К вопросу о вхождении редкоземельных элементов в структуру хромпироповых гранатов

Abstract

Rare earth elements (REE) in garnet are of interest in various fields of modern geology. The geochemistry of REEs in magmatic minerals is widely used in determining the distribution coefficients of crystal/melt and crystal/fluid, modeling the processes of melting and crystallization of magmatic rocks, studying deep mantle processes, age estimates and other issues of petrogenesis. The aim of the present work was a synthesis of a peridotite mineral association including the garnet containing REE at high pressure and high temperature. The initial sample consisted mainly of natural serpentine collected from ophiolites of the Eastern Sayan (Russia). As is known, the extreme stage of the regressive metamorphism of peridotites is serpentinization. It is depleted in calcium, but can recrystallize at high PT conditions into a harzburgite paragenesis, and at the initial stage of the experiment the chemical composition of the sample was a model harzburgite depleted in calcium and chromium, as well as a fluid of predominantly aqueous composition. As a source of chromium, chromite grains of 1–2 mm in size from peridotite xenoliths of the Udachnaya kimberlite pipe (Yakutia) were used. REE were added to the initial charge in the form of water-soluble salts. The experiment at a pressure of 5 GPa and temperature 1300 was performed on a multi-anvil high-pressure apparatus of the “split sphere” type (BARS) designed and developed at the V.S. Sobolev Institute of Geology and Mineralogy SB RAS. A container based on refractory oxide ZrO2 was used as a highpressure medium. The pressure in the cell before sample heating was estimated using the reference substances Bi and PbSe. The temperature was measured by a platinum-platinum-rhodium thermocouple PtRh30-PtRh6. The quenched was performed by switching off the voltage in the heater circuit. The experiment products contain an association of olivine + garnet + orthopyroxene + newly formed spinel. The predominant phase was olivine of a forsterite composition. A low-Fe orthopyroxene (1.49 – 1.68 wt% FeO) was found in elongated grains uniformly distributed throughout the sample. The newly formed spinel shows the faceted grains. The chromium content in the spinel significantly exceeds that of the initially added to the initial charge, 61.63 and 54.04 wt% Cr2O3, respectively. The garnet is characterized by a purple color, and was identified in the sample volume between olivine grains in the form of individual faceted crystals or their clusters. The largest garnets reached 0.5 mm in size. The synthesized garnet was determined as a high-Cr low-Ca pyrope variety. The contents of Cr2O3 and CaO are 10.15-11.21 and 0.06-0.11 wt%, respectively. The total content of REE in the garnet identified by the microprobe analysis is relatively high reaching 5-7 wt%. As a result of the work a mineral association corresponding to the peridotite paragenesis was obtained, including the subcalcic Crrich pyrope containing rare earth elements in significant amounts. It was estimated that their content in garnet mainly depends on the size of the ionic radius and, accordingly, on the atomic weight. This is consistent with the known facts about the preferable position of heavy REEs into the garnet structure compared to the light REEs.