Conditions of accumulation and fractionation of zirconium and hafnium in alkaline-carbonatite systems

The patterns of the distribution and fractionation of strategic metals (Zr, Hf) in the Kugda intrusion (Polar Siberia) have been studied. The contents of these elements significantly exceed their concentrations in other rocks (Zr 246 ppm, Hf 7.4 ppm). A significant increase in Zr and Hf from early rocks (olivinite and melilite rocks) to later differentiation products, syenites with up to 570 ppm of Zr and 16 ppm of Hf, has been revealed. During the evolution of the Kuga magmatic system, notable fractionation of Zr and Hf occurred. The Zr/Hf ratios in the dike rock, similar in composition to the primary Kugda Massif magma, and the early intrusions are fairly close to that of chondrite (Zr/Hf = 37 [1]), while in the latest phases this ratio increases by almost 5-fold. Our study showed that the distribution coefficient of Hf (Kd = 0.58) in alkaline pyroxenes is noticeably higher than that of Zr (Kd = 0.40). Consequently, fractionation of this mineral leads to an increase in the Zr/Hf ratio in the residual liquids. Another mineral concentrating up to 400 ppm of Zr and up to 1520 ppm of Hf is perovskite, which has a very wide crystallization field in the rocks of the Kugda Massif, especially in the earliest olivinite. The data obtained showed that the Zr/Hf ratio in the perovskite of olivinite varies between 2327, that is, noticeably below both the chondritic and the primary magma values. Early crystallization of perovskite is the main reason for increasing the Zr/Hf ratio in melilitolites (up to 54). Thus, the main process of forming the Kugda Massif was continuous crystallization differentiation, accompanied by a noticeable fractionation of rock-forming and accessory minerals (pyroxene and perovskite).

PHASE EQUILIBRIUM IN SYSTEM (LiF)2 – Li2CO3 – Li2SO4

The liquidus surface of the system (LiF)2-Li2SO4-Li2CO3 was studied by the calculated and differential thermal method of physicochemical analysis. An analysis of the systems of lower dimensionality of the facets of the investigated object showed that the most informative, for the experimental study, is the sections located in the crystallization field of lithium fluoride. A study of the DTA of a number of compositions located at the initially chosen polythermal section in the lithium fluoride crystallization field, the ratios of lithium sulfate and carbonate in the eutectic are determined. The composition of the triple eutectic was revealed by studying a non-invariant cut from the vertex of the triangle (LiF), through a point showing a constant ratio of sulfate and lithium carbonate in the eutectic, to the fusion of the thermal effects of the primary and tertiary crystallizations. The complexity of the study was that lithium carbonate is the most fusible component in the system, and according to the literature, after the melting of lithium carbonate, decomposition begins, which greatly complicates the interpretation of research results. In order to avoid the decomposition of lithium carbonate, each experimentally studied composition was heated to the melting temperature of lithium carbonate and kept in isothermal mode, at a temperature below its melting. Thus, the theoretical melting calculations and the region of location of the non-invariant composition have been extrapolated, allowing to limit the number of experimentally studied samples, and the subsequent experimental investigation of DTA of two polythermal sections revealed a eutectic composition crystallizing at 476 ° C and containing LiF-20 eq.%, Li2SO4 - 51 eq.%, Li2CO3 – 29 eq.%. The discrepancies between theoretical calculations and experimental studies are 8.3% in temperature and 5.05% in composition.

Metastable Phase Equilibria in the Aqueous Ternary System Containing Potassium, Lithium and Chloride Ions at 298.15 K

The metastable phase equilibrium in the ternary system containing potassium, lithium and chloride ions was studied at 298.15 K using an isothermal evaporation method. The solubility, density and refractive index of the equilibrated solution were measured. The crystalloid forms of the solid phase were determined using a schreinermarks wet residue method. On the basis of the experimental data, the metastable equilibrium phase diagram and the physicochemical properties vs composition in the ternary system at 298.15 K were plotted. The experimental results show that this system is of a simple eutectic type system, no double salt or solid solution formed at 298.15 K. The phase diagram consists of one invariant point, two uninvariant curves, and two crystallization regions. The crystallization regions correspond to potassium chloride (KCl) and lithium chloride monohydrate (LiCl·H2O), respectively. Salt KCl has the largest crystallization field, whereas salt LiCl·H2O has the smallest crystallization field. Salt LiCl has strong salting-out effect on salt KCl.