Reducing role of sulfides and diamond formation in the Earth's mantle

Sulfides are abundant inclusions in diamond, but their role in the diamond genesis is still debatable. To address this issue, experimental modeling of natural diamond-forming processes with the participation of sulfides has been performed with the MgCO3–SiO2–Al2O3–FeS system at 6.3 GPa in the temperature range of 1250–1800 °C, using a multi-anvil high pressure apparatus of the “split-sphere” type. As a result of redox reactions involving carbonate, oxides and sulfide, diamond and/or graphite are produced in association with garnet, orthopyroxene, coesite and sulfides (pyrite, pyrrhotite). Diamond crystals, formed from the carbon of initial carbonate, are found to contain nitrogen impurity with total concentration of approximately 1500 ppm, and defects related to hydrogen impurity. Based on the experimental data and thermodynamic calculations, the processes of the carbonate–oxide–sulfide interaction are reconstructed, revealing the role of sulfides as a reducing agent for CO2-fluid. It is established that pyrrhotite acts as the reducing agent irrespective of its aggregate state (solid or melt). At temperatures below melting, pyrrhotite is enriched with sulfur and depleted with iron from FeS to Fe0.85S. At higher temperatures, sulfide melt is enriched with sulfur and crystallizes as pyrite and pyrrhotite during quenching. The medium in which diamond and/or graphite crystallize is a CO2-dominated fluid containing dissolved carbon, silicates, oxides and sulfides. The investigated processes and mechanisms of diamond crystallization can be considered as a possible model of the diamond formation in sulfide-bearing paragenesis in mantle metasomatism or UHP metamorphism of crustal material.