Search Results (12)

A simple method for the direct transformation of Sr-exchanged titanosilicate with the sitinakite structure (IONSIV) into ceramic material through cold pressing and subsequent sintering at 1100 °C for 4 h is presented. The temperature transformation of Sr-exchanged sitinakite showed the stages of recrystallization of the material with the formation of Sr-Ti phases matsubaraite (Sr₄Ti₅[Si₂O₇]₂O₈), jeppeite (SrTi₆O₁₃), tausonite (SrTiO₃), and rutile. Leaching experiments showed the efficiency of fixation of Sr cations in a ceramic matrix; extraction into water does not exceed 0.01% and desorption in 1 M HNO₃ solution is only 0.19% within three days. The leaching rates of immobilized Sr demonstrate the structural integrity of the formed phases in the ceramic (2.8 × 10⁻⁵–1.0 × 10⁻⁵ g/(m²·day). The decrease in the crystallinity of the initial Na-sitinakite, which is achieved by reducing the synthesis temperature from 250 to 210 °C, does not affect the sorption capacity and the fixation of cations in the ceramic matrix. The obtained results confirm the prospect of using inexpensive precursors, titanium ore enrichment waste, for the synthesis of sorption materials. Full article

Titanosilicates comprise a broad class of materials with promising technological applications. The typical obstacle that restricts their industrial applicability is the high manufacturing cost due to the use of specific organotitanium precursors. We herein report a new approach to the synthesis of titanosilicates using an inexpensive inorganic precursor, ammonium titanyl sulfate (ATS or STA), (NH₄)₂TiO(SO₄)₂∙H₂O. The latter is an intermediate in the processing of titanium-bearing concentrates produced from apatite-nepheline ores. In this paper, the new synthetic approach is exemplified by the microwave-assisted synthesis of IONSIVE-911, one of the most effective Cs-ion scavengers. The method can be modified to synthesize various titanosilicate compounds. Full article

The crystal structure of manganotychite has been refined using the holotype specimen from the Alluaiv Mountain, Lovozero massif, Kola peninsula, Russia. The mineral is cubic, Fd$\overline{3}$, a = 14.0015(3) Å, V = 2744.88(18) ų, Z = 8, R₁ = 0.020 for 388 independently observed reflections. Manganotychite is isotypic to tychite and ferrotychite. Its crystal structure is based upon a three-dimensional infinite framework formed by condensation of MnO₆ octahedra and CO₃ groups by sharing common O atoms. The sulfate groups and Na⁺ cations reside in the cavities of the octahedral-triangular metal-carbonate framework. In terms of symmetry and basic construction of the octahedral-triangular framework, the crystal structure of manganotychite is identical to that of northupite, Na₃Mg(CO₃)₂Cl. The transition northupite → tychite can be described as a result of the multiatomic 2Cl⁻ → (SO₄)²⁻ substitution, where both chlorine and sulfate ions are the extra-framework constituents. However, the positions occupied by sulfate groups and chlorine ions correspond to different octahedral cavities within the skeletons of Na atoms. The crystal structure of northupite can be considered as an interpenetration of two frameworks: anionic [Mg(CO₃)₂]²⁻ octahedral-triangular framework and cationic [ClNa₃]²⁻ framework with the antipyrochlore topology. Both manganotychite and northupite structure types can be described as a modification of the crystal structure of diamond (or the dia net) via the following steps: (i) replacement of a vertex of the dia net by an M₄ tetrahedron (no symmetry reduction); (ii) attachment of (CO₃) triangles to the triangular faces of the M₄ tetrahedra (accompanied by the Fd$\overline{3}$m → Fd$\overline{3}$ symmetry reduction); (iii) filling voids of the resulting framework by Na⁺ cations (no symmetry reduction); and (iv) filling voids of the Na skeleton by either sulfate groups (in tychite-type structures) or chlorine atoms (in northupite). As a result, the information-based structural complexity of manganotychite and northupite exceeds that of the dia net. Full article

The production of electrolytic nickel includes the stage of leaching of captured firing nickel matte dust. The solutions formed during this process contain considerable amounts of Pb, which is difficult to extraction due to its low concentration upon the high-salt background. The sorption of lead from model solutions with various compositions by synthetic and natural titanosilicate sorbents (synthetic ivanyukite-Na-T (SIV), ivanyukite-Na-T, and AM-4) have been investigated. The maximal sorption capacity of Pb is up to 400 mg/g and was demonstrated by synthetic ivanyukite In solutions with the high content of Cl⁻ (20 g/L), extraction was observed only with a high amount of Na (150 g/L). Molecular mechanisms and kinetics of lead incorporation into ivanyukite were studied by the combination of single-crystal and powder X-ray diffraction, microprobe analysis, and Raman spectroscopy. Incorporation of lead into natural ivanyukite-Na-T with the R3m symmetry by the substitution 2Na⁺ + 2O²⁻ ↔ Pb²⁺ + □ + 2OH⁻ leds to its transformation into the cubic P−43m Pb-exchanged form with the empirical formulae Pb_1.26[Ti₄O_2.52(OH)_1.48(SiO₄)₃]·3.32(H₂O). Full article

The microporous titanosilicate sitinakite, KNa₂Ti₄(SiO₄)₂O₅(OH)·4H₂O, was first discovered in the Khibiny alkaline massif. This material is also known as IONSIV IE-911 and is considered as one of the most effective sorbents for Cs⁺ and Sr²⁺ from water solutions. We investigate a mechanism of cooperative crystal chemical adaptation caused by the incorporation of La³⁺ ions into sitinakite structure by the combination of theoretical (geometrical–topological analysis, Voronoi migration map calculation, structural complexity calculation) and empirical methods (PXRD, SCXRD, Raman spectroscopy, scanning electron microscopy). The natural crystals of sitinakite (a = 7.8159(2), c = 12.0167(3) Å) were kept in a 1M solution of La(NO₃)₃ for 24 h. The ordering of La³⁺ cations in the channels of the ion-exchanged form La³⁺Ti₄(SiO₄)₂O₅(OH)·4H₂O (a = 11.0339(10), b = 11.0598(8), c = 11.8430(7) Å), results in the symmetry breaking according to the group–subgroup relation P4₂/mcm → Cmmm. Full article

The Lovozero peralkaline massif (Kola Peninsula, Russia) has several deposits of Zr, Nb, Ta and rare earth elements (REE) associated with eudialyte-group minerals (EGM). Eudialyte from the Alluaiv Mt. often forms zonal grains with central parts enriched in Zr (more than 3 apfu) and marginal zones enriched in REEs. The detailed study of the chemical composition (294 microprobe analyses) of EGMs from the drill cores of the Mt. Alluaiv-Mt. Kedykvyrpakhk deposits reveal more than 70% Zr-enriched samples. Single-crystal X-ray diffraction (XRD) was performed separately for the Zr-rich (4.17 Zr apfu) core and the REE-rich (0.54 REE apfu) marginal zone. It was found that extra Zr incorporates into the octahedral M1A site, where it replaces Ca, leading to the symmetry lowering from R$\overline{3}$m to R32. We demonstrated that the incorporation of extra Zr into EGMs makes the calculation of the eudialyte formula on the basis of Si + Al + Zr + Ti + Hf + Nb + Ta + W = 29 apfu inappropriate. Full article

The Lovozero peralkaline massif (Kola Peninsula, Russia) is widely known for its unique mineral diversity, and most of the rare metal minerals are found in pegmatites, which are spatially associated with poikilitic rocks (approximately 5% of the massif volume). In order to determine the reasons for this relationship, we have investigated petrography and the chemical composition of poikilitic rocks as well as the chemical composition of the rock-forming and accessory minerals in these rocks. The differentiation of magmatic melt during the formation of the rocks of the Lovozero massif followed the path: lujavrite → foyaite → urtite (magmatic stage) → pegmatite (hydrothermal stage). Yet, for peralkaline systems, the transition between magmatic melt and hydrothermal solution is gradual. In the case of the initially high content of volatiles in the melt, the differentiation path was probably as follows: lujavrite → foyaite (magmatic stage) → urtitization of foyaite → pegmatite (hydrothermal stage). Poikilitic rocks were formed at the stage of urtitization, and we called them pre-pegmatites. Indeed, the poikilitic rocks have a metasomatic texture and, in terms of chemical composition, correspond to magmatic urtite. The reason for the abundance of rare metal minerals in pegmatites associated with poikilitic rocks is that almost only one nepheline is deposited during urtitization, whereas during the magmatic crystallization of urtite, rare elements form accessory minerals in the rock and are less concentrated in the residual solution. Full article

The Lovozero Alkaline Massif intruded through the Archean granite-gneiss and Devonian volcaniclastic rocks ca. 360 Ma ago and formed a large laccolith-type body. The lower part of the massif (the Layered complex) is composed of regularly repeating rhythms: melanocratic nepheline syenite (lujavrite, at the top), leucocratic nepheline syenite (foyaite), foidolite (urtite). The upper part of the massif (the Eudialyte complex) is indistinctly layered, and lujavrite enriched with eudialyte-group minerals (EGM) prevails there. In this article, we present the results of a study of the chemical composition and petrography of more than 400 samples of the EGM from the main types of rock of the Lovozero massif. In all types of rock, the EGM form at the late magmatic stage later than alkaline clinopyroxenes and amphiboles or simultaneously with it. When the crystallization of pyroxenes and EGM is simultaneous, the content of ferrous iron in the EGM composition increases. The Mn/Fe ratio in the EGM increases during fractional crystallization from lujavrite to foyaite and urtite. The same process leads to an increase in the modal content of EGM in the foyaite of the Layered complex and to the appearance of primary minerals of the lovozerite group in the foyaite of the Eudialyte complex. Full article

The Lovozero Alkaline Massif intruded through the Archaean granite-gneiss and Devonian volcaniclastic rocks about 360 million years ago, and formed a large (20 × 30 km) laccolith-type body, rhythmically layered in its lower part (the Layered Complex) and indistinctly layered and enriched in eudialyte-group minerals in its upper part (the Eudialyte Complex). The Eudialyte Complex is composed of two groups of rocks. Among the hypersolvus meso-melanocratic alkaline rocks (mainly malignite, as well as shonkinite, melteigite, and ijolite enriched with the eudialyte-group minerals, EGM), there are lenses of subsolvus leucocratic rocks (foyaite, fine-grained nepheline syenite, urtite with phosphorus mineralization, and primary lovozerite-group minerals). Leucocratic rocks were formed in the process of the fractional crystallization of melanocratic melt enriched in Fe, high field strength elements (HFSE), and halogens. The fractionation of the melanocratic melt proceeded in the direction of an enrichment in nepheline and a decrease in the aegirine content. A similar fractionation path occurs in the Na₂O-Al₂O₃-Fe₂O₃-SiO₂ system, where the melt of the “ijolite” type (approximately 50% of aegirine) evolves towards “phonolitic eutectic” (approximately 10% of aegirine). The temperature of the crystallization of subsolvus leucocratic rocks was about 550 °C. Hypersolvus meso-melanocratic rocks were formed at temperatures of 700–350 °C, with a gradual transition from an almost anhydrous HFSE-Fe-Cl/F-rich alkaline melt to a Na(Cl, F)-rich water solution. Devonian volcaniclastic rocks underwent metasomatic treatment of varying intensity and survived in the Eudialyte Complex, some remaining unchanged and some turning into nepheline syenites. In these rocks, there are signs of a gradual increase in the intensity of alkaline metasomatism, including a wide variety of zirconium phases. The relatively high fugacity of fluorine favored an early formation of zircon in apo-basalt metasomatites. The ensuing crystallization of aegirine in the metasomatites led to an increase in alkali content relative to silicon and parakeldyshite formation. After that, EGM was formed, under the influence of Ca-rich solutions produced by basalt fenitization. Full article

The world largest phoscorite-carbonatite complexes of the Kovdor (Russia) and Palabora (South Africa) alkaline-ultrabasic massifs have comparable composition, structure and metallogenic specialization, and can be considered close relatives. Distribution of rock-forming sulfides within the Kovdor phoscorite-carbonatite complex reflects gradual concentric zonation of the pipe: pyrrhotite with exsolution inclusions of pentlandite in marginal (apatite)-forsterite phoscorite, pyrrhotite with exsolution inclusions of cobaltpentlandite in intermediate low-carbonate magnetite-rich phoscorite and chalcopyrite (±pyrrhotite with exsolution inclusions of cobaltpentlandite) in axial carbonate-rich phoscorite and phoscorite-related carbonatite. Chalcopyrite (with relicts of earlier bornite and exsolution inclusions of cubanite and mackinawite) predominates in the axial carbonate-bearing phoscorite and carbonatite, where it crystallizes around grains of pyrrhotite (with inclusions of pentlandite-cobaltpentlandite and pyrite), and both of these minerals contain exsolution inclusions of sphalerite. In natural sequence of the Kovdor rocks, iron content in pyrrhotite gradually increases from Fe₇S₈ (pyrrhotite-4C, Imm2) to Fe₉S₁₀ (pyrrhotite-5C, C2 and P2₁) and Fe₁₁S₁₂ (pyrrhotite-6C) due to gradual decrease of crystallization temperature and oxygen fugacity. Low-temperature pyrrhotite 2C (troilite) occurs as lens-like exsolition inclusions in grains of pyrrhotite-4C (in marginal phoscorite) and pyrrhotite-5C (in axial phoscorite-related carbonatite). Within the phoscorite-carbonatite complex, Co content in pyrrhotite gradually increases from host silicate rocks and marginal forsterite-dominant phoscorite to axial carbonate-rich phoscorite and carbonatite at the expense of Ni and Fe. Probably, this dependence reflects a gradually decreasing temperature of the primary monosulfide solid solutions crystallization from the pipe margin toward its axis. The Kovdor and Loolekop phoscorite-carbonatite pipes in the Palabora massif have similar sequences of sulfide formation, and the copper specialization of the Palabora massif can be caused by higher water content in its initial melt allowing it to dissolve much larger amounts of sulfur and, correspondingly, chalcophile metals. Full article

The Kovdor alkaline-ultrabasic massif (NW Russia) is formed by three consequent intrusions: peridotite, foidolite–melilitolite and phoscorite–carbonatite. Forsterite is the earliest mineral of both peridotite and phoscorite–carbonatite, and its crystallization governed evolution of magmatic systems. Crystallization of forsterite from Ca-Fe-rich peridotite melt produced Si-Al-Na-K-rich residual melt-I corresponding to foidolite–melilitolite. In turn, consolidation of foidolite and melilitolite resulted in Fe-Ca-C-P-F-rich residual melt-II that emplaced in silicate rocks as a phoscorite–carbonatite pipe. Crystallization of phoscorite began from forsterite, which launched destruction of silicate-carbonate-ferri-phosphate subnetworks of melt-II, and further precipitation of apatite and magnetite from the pipe wall to its axis with formation of carbonatite melt-III in the pipe axial zone. This petrogenetic model is based on petrography, mineral chemistry, crystal size distribution and crystallochemistry of forsterite. Marginal forsterite-rich phoscorite consists of Fe²⁺-Mn-Ni-Ti-rich forsterite similar to olivine from peridotite, intermediate low-carbonate magnetite-rich phoscorite includes Mg-Fe³⁺-rich forsterite, and axial carbonate-rich phoscorite and carbonatites contain Fe²⁺-Mn-rich forsterite. Incorporation of trivalent iron in the octahedral M1 and M2 sites reduced volume of these polyhedra; while volume of tetrahedral set has not changed. Thus, trivalent iron incorporates into forsterite by schema (3Fe²⁺)_oct → (2Fe³⁺ + □)_oct that reflects redox conditions of the rock formation resulting in good agreement between compositions of apatite, magnetite, calcite and forsterite. Full article

The Kovdor phoscorite-carbonatite ore-pipe rocks form a natural series, where apatite and magnetite first gradually increase due to the presence of earlier crystallizing forsterite in the pipe marginal zone and then decrease as a result of carbonate development in the axial zone. In all lithologies, magnetite grains contain (oxy)exsolution inclusions of comparatively earlier ilmenite group minerals and/or later spinel, and their relationship reflects the concentric zonation of the pipe. The temperature and oxygen fugacity of titanomagnetite oxy-exsolution decreases in the natural rock sequence from about 500 °C to about 300 °C and from NNO + 1 to NNO − 3 (NNO is Ni-NiO oxygen fugacity buffer), with a secondary positive maximum for vein calcite carbonatite. Exsolution spinel forms spherical grains, octahedral crystals, six-beam and eight-beam skeletal crystals co-oriented with host magnetite. The ilmenite group minerals occur as lamellae oriented along {111} and {100} planes of oxy-exsolved magnetite. The kinetics of inclusion growth depends mainly on the diffusivity of cations in magnetite: their comparatively low diffusivities in phoscorite and carbonatites of the ore-pipe internal part cause size-independent growth of exsolution inclusions; while higher diffusivities of cations in surrounding rocks, marginal forsterite-rich phoscorite and vein calcite carbonatite result in size-dependent growth of inclusions. Full article