Vol 69, No 7 (2024)
- Year: 2024
- Articles: 5
- URL: https://journals.eco-vector.com/0016-7525/issue/view/11462
- DOI: https://doi.org/10.31857/S0016-7525697
Full Issue
Articles
Cryolite as a reference mineral for rare metal mineralization (experimental study)
Abstract
The phase relationships and distributions of rare earth elements, Sc, Y and Li between aluminofluoride and aluminosilicate melts in the model granite system Si-Al-Na-K-Li-F-O-H at 700 °C, 1 and 2 kbar with a water content from 3 to 50 wt. %. were experimentally studied. Based on the obtained and available experimental data on phase relationships in a granite system saturated with water, fluorine and containing rare elements, a comparison was made with the parageneses of rare-metal cryolite-containing granites from three deposits in Eastern Siberia are Zashikhinsky, Katuginsky and Ulug-Tanzeksky. It has been shown that the processes of liquid immiscibility between granite and salt aluminofluoride melts, which manifest themselves at high contents of fluorine and lithium in the system, contribute to the accumulation of rare elements in salt cryolite-like melts. At a temperature of 700 °C and a pressure of 1 and 2 kbar, crystallization of the aluminofluoride melt occurs in the granite system, from which cryolite is formed. It is in association with cryolite and lithium micas that the considered natural objects contain minerals of rare and rare earth elements containing fluorine, such as pyrochlore, gagarinite, etc. As a result of a comparison of experimental and natural data, the hypothesis about the important role of liquid immiscibility in the formation of cryolite is confirmed. It is assumed that cryolite can serve as a reference mineral for rare metal-rare earth mineralization in granites with high lithium and fluorine content.



EPR spectroscopic and calorimetric study of minerals of the amblygonite–montebrasite series from rare-metal pegmatite of the Voroniye tundry (Kola peninsula) and Sangilen highlands (Tuva)
Abstract
For the first time, a comprehensive physicochemical study of minerals of the amblygonite LiAlPO4F — montebrasite LiAlPO4(OH) series was carried out. An EPR spectroscopic and calorimetric study of montebrasite LiAlPO4(OH)0.9F0.1 from rare-metal granite pegmatites Shuk-Byul (Sangilen Highlands, Tuva) and amblygonite LiAlPO4F0.5(OH)0.5 from pegmatites of the Voroniye tundras (Kola Peninsula) was carried out. Using the EPR method, radiation-sensitive paramagnetic O– centers were discovered, they were formed without the participation of impurity elements in regular sites of the crystal lattice. For the first time, the possibility of carrying out EPR geochronometry on minerals of the amblygonite–montebrasite series has been demonstrated. Using the method of high-temperature melt dissolution calorimetry on a Tiana-Calvé microcalorimeter, the enthalpies of formation from the elements ΔfH0el(298.15 K) = –2326.3 ± 2.2 kJ/mol of montebrasite with the composition LiAl(PO4)(OH)0.9F0.1 and of amblygonite with the composition LiAl(PO4) F0.5(OH)0.5 (–2347.9 ± 3.1 kJ/mol) were obtained; and the values of this parameter were calculated for the end members with ideal composition of the series: for montebrasite (–2315.5 ± 2.2 kJ/mol) and for amblygonite (–2401.6 ± 3.1 kJ/mol). The values of the standard entropy S0(298.15 K) and the Gibbs energy of formation ΔfG0el(298.15 K) for intermediate and end members of the amblygonite–montebrasite series are estimated.



Biogeochemical aspects of humic substances and silicate rocks transformation during freezing-thawing
Abstract
In the northern regions, as a result of seasonal temperature changes, cyclic thawing and freezing of soils and rocks occurs, which is accompanied by dangerous natural phenomena, including landslides. Special conditions arise on the mountain slopes of many reservoirs due to fluctuations of water levels and the interaction of humified waters with rocks. The paper presents the results of an experimental study of the biotransformation of sodium humate (SH) and changes in the microstructure of the surface of silicate rock that is part of the body of the Bureya landslide under various conditions of cyclic freezing-thawing (CFT). Freezing of samples was carried out at a temperature of –18 °C, and thawing at different temperature ranges (+4 °C and +23 °C). The role of biogenic factor was played by 4 strains of microorganisms isolated from the surface and bottom layers of water in the Bureiskoe Reservoir above and below the landslide body. The nature of the biotransformation of SH during CFT was studied by spectral methods at different wavelengths (254 nm, 275 nm, 465 nm). Analysis of the composition of water-soluble forms of chemical elements in an aqueous environment during rock destruction was carried out with use of the ICP-MS method, and changes in the microstructure of its surface with use of scanning electron microscopy. It was found that the transformation of aromatic component of SH occurred most active. After CFT, the strain Actinomyces sp. 45 VD, isolated from bottom layers of water, showed maximum activity at a thawing temperature of +4 °C in relation to SH and leaching of elements from rock (Al, Ca, Mg, Mn). Its activity was comparable to the intensity of leaching of elements by a natural microbial consortium of non-sterile rock. For comparison, we used rocks subjected to CFT in deionized water; in this case, the content of water-soluble forms of many chemical elements (Fe, Ni, Cu, Zn, As, Mo, Ag, Cd, Tl, Bi, As) was below the detection limits of the device (<0.001). High biogeochemical activity of Actinomyces sp. 45 VD is confirmed by analysis of SEM-images of the microstructure of the silicate rock surface and the formation of a wide variety of isomorphic biominerals.



Geochemistry and age of paleoproterozoic metavolcanoic and metasedimentary rocks of the Don terrane of the Volga-Don orogen
Abstract
The Don terrane, which is extensively reworked by metamorphism and granitoid intrusions, is part of the Volga–Don orogen stretching along the eastern margin of the Sarmatian segment of the East European Craton. The terrane consists of gneiss-granites of the Pavlovsk complex, metavolcanic rocks, ranging from basaltic andesites to dacites (amphibolites and gneisses), and metasedimentary rocks (marbles and calc-silicate rocks) of the Don Group. The volcanic rocks are typically enriched in LILE and LREE and show negative HFSE anomalies, indicating fluid-assisted melting of the mantle wedge in a subduction zone. The Nd isotopic composition (εNd2200 = –1.2 to +3.4, model age 2180–2550 Ma) and Hf isotopic composition (εHf = –4.3 to +3.3, model age 2290–2640 Ma) indicate an enriched mantle or a mixed crustal–mantle source of the parental melts of the volcanics and a juvenile source for sediments of the Don Group. The U–Pb zircon metamorphic age of the gneisses and amphibolites is 2047 ± 7 Ma, and that of the thermal effect of the granitoid batholith on the host rocks is 2060 ± 4 Ma. According to isotope geochemical and geochronological data, the Don Group is underlain by Archean rocks, contains Archean detrital zircons, but the age of this group is no older than 2300 Ma. A facies and age analogue of the Don Group is the Temryuk Formation of the Central Azov Group of the Ukrainian shield. In the Paleoproterozoic, the eastern margin of Sarmatia was likely a continental arc, which was nearly coeval with the island arc–backarc basin system of the Losevo Group.



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