Vol 54, No 7 (2016)

Crystallization of garnet in high-chromium restite formed under the conditions of partial melting in the spinel facies and subsequently subducted into the garnet depth facies was studied experimentally in the MgO–Al₂O₃–Cr₂O₃–SiO₂ system. The crystallization of garnet and the dependence of its composition on the temperature and bulk composition of the system with low Al concentration were studied as well. Experiments in the knorringite–majorite–pyrope system with 5, 10, and 20 mol % Prp were carried out at 7 GPa. The phase associations for the starting composition of pure knorringite Mg₃Cr₂Si₃O₁₂ included chromiumbearing enstatite MgSiO₃ (up to 3.2 wt % Cr₂O₃) and eskolaite Cr₂O₃. Addition of Al resulted in crystallization of high-chromium majoritic garnet. The portion of garnet in the samples always exceeded the concentration of pyrope in the starting composition owing to the formation of the complex majorite–knorringite–pyrope series of solid solutions. With increasing content of pyrope (from 5 to 20 mol %) and increasing temperature, the modal concentration of garnet increased significantly (from 6–12 to 22–37%). The garnet was characterized by high concentrations of the pyrope (23–80 mol %) and knorringite (22–70 mol %) components. The excess of Si (>3 f.u.) with decreasing Cr concentration provided evidence for the contribution of the majorite–knorringite trend to the variation in garnet composition. On the basis of the natural data, most of the garnets composing xenoliths of ultrabasic rocks in kimberlites and occurring as inclusions in diamonds are low-chromium; i.e., their protolith was not subjected to partial melting, at least in the spinel depth facies.

The possible origin of the Moon’s metallic core at the precipitation of iron–sulfide phases during the partial melting of ultramafic material under various redox conditions was experimentally modeled by partially melting the model system olivine (85 wt %) + ferrobasalt (10 wt %) + metallic phase Fe₉₅S₅ (wt %) in a high-temperature centrifuge at 1430–1450°C. The oxygen fugacity fO₂ was determined from the composition of the quenched experimental silicate melts (glasses). A decrease in fO₂ is proved to be favorable for the segregation of iron–sulfide melt from the silicate matrix. The metallic phase is most effectively segregated in the form of melt droplets, and these droplets are accumulated in the lower portions of the samples under strongly reduced conditions, at fO₂ ∼ 4.5–5.5 orders of magnitude lower than the iron–wüstite buffer.

The contents of dissolved rhodium species in the near-neutral environments have been studied for the first time and data on the interaction of Rh with organic matters of natural waters and its sorption behavior during contact with the components of geochemical barriers were obtained. The solubility method was used to analyze the behavior of rhodium hydroxide in the Rh(OH)_x–H₂O and Rh(OH)_x–H₂O–FA (fulvic acids) systems. The possible contents of inorganic species of rhodium and its compounds with humic organic ligands were determined within the pH range typical of surface waters. The solubility of rhodium shows a twoorder- of magnitude increase in the presence of humic matters (FA). The sorption interaction of the soluble rhodium species with the main components of geochemical barriers such as iron oxyhydroxides (III), (including fulvic-acid modified ones), alumosilicates, and precipitates of humic acids in contact with natural waters was studied. It was revealed that rhodium has the high affinity to all studied materials; its species are sorbed by ferrihydrite within several hours. It is suggested that rhodium is mainly transferred as colloid with suspended particulate matters of waters and then is accumulated in bottom sediments. The differences revealed in the sorption behavior of Pt(IV), Pd(II) and Rh(III) may be used to predict the distribution of the considered platinum group elements between the components of ecosystems.