CMB using magnetic observations and thermodynamic calculations, and thus, supports the hypothesis of a layered CMB-outermost core structure in the present-day interior of Mercury. We propose that the layered CMB-outer core structure is possibly electrically insulating, which may influence the planet's structure and cooling history.