Ella V. Sokol

Hollow silicate microspheres from fly ashes of the Chelyabinsk brown coals (South Urals, Russia)

Abstract Fly ashes from the South Uralian thermal power stations (TPS), using brown coals of the Chelyabinsk basin as combustible, were under study. The phase formation processes, proceeding in an ash fraction of these coals during their combustion, were investigated. The data on chemical composition of fly ashes are presented. Special attention was given to hollow silicate microspheres extracted from the wastes. With the use of a complex of physicochemical methods, morphology and chemical composition of microspheres are described in detail. Globules of all known morphological types made up of silicate glasses of the two discrete compositions, K–Al–Si and Fe–Al–Si, with a predominance of the first type, were found. The phase composition of mineral impurities in the Chelyabinsk coals is recognised optimal for originating hollow silicate microspheres during industrial coal combustion. The microspheres from the South Uralian fly ashes are comparable to microspheres having practical application in size, wall thickness, shape, morphology of a surface, chemical composition and homogeneity.

Chromatite and its Cr3+- and Cr6+-bearing precursor minerals from the Nabi Musa Mottled Zone complex, Judean Desert

Abstract Chromatite (CaCrO4, tetragonal) is mainly known from Cr6+-contaminated soils associated with chromium ore processing residue. This extremely rare mineral was found at the Nabi Musa locality (Judean Desert, Israel), in a peculiar rock complex of the Mottled Zone. We have explored the possible mechanisms responsible for leaching Cr6+ from natural rocks, by means of field observations, batch experiments, thermodynamic modeling, and mineralogical analyses of the Nabi Musa rocks (XRPD, EMPA, SEM, FTIR, and optical microscopy). A remarkable feature of the Mottled Zone rocks is a broad occurrence of high- and ultrahigh-temperature combustion metamorphic rocks, with Cr3+ accumulated mainly in opaque minerals such as Fe-spinel, brownmillerite, and perovskite. Another feature of the Mottled Zone sequence is abundant Cr3+ (bentorite and volkonskoite) and Cr6+ mineralization (Cr6+-bearing ettringite and baryte-hashemite solid solution) in low-temperature hydrothermal veins. Field, mineralogical, and thermodynamic modeling data suggest that Cr was leached from Cr3+-bearing opaque minerals during late hydrothermal alteration of combustion metamorphic rocks by unusual hyperalkaline waters (pH up to 12). The Cr3+ was then oxidized to Cr6+, and subsequently partially immobilized in Cr6+-bearing ettringite. As a consequence of the highway construction across Nabi Musa hill in 2006, the buried veins filled by Cr6+-substituted ettringite were exhumed and exposed to supergene alteration. The ensuing decomposition of Cr6+-bearing ettringite was followed by Cr6+ release into pore waters in rainy seasons, and then by precipitation of chromatite on the evaporation barrier under the hard desert insolation in dry seasons. The chromatite formation has been due to both unique rock and water chemistry of the Mottled Zone sequence and to the arid climate of the Judean Desert.

Fayalite and kirschsteinite solid solutions in melts from burned spoil-heaps, South Urals, Russia

Individual grains of calcian fayalite and ferroan kirschsteinite, as well as fayalite-kirschsteinite intergrowths are observed in the groundmass of basic crystallised melts, or parabasalts, from burned spoil-heaps of the Chelyabinsk brown-coal basin. Exsolved fayalite and kirschsteinite rims surround the grains of fayalite and early Mg-Fe olivine. The chemical study of the olivines has shown that during their crystallisation they were becoming enriched in fayalite and larnite and depleted in forsterite. The intergrowths of ferroan kirschsteinite (> 20 wt.% of CaO) and calcian fayalite ( 8.5 wt.%. The exsolution temperatures were estimated to 980-800 °C. The main reasons for the appearance of the Ca-Fe olivine in the parabasalts are the composition of the initial melt enriched in FeO and CaO, fractional crystallisation resul ting in further enrichment in iron of the residual low-silica melt, and reducing conditions during olivine crystallisation and exsolution.

Natural analogs of belite sulfoaluminate cement clinkers from Negev Desert, Israel

Abstract Ye’elimite-larnite rocks in the Hatrurim formation of the Negev Desert, Israel, are natural analogs of belite sulfoaluminate (BSA) cement clinkers. They have been produced by ultrahigh-temperature combustion metamorphism at ambient pressure of a calcareous sedimentary precursor. Their mineralogy consists of 35-50 vol% β-Ca2SiO4, 15-20 vol% ye’elimite, 7-15 vol% ferrites, and 15-20 vol% fluorapatite and/or fluorellestadite. A few grains of hatrurite (Ca3SiO5) and α′-Ca2SiO4 have been observed as well. The composition of α′- and β-Ca2SiO4 polymorphs by EPMA are near Ca1.96-1.98Na0.01-0.02 Si0.96P0.03Al0.01O4, whereas ye’elimite has an approximate composition by EPMA of Ca3.99Mg0.02Ba0.01 Na0.02K0.02Al5.73Fe3+0.16Si0.10S0.97P0.02O16. The Al content of brownmillerite Ca2(Fe1-xAlx)2O5 ranges from x = 0.20-0.27. Fe-analog of shulamitite (Ca3Fe2TiO8) contains up to 15.1 wt% TiO2. Ye’elimite-larnite rocks were derived from chalky sediments by burning of combustible gas with a Tmax at 1200-1350 °C. The mineral content, microstructure, and texture/fabric of the ye’elimite-larnite rocks imply that chalky and/or marly sediments with randomly distributed clay, phosphorite, and gypsum may be utilized as cheap naturally homogenized and pulverized mixtures for industrial production of BSA cement clinker, as an environment-friendly alternative to ordinary Portland cement (OPC).

Intermediate members of the lime-monteponite solid solutions (Ca1−xCdxO, x = 0.36–0.55): Discovery in natural occurrence

Abstract Lime-monteponite solid solutions [(Ca,Cd)O ss] with 58.5–73.3 wt% CdO were discovered as an accessory phase in medium-temperature combustion metamorphic (CM) spurrite-fluorellestadite/ fluorapatite marbles from central Jordan. The type locality is situated in the northern part of the Siwaqa complex (Tulul Al Hammam area), the largest area of the “Mottled Zone” Formation in the Dead Sea region. The marbles were derived from bitumen-rich calcareous marine sediments of the Muwaqqar Chalk Marl Formation, which have high Cd, Zn, U, and Ni enrichments and contain Cd-rich wurtzite and sphalerite. Oxidative sintering of these sediments at 800–850 °C gave rise to unusual oxide accessories: lime-monteponite solid solutions, Cd-bearing Ca and Zn aluminate—tululite, zincite, and Zn-, Ni-, and Cu-rich periclase. Cadmium incorporation into different oxides was controlled by steric factors, while Cd[6] → Ca[6] was the principal isomorphic substitution. The intermediate members (Ca0.645Cd0.355)O–(Ca0.453Cd0.547)O with a halite-type structure have a cadmium incorporation ratio (KCd = Cdmineral/Cdrock) of about 843 and are the main sites for cadmium in CM marbles. In supergene environments, at low water/rock ratios, (Ca1−xCdx)(OH)2 ss (x ≤ 0.5) constitute the main secondary phase after (Ca,Cd)O ss. At higher water/rock ratios and in the presence of Cl− and F− in the solutions, calcium, and cadmium precipitated as separate phases ﹛fluorite (CaF2) and basic cadmium chloride [Cd(OH)2–xClx)]﹜. A part of cadmium becomes retained in calcium silicate hydrates. The common occurrence of anhydrous (Ca,Cd)O grains in natural rocks, only partly altered to (Ca,Cd)-hydroxide after at least 100 ka exposure to weather and climate, proves that both phases are effective long-term Cd immobilizers.

CaC2O4·H2O spherulites in human kidney stones morphology, chemical composition, and growth regime

Among the mineral phases composing human kidney stones, spherulites of whewellite, i.e., calcium oxalate monohydrate (CaC2O4-H2O), are the most widespread. The composition and morphology, especially the internal structure of these aggregates and their formation conditions have been studied using mineralogical tools. The stones result from heterogeneous nucleation and growth under conditions of high supersaturation existing in the kidney. In most cases nuclei of two types - calcium phosphates + organic matrix, or CaC2O4·H2O microcrystallites - have been distinguished, although whewellite crystallization on seeds of uric acid are also noted. The spherulitic aggregates have a fine-fibered structure complicated by helicoidal torsion, which accounts for their abnormal strength and resistance to disintegration. These distinctive physical characteristics of CaC2O4·H2O spherulitic aggregates requires high-energy impulses extracorporeal shock-wave lithotripsy (ESWL) for their disintegration and removal from the body, although it is not an optimal method for the patient.

Pyrometamorphic osumilite : occurrence, paragenesis, and crystal structure as compared to cordierite

A detailed mineralogical study and single-crystal X-ray analysis were carried out on K-Mg osumilite from high temperature pyrometamorphic rocks. These rocks were generated during spontaneous combustion of coal-bearing spoil-heaps in the South Urals, Russia. The osumilite-bearing metapelitic rocks – clinkers – contain K-Na- and K-Na-Ca feldspars, tridymite, mullite as main phases and magnesian K-bearing cordierite, corundum, native iron, pyrrhotite, cohenite, graphite, black carbon, and iron phosphide as minor phases. The composition of pyrometamorphic osumilites approaches the synthetic compound KMg 2 Al 3 (Al 2 Si 10 )O 30 . Pyrometamorphic alterations of sedimentary protolith during coal combustion proceeded at atmospheric pressure. The osumilite-bearing parageneses are formed under the conditions of low f O2 and water activity, at temperatures above 900 °C and below the melting point for the osumilite-bearing associations. The crystal structure of osumilite was refined from X-ray single-crystal data. Its crystal-chemical formula is K 0.83 C Na 0.10 B′ (Mg 1.78 Fe 0.16 Mn 0.03 Ti 0.03 ) A (Al 2.88 Fe 0.12 ) T2 (Al 1.91 Si 10.09 ) T1 O 30 . K cations occupy the standard 12-coordinated C site, whereas Na cations populate the B′position, located between three 6-membered double rings above the A position. The comparative crystal-chemical analysis shows that in the structure of osumilite, in contrast to cordierite, potassium not only compensates for the framework charge, but also stabilizes the structure. The role of sodium in cordierite and osumilite is similar and consists in a charge compensating function.

Na-Li-Be-rich cordierite from the Murzinka pegmatite field, Middle Urals, Russia

Na-Li-Be-rich cordierite (0.16 Be, 0.05 Li, and 0.21–0.31 Na atom p.f.u.) enriched in Rb (64 ppm), Cs (217 ppm), Ce (26 ppm) and U (56 ppm) has been discovered in an Mg-enriched vein of granite pegmatite in the Murzinka field of beryllian granitic pegmatites in the Middle Ural Mts of Russia. The crystal-chemical formula of the cordierite, based on the refined structure, is |Na 0.24 Ch0 (H 2 O) 0.64 Ch1/4 |(Mg 1.66 Fe 0.26 2+ Li 0.06 Mn 0.02 ) ∑2.00 M [(Al 1.80 Be 0.16 Fe 0.04 2+ Si 1.00 ) ∑3.00 T1 (Si 4.00 Al 2.00 ) ∑6.00 T2 O 18 ]. The molecules in the channels are dominated by class II and class I H 2 O (2.21 wt%). According to the paragenesis, chemical composition and structural features of this corderite, the occurrence is typical for peraluminous granitic pegmatite. Cordierite within the Murzinka pegmatite field is generally restricted to pegmatite veins contaminated by interaction with peraluminous or silica-undersaturated country rocks. Cordierite, together with or instead of beryl, appears to have crystallized from aqueous weakly acidic chloride solutions rich in Na. The preservation of cordierite from subsequent replacement is achieved by low fluid-to-rock ratio.

Quaternary travertine of the Kurai fault zone (Gorny Altai)

In the Kurai fault zone, travertine forms a matrix cementing clastic material of colluvial and glacial deposits or rarely forming a stockwork in a system of fractures in Palaeozoic rocks. The regular change of composition of solutions in the process of travertine formation has resulted in change of stable Mg–calcite by Sr–aragonite. According to the carbon isotopic composition, the travertine has intermediate genesis between thermal and meteogene. The light oxygen isotopic composition of CaCO3 indicates formational water input. The carbonates inherited Y, Sr, U, and Ni and in some areas, V, As, and Zn from the endogeneous water sources. Given that the Kurai zone travertine cements the Late Pleistocene–Holocene sediments and 14C dating of the carbonates gives a range of >40 000–3475 ± 35 years, the faults serving as routes of migration of the solutions forming the travertine should be considered as active structures.

Numerical simulation of an oil–gas fire: A case study of a technological accident at Tengiz oilfield, Kazakhstan (June 1985–July 1986)

A gusher from accident well 37 at the Tengiz oilfield (Kazakhstan) led to a catastrophic fire and produced melt combustion metamorphic rocks in its thermal halo (aureole). According to the obtained data on the mineralogy and petrology of the combustion metamorphic rocks and inferred thermal conditions of metamorphism, the protolith sand and clay can become fully molten at a temperature no lower than 1200℃. Four models have been tested for the thermal effect of the Tengiz fire on the country rocks: (a) a single straight-flow vertical gas flare, (b) a single vertical gas flare with oil droplets, (c) a single oil–gas flare with lateral wind load, and (d) a composite oil–gas flare consisting of one vertical and two horizontal spouts. Modeling with SigmaFlow software takes into account the spatial turbulent airflow mechanics of the flare, convective, and radiative heat transfer, burning of gas and oil droplets, as well as conductive heat flux in soil. Model 4 simulates the best the Tengiz fire in the period from 26 June 1985 to 05 September 1986. As the model predicts, a flare with the parameters as in the Tengiz case can cause partial melting of sedimentary material (1100℃) in a local zone but cannot maintain its bulk melting which requires higher temperatures (1200–1400℃). Additional heat may have come from ignition of oil spilled over the surface. The heat from a single oil–gas flare from a wellhead with a 0.5-m stickup turns out to be insufficient for combustion metamorphism (T = 1000–1400℃).