Wüstite stability in the presence of a CO2-fluid and a carbonate-silicate melt: Implications for the graphite/diamond formation and generation of Fe-rich mantle metasomatic agents

• Interaction of FeO, CO2 and carbonate-silicate melt under mantle P–T is realized.
• Graphite and diamond formation via wüstite–CO2 interaction is shown.
• Fe2 +,Fe3 +-enriched carbonate-silicate melts are generated.

Experimental simulation of the interaction of wüstite with a CO2-rich fluid and a carbonate-silicate melt was performed using a multianvil high-pressure split-sphere apparatus in the FeO-MgO-CaO-SiO2-Al2O3-CO2 system at a pressure of 6.3 GPa and temperatures in the range of 1150 °C–1650 °C and with run time of 20 h. At relatively low temperatures, decarbonation reactions occur in the system to form iron-rich garnet (Alm75Prp17Grs8), magnesiowüstite (Mg# ≤ 0.13), and CO2-rich fluid. Under these conditions, magnesiowüstite was found to be capable of partial reducing CO2 to C0 that leads to the formation of Fe3+-bearing magnesiowüstite, crystallization of magnetite and metastable graphite, and initial growth of diamond seeds. At T ≥ 1450 °C, an iron-rich carbonate-silicate melt (FeO ~ 56 wt.%, SiO2 ~ 12 wt.%) forms in the system. Interaction between (Fe,Mg)O, SiO2, fluid and melt leads to oxidation of magnesiowüstite and crystallization of fayalite-magnetite spinel solid solution (1450 °C) as well as to complete dissolution of magnesiowüstite in the carbonate-silicate melt (1550 °C–1650 °C). In the presence of both carbonate-silicate melt and CO2-rich fluid, dissolution (oxidation) of diamond and metastable graphite was found to occur. The study results demonstrate that under pressures of the lithospheric mantle in the presence of a CO2-rich fluid, wüstite/magnesiowüstite is stable only at relatively low temperatures when it is in the absolute excess relative to CO2-rich fluid. In this case, the redox reactions, which produce metastable graphite and diamond with concomitant partial oxidation of wüstite to magnetite, occur. Wüstite is unstable under high concentrations of a CO2-rich fluid as well as in the presence of a carbonate-silicate melt: it is either completely oxidized or dissolves in the melt or fluid phase, leading to the formation of Fe2 +- and Fe3 +-enriched carbonate-silicate melts, which are potential metasomatic agents in the lithospheric mantle.