Subduction tectonics imposes an important role in the evolution of the interior of the Earth and its global carbon cycle; however, the mechanism of the mantle-slab interaction remains unclear. Here, we demonstrate the results of high-pressure redox-gradient experiments on the interactions between Mg-Ca-carbonate and metallic iron, modeling the processes at the mantle-slab boundary; thereby, we present mechanisms of diamond formation both ahead of and behind the redox front. It is determined that, at oxidized conditions, a low-temperature Ca-rich carbonate melt is generated. This melt acts as both the carbon source and crystallization medium for diamond, whereas at reduced conditions, diamond crystallizes only from the Fe-C melt. The redox mechanism revealed in this study is used to explain the contrasting heterogeneity of natural diamonds, as seen in the composition of inclusions, carbon isotopic composition, and nitrogen impurity content.carbonate-iron interaction | high-pressure experiment | mantle mineralogy | deep carbon cycle S ubduction of crustal material plays an important role in the global carbon cycle (1-6). Depending on oxygen fugacity and pressure-temperature (P-T) conditions, carbon exists in the Earth's interior in the form of carbides, diamond, graphite, hydrocarbons, carbonates, and CO 2 (7-11). In the upper mantle, the oxygen fugacity (fO 2 ) varies from one to five log units below the fayalitemagnetite-quartz (FMQ) buffer, with a trend of a decrease with depth (6,(12)(13)(14)(15). At a depth of ∼250 km, mantle is reported to become metal saturated (16, 17), which holds true for all mantle regions below, including the transition zone and lower mantle. The subduction of the oxidized crustal material occurs to depths greater than 600 km (4-6). The main carbon-bearing minerals of the subducted materials are carbonates, which are thermodynamically stable up to P-T conditions of the lower mantle (10,11,18). As evidenced by the compositions of inclusions in diamond, which vary from strongly reduced, e.g., metallic iron and carbides (19-23), to oxidized, e.g., carbonates and CO 2 (6,20,(24)(25)(26)(27)(28), carbonates may be involved in the reactions with reduced deep-seated rocks, including Fe 0 -bearing species (29-31). A scale of these reactions is determined mainly by the capacity of subducted carbonate-bearing domains. An important consequence of such an interaction is that it can produce diamond. However, studies on diamond synthesis via the reactions between oxidized and reduced phases are limited (32-35).To understand the mechanisms of the interaction of carbonbearing oxidized-and reduced-mineral assemblages, we performed high-pressure experiments with an iron-carbonate system; an approach was used that enabled the creation of an oxygen fugacity gradient in the capsules (Materials and Methods and SI Materials and Methods). Results and DiscussionThe experimental results and the phase compositions are given in Table 1 and Table S1, respectively. At temperatures of 1,000 and 1,100°C, the iron-car...

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Diamond crystallization in the Mg-Si-C system has been studied at high pressure high temperature conditions of 7 GPa and 1500-1900 ºC. The features of nucleation and growth of diamond from the carbon solution in the Mg-Si melt are established. The degree of the graphiteto-diamond transformation is found to depend significantly on the crystallization temperature. As opposed to the pure Mg-C system where the cubic morphology dominates, the octahedron with the antiskeletal structure of faces is the dominant form of growth in the Mg-Si-C system over the entire temperature range. The possibility of epitaxial growth of silicon carbide tetrahedral crystals on diamond upon their co-crystallization was noted. Synthesized diamond are found to contain optically active silicon-vacancy (Si-V) centers and inactive substituional silicon defects, giving rise to the 1.68 eV system in the photoluminescence spectra and an absorption peak at 1338 cm -1 in the infrared absorption spectra, respectively.