Carbonate Melt Research Articles

Geochemical, isotopic and U-Pb geochronological investigation of the late Cretaceous Karaçayır carbonatite (Sivas, Turkey): Insights into mantle sources within a post-collisional tectonic setting

The Karaçayır carbonatite is located within the northeastern edge of the Central Anatolian Crystalline Complex, and represents one of the significant rare earth element (REE) mineralizations in Turkey. The carbonatite intrudes the associated syenite as dikes and veins, and is mainly composed of medium- to coarse-grained calcite, and lesser amounts of apatite, mica, amphibole, pyroxene, and magnetite. This study reports new and combined geochemical, radiogenic (Sr, Pb), stable (O and C), and for the first time B and Nd isotopic ratios and in-situ U-Pb age data from the Karaçayır carbonatite. The carbonate separates from the Karaçayır carbonatite are characterized by high Ba (30 to 484 ppm), Sr (613 to 9106 ppm) and total rare earth element (TREE) concentrations (172 to 2892 ppm), which are consistent with geochemical signatures for mantle-derived carbonate melts. The combined δ18OV-SMOW (+10.7 to +19.0 ‰), δ13CV-PDB (−2.9 to +1.8 ‰) and δ11B (−13.9 to −2.9 ‰) data for a majority of the carbonate separates investigated here in contrast indicate that they are the result of open system behavior involving contamination by the country rock (marble), and/or sub-solidus, low temperature alteration. Based on the combined stable and radiogenic isotopic signatures for the least altered/contaminated samples, the carbonatite magma at Karaçayır most likely represents a low-degree partial melt of an isotopically heterogeneous (metasomatized) mantle source containing EM (enriched mantle)-like components and recycled crustal carbon; the latter finding is consistent with those recorded for young (<300 Ma old) carbonatites worldwide. A weighted mean 206Pb/238U age of 69.3 ± 1.7 Ma is obtained for apatite from the Karaçayır carbonatite, and indicates its emplacement within a post-collisional tectonic setting during the late Cretaceous.

MARBLE MÉLANGE: COMPOSITION VARIATIONS AND FORMATION MECHANISMS

The Olkhon terrane in the Western Baikal area accommodates four types of carbonate-silicate mixtures: injection (protrusion), metamorphic-boudinated, mingling, and tectonite marble mélange. The outcrops of injection mélange consist of a carbonate matrix with inclusions of native silicic rocks found in the immediate vicinities, commonly cover large areas and lack any distinct linearity in the map view. Mélange of the metamorphic boudinage type comprises diopsidite and tremilote-diopsidite fragments in a dolomitic or calcite-dolomitic matrix. Its origin is apparently due to tectonism and related metamorphism of quartz sandstones in Neoproterozoic strata on the passive margin of the Siberian craton. Mingling mélange appears as calcite marble or carbonate-silicate (calciphyre) veins with metadolerite and granite inclusions of different sizes. The veins formed by intrusion of carbonate and silicate melt batches and subsequent fragmentation of silicate rocks that crystallized earlier. Marble tectonites localized in narrow zones record the late phase of ductile marble injection.

Economic performance assessment of elemental sulfur recovery with carbonate melt desulfurization process

This study develops an elemental sulfur recovery (ESR) process from sulfur dioxide (SO2) as a hazardous material removed from flue gas emitted at thermal coal-fired power plants with a carbonate melt flue gas desulfurization (CMFGD) process. The carbonyl sulfide (COS) generated as a byproduct after removing SO2 from flue gas using carbonate melt in the CMFDG is utilized as a resource to produce elemental sulfur by applying the hydrolysis and Claus processes in the ESR process. In addition, to increase energy independence in the integrated CMFGD-ESR process, heat integration was applied by introducing new heat exchanger networks that utilize the waste heat in the proposed process. The levelized cost of the integrated CMFGD-ESR process was determined to be US$ 811 per ton SO2 removed; from this result, the proposed process to remove hazardous material from flue gas emitted at thermal coal-fired power plants is economically benign compared to conventional SO2 removal processes (US$ 500 ~ US$ 1200 per ton SO2 removed), which use limestone as the raw material.

Changes in the microbial community structure triggered by permafrost peat thawing

An increase in permafrost temperature, accompanied by the melting and release of buried organic carbon, is one of the elements of the global warming scenario. To understand the way ecosystems respond to environmental changes, it is necessary to elucidate the factors affecting the distribution and activity of microbes in permafrost soils, which have been poorly studied so far. Meanwhile, they can have significant implications for nutrient cycling and related processes. Our research is devoted to assessing changes in the structure of the microbial community due to the melting of the palsa permafrost layer caused by the fire in 2007. The ecological-trophic groups of microorganisms of the territories changed under the influence of a natural fire in comparison with undisturbed analogs have been studied. It was revealed that the number of microorganisms in most groups on the palsa, affected by fire, is statistically significantly higher than the number of microorganisms in the undisturbed area.

Evidence for carbonatite derived from the earth's crust: The late Paleoproterozoic carbonate-rich magmatic rocks in the southeast Tarim Craton, northwest China

Carbonatites are generally accepted as derived from the mantle, whereas viewpoint of carbonatitic melt formed at crust level is considered marginal. Here we document large-scale (∼17 km2) igneous carbonate-rich rocks in the southeast Tarim Craton that were formed within the crust. These rocks exhibit clear intrusive contact with the wall-rocks and contain diverse xenolith, indicating an igneous origin. Zircon U-Pb dating reveals that they were emplaced at ca. 1.94–1.92 and 1.87–1.86 Ga, respectively. δ18O values in zircons (5.7–13.7‰) are higher than those crystallized in equilibrium with mantle melt. Total REE content is 1–2 magnitude lower than that of mantle carbonatite and shows weak fractionation of HREE. REE modeling reveals that the samples cannot be produced by partial melting of carbonated MORB at mantle conditions. The studied samples have positive δ13CV-PDB values (4.2–15.7‰), which are distinct from the mantle carbonatite but comparable to sedimentary carbonates. C-O-Sr-Nd isotope modelling indicates that the compositions of the studied samples cannot be produced by evolution of mantle carbonatite. Integrating these lines of evidence, we conclude that the studied carbonate-rich magmatic rocks were derived from partial melting of impure marble at crustal level via fluid-present melting. These carbonatites probably represent the initial magmatic record of tectonic extension of the late Paleoproterozoic collisional orogenic belt in the southern margin of the Tarim craton. The positive carbon excursion recorded by the high δ13CV-PDB values probably corresponds to the global Paleoproterozoic Lomagundi-Jatuli event. Our study implies that partial melting of sedimentary carbonates is more common than previously thought, which has significant impacts on crust rheology and global carbon cycling

Experimental Modeling of Ankerite–Pyrite Interaction under Lithospheric Mantle P–T Parameters: Implications for Graphite Formation as a Result of Ankerite Sulfidation

Experimental modeling of ankerite–pyrite interaction was carried out on a multi-anvil high-pressure apparatus of a “split sphere” type (6.3 GPa, 1050–1550 °C, 20–60 h). At T ≤ 1250 °C, the formation of pyrrhotite, dolomite, magnesite, and metastable graphite was established. At higher temperatures, the generation of two immiscible melts (carbonate and sulfide ones), as well as graphite crystallization and diamond growth on seeds, occurred. It was established that the decrease in iron concentration in ankerite occurs by extraction of iron by sulfide and leads to the formation of pyrrhotite or sulfide melt, with corresponding ankerite breakdown into dolomite and magnesite. Further redox interaction of Ca,Mg,Fe carbonates with pyrrhotite (or between carbonate and sulfide melts) results in the carbonate reduction to C0 and metastable graphite formation (±diamond growth on seeds). It was established that the ankerite–pyrite interaction, which can occur in a downgoing slab, involves ankerite sulfidation that triggers further graphite-forming redox reactions and can be one of the scenarios of the elemental carbon formation under subduction settings.

The Structure and Microhardness of Binding for Diamond Tools Based on Tungsten Carbide Obtained by Impregnation with an Iron–Carbon Melt

The Structure and Microhardness of Binding for Diamond Tools Based on Tungsten Carbide Obtained by Impregnation with an Iron–Carbon Melt

Molten salt oxidation and process analysis of anionic exchange resin in Na2CO3-K2CO3 melt

ABSTRACT The oxidation characteristics of anionic exchange resins (AERs) during molten salt oxidation (MSO) were investigated in carbonate melt. The residue after MSO of AERs were carbon, which was confirmed by the X-ray diffraction (XRD) and Raman spectra. The remaining amount of salt-free residue after MSO was evaluated by destruction and removal efficiency (DRE), which indicates that 2 hours is a suitable oxidation time. The morphologies of the AERs after MSO were observed by scanning electron microscopy (SEM). The oxidation process of AERs in MSO was investigated by thermogravimetric analysis (TG) and Fourier Transform Infrared Spectrometer (FT-IR), which revealed that initial AERs, experienced four reaction stages in MSO: dehydration, thermal decomposition of functional groups, carbonization of styrene-divinylbenzene copolymer (ST-DVB), and gasification of carbon. The TG data proved that the presence of carbonate promotes the carbonization process of ST-DVB in AERs. The reason why salt catalyzes this stage had been proved to be that the carbonate captures the nitrogen-containing exhaust gas generated by the oxidation of the anion resin, and produces nitrate with catalytic oxidation ability, which catalyzes the oxidation of the resins effectively. This means that MSO will be an environmentally friendly and efficient method for catalytic oxidation of AERs.

Diamond formation during sulfidation of metal–carbon melts

Experimental studies modeling the mechanism of diamond crystallization during sulfidation of metal–carbon melts were performed on a multi-anvil high-pressure apparatus BARS at pressure of 6.3 GPa, temperature range of 1270–1470 °C, and run duration of 20 to 35 h. Sandwich experiments with layer filling were carried out using schemes FeS2-[Fe(Fe90Ni10) + C]-FeS2, FeS2-Ol-[Fe90Ni10 + C]-Ol-FeS2 and S-Ol-[Fe90Ni10 + C]-Ol-S. The experiments have revealed that crystallization of diamond and/or graphite occurs during sulfidation of a metal–carbon melt either due to mixing of metal–carbon and sulfide melts or due to influx of sulfur from external sources through a polycrystalline olivine layers. Transport of a sulfur fluid or a metal–sulfide–carbon melt through a silicate matrix occurs through the intergranular space and microcracks as well as by recrystallization of olivine. Sulfidation is accompanied by a decrease in the solubility of carbon and leads to supersaturation that is necessary for crystallization of diamond or graphite. The inhibitory effect of the sulfide component is the cause for changes in the diamond morphology and transition of carbon phase crystallization from diamond to metastable graphite. The synthesized diamond crystals are classified as low-nitrogen or nitrogen-free diamonds. The revealed regularities may be used to explain the genesis of diamonds with central inclusions and nitrogen-free CLIPPIR diamonds.

Dynamic Metasomatism Experiments Investigating the Interaction between Migrating Potassic Melt and Garnet Peridotite

Dynamic metasomatism experiments were performed by reacting a lamproite melt with garnet peridotite by drawing melt through the peridotite into a vitreous carbon melt trap, ensuring the flow of melt through the peridotite and facilitating analysis of the melt. Pressure (2–3 GPa) and temperature (1050–1125 °C) conditions were chosen where the lamproite was molten but the peridotite was not. Phlogopite was formed and garnet and orthopyroxene reacted out, resulting in phlogopite wehrlite (2 GPa) and phlogopite harzburgite (3 GPa). Phlogopites in the peridotite have higher Mg/(Mg + Fe) and Cr2O3 and lower TiO2 than in the lamproite due to buffering by peridotite minerals, with Cr2O3 from the elimination of garnet. Compositional trends in phlogopites in the peridotite are similar to those in natural garnet peridotite xenoliths in kimberlites. Changes in melt composition resulting from the reaction show decreased TiO2 and increased Cr2O3 and Mg/(Mg + Fe). The loss of phlogopite components during migration through the peridotite results in low K2O/Na2O and K/Al in melts, indicating that chemical characteristics of lamproites are lost through reaction with peridotite so that emerging melts would be less extreme in composition. This indicates that lamproites are unlikely to be derived from a source rich in peridotite, and more likely originate in a source dominated by phlogopite-rich hydrous pyroxenites. Phlogopites from an experiment in which lamproite and peridotite were intimately mixed before the experiment did not produce the same phlogopite compositions, showing that care must be taken in the design of reaction experiments.

Non-Arrhenian Temperature-Dependent Viscosity of Alkali(ne) Carbonate Melts at Mantle Pressures

The viscosity of carbonate melts is a fundamental parameter to constrain their migration and ascent rates through the mantle and ultimately, their role as carbon conveyors within the deep carbon cycle. Yet, data on the viscosity of carbonate melts have remained scarce due to experimental limitations and the lack of appropriate theoretical descriptions for molten carbonates. Here, we report the viscosity of K2Mg(CO3)2 and K2Ca(CO3)2 melts up to 13 GPa and 2,000 K by means of classical molecular dynamics (MD) simulations using optimized force fields and provide first evidence for non-Arrhenian temperature-dependent viscosity of molten carbonates at mantle pressures. The viscosity of K2Mg(CO3)2 and K2Ca(CO3)2 melts ranges respectively between 0.0056–0.0875 Pa s and 0.0046–0.0650 Pa s in the investigated pressure-temperature interval. Alkali(ne) carbonate melts, i.e. mixed alkali and alkaline earth carbonate melts -K2Mg(CO3)2 and K2Ca(CO3)2− display higher viscosity than alkaline earth carbonate melts -CaCO3 and MgCO3− at similar conditions, possibly reflecting the change in charge distribution upon addition of potassium. The non-Arrhenian temperature-dependence of the viscosity is accurately described by the Vogel-Fulcher-Tammann model with activation energies Ea for viscous flow that decrease with temperature at all investigated pressures, e.g. from ∼100 kJ/mol to ∼30 kJ/mol between 1,300 and 2,000 K at 3 GPa. Pressure is found to have a much more moderate effect on the viscosity of alkali(ne) carbonate melts, with activation volumes Va that decrease from 4.5 to 1.9 cm3/mol between 1,300 and 2,000 K. The non-Arrhenian temperature-viscosity relationship reported here could be exhibited by other carbonate melt compositions as observed for a broad range of silicate melt compositions and it should be thus considered when modeling the mobility of carbonate melts in the upper mantle.

The glass transition and the non-Arrhenian viscosity of carbonate melts

Abstract We report the first calorimetric observation of the glass transition for a carbonate melt. A carbonate glass [55K2CO3–45MgCO3 (molar)] was quenched from 780 °C at 0.1 GPa. The activation energy of structural relaxation close to the glass transition was derived through a series of thermal treatments comprising excursions across the glass transition at different heating rates. Viscosities just above the glass transition temperature were obtained by applying a shift factor to the calorimetric results. These viscosity measurements (in the range of 109 Pa·s) at supercooled temperatures (ca. 230 °C) dramatically extend the temperature range of data for carbonates, which were previously restricted to super-liquidus viscosities well below 1 Pa·s. Combining our calorimetrically derived results with published alkaline-earth carbonate melt viscosities at high temperatures yields a highly non-Arrhenian viscosity-temperature relationship and confirms that carbonate liquids are “fragile.” Based on simulations, fragile behavior is also exhibited by Na2CO3 melt. In both cases, the fragility presumably relates to the formation of temperature-dependent low-dimensional structures and Vogel-Fulcher-Tammann (VFT) curves adequately describe the viscosity-temperature relationships of carbonate melts below 1000 °C.

Carbonatitic Melts and Their Role in Diamond Formation in the Deep Earth

Carbonatitic high-density fluids and carbonate mineral inclusions in lithospheric and sub-lithospheric diamonds reveal comparable compositions to crustal carbonatites and, thus, support the presence of carbon-atitic melts to depths of at least the mantle transition zone (~410–660 km depth). Diamonds and high pressure–high temperature (HP–HT) experiments confirm the stability of lower mantle carbonates. Experiments also show that carbonate melts have extremely low viscosity in the upper mantle. Hence, carbonatitic melts may participate in the deep (mantle) carbon cycle and be highly effective metasomatic agents. Deep carbon in the upper mantle can be mobilized by metasomatic carbonatitic melts, which may have become increasingly volumetrically significant since the onset of carbonate subduction (~3 Ga) to the present day.

Relics of Deep Alkali–Carbonate Melt in the Mantle Xenolith from the Komsomolskaya–Magnitnaya Kimberlite Pipe (Upper Muna Field, Yakutia)

Relics of Deep Alkali–Carbonate Melt in the Mantle Xenolith from the Komsomolskaya–Magnitnaya Kimberlite Pipe (Upper Muna Field, Yakutia)

Differentiation in corrosion performance of alumina forming alloys in alkali carbonate melts

Alkali carbonate melts are promising high temperature thermal storage media. In this work five alumina forming alloys have been exposed to a ternary LiNaK carbonate melt and CO2 at 800 °C. The corrosion propagation was found to depend on the formation of a slow-growing LiAlO2 scale. Furthermore, the two polymorphs contributing to the LiAlO2 phase were monitored for up to 1000 h: a dense α-LiAlO2 scale and γ-LiAlO2 crystallites. We suggest a growth stress assisted formation of α-LiAlO2 relaxing into the outwards growing γ-LiAlO2 phase. This implies a deceleration of the α-LiAlO2 scale growth towards a steady state-thickness.

Переработка висмутистых окислов

Introduction. The paper is devoted to the creation of an environmentally safe, technologically efficient and cost-effective high-performance integrated scheme for the recycling of lead-containing industrial products and waste, in particular, bismuth oxides and drosses formed during the melting of copper-electrolyte sludge, with the production of commodity monoelement products. To solve the problem, a combined technology is used, which is based on hydrometallurgical operations that allow separating chemical elements with similar properties with high extraction into finished products. The aim of the work is to study and develop fundamental approaches and rational integrated technologies for recycling bismuth drosses and oxides-industrial products of refining rough lead, using reducing melts of raw materials and bismuth-enriched sludge, electrolysis of bismuth lead to obtain rough bismuth containing ≥ 90 % Bi with its direct extraction of ≥ 70 %. Methods and approaches: melting at a temperature of 1,100…1,150 oC a charge of optimal composition containing bismuth oxides, sodium carbonate, silicon dioxide and carbon. Novelty: a decrease in the content of noble metals and accompanying chalcogenes in secondary copper-containing raw materials with an increase in the amount of impurity elements. Results and discussion: joint melting (1,100…1,150 °C) of bismuth oxides, sodium carbonate, silicon dioxide and carbon, taken in the mass ratio 100 : (15‒66) : (11‒25) : (5‒7), allows to transfer 89.0 – 93.6 % of bismuth and 99.5 ‒ 99.7 % of lead from the initial oxides to bismuth lead containing ~7 % Bi and ~80 % Pb. The main phase of the Pb-Bi alloy is elemental lead. The increased flux consumption leads to an increase in the amount of recycled silicate slags that are poor in target metals, into which it passes,%: 1.4 Bi; 2 Pb; 47 Zn; 23 Sb; 33 Sn. Main slag phases are following: Na2CaSiO4, Na4Mg2Si3O10, MgO, Pb, ZnS, PbS. The practical relevance is determined by the optimal mode of reducing melting of bismuth oxides (100 %) to obtain lead bismuth, %: 66 Na2CO3, 25 SiO2, 5 C; the process temperature is 1,150 ° C. The presence of impurities makes it necessary to introduce reagent treatment of lead bismuth into the technological scheme for recycling bismuth oxides. Decontamination and alkaline softening will make it possible to obtain a Pb-Bi alloy suitable for pyroelectrometallurgical recycling.

The Oldoynio Lengai volcano, Tanzania: the essence of its recent eruptions

The article considers the nature of the volcanic fluxes that are traditionally interpreted as the only example of recent mantle-derived carbonatite lavas (carbonate magmas or melts) on the Earth. However, it turns out that this is not correct. These fluxes represent muddy soda masses with organics. Their source are masses of solutions and sediments of the Natron alkaline lake, that penetrate deep to the above-chamber space of the volcano along riftogenic faults, where they are heated and then erupt as fluxes, geysers, and ash masses. The eruption products in turn get to the lake again. At the recent stage of development, the Oldoynio Lengai volcano represents an epimagmatic phreatic hydrothermal recycling system.

A reversed redox gradient in Earth's mantle transition zone

The Earth's mantle hosts a variety of reduced and oxidized phases, including iron-bearing alloys, diamond, and sulfide and carbonate melts. In the upper mantle, increasing pressure favors the stabilization of reduced iron-bearing phases via disproportionation of ferrous iron into ferric and metallic iron. Pressure-driven disproportionation is thought to continue into the transition zone, based on the extrapolation of experiments conducted at lower pressures. To test this hypothesis, we performed high-temperature and high-pressure experiments on basaltic and peridotitic compositions at pressures of 10 to 20 GPa, buffered at different oxygen fugacities. Under these conditions, majoritic garnet is the dominant ferric-iron bearing phase. We analyze our experimental run products for their ferric iron concentrations with EELS and Mössbauer spectroscopy. Contrary to expectations, results show that at iron saturation, ferric iron content of majorite peaks in the upper transition zone and then decreases between 500 and 650 km depth, destabilizing and resorbing reduced phases. This peak can be explained by decreases in the effective volume of ferrous minerals in transition zone assemblages. We also show that natural diamond-hosted majorite inclusions that equilibrated in the sublithospheric mantle grew from variably reduced fluids. These results are consistent with the idea that these diamonds formed during progressive reduction of an originally carbonatitic melt.

Three-stage modification of lithospheric mantle: Evidence from petrology, in-situ trace elements, and Sr isotopes of mantle xenoliths in the Cenozoic basalts, northeastern North China Craton

Abstract We present mineralogical and geochemical compositions of mantle xenoliths from two Cenozoic basalt localities of the northeastern North China Craton. These xenoliths include lherzolite, harzburgite, and websterite. They are generally fertile in major elements and different from the typical cratonic lithosphere, which is consistent with previous hypotheses regarding craton destruction. The ratios of 87Sr/86Sr and (La/Yb)N of clinopyroxenes (Cpx) in one lherzolite are relatively low in the core but high in the rim. The center of the Cpx grain has a high U concentration. Changes in trace elements and Sr isotopes indicate that later stage high 87Sr/86Sr melt metasomatism superimposed on the early hydrous melt/fluid. The Cpxs in some xenoliths are low in Ti/Eu but high in Ca/Al and light rare earth elements, which indicates carbonate melt metasomatism. 87Sr/86Sr is increased in the core and decreased in the rim of most Cpx grains, which reflects the superposition of two-stage metasomatism. The early agent should be high in 87Sr/86Sr, and the recent agent should be low in 87Sr/86Sr. The Cpxs in olivine websterite are low in 87Sr/86Sr (0.70220–0.70320), which reflects the recent metasomatism of asthenosphere-derived melt. Collectively, these observations reflect a three-stage modification of the lithospheric mantle. First-stage hydrous melt/fluid could come from the dehydration of young subducted plates. Second-stage melt/fluid of high 87Sr/86Sr could derive from the partial melting of the subducted altered oceanic crust, and the recent melt/fluid of low 87Sr/86Sr should be from the asthenosphere.

Extremely low-Ni olivine as a tracer of carbonate-rich sediment recycling beneath the southwestern Okinawa Trough

ABSTRACT Carbonate recycling in subduction zones has a strong influence on arc magmatism and carbon reservoirs in the mantle. However, geochemical evidence of carbonate recycling during subduction, especially at sub-arc depths, is rare and the related process is poorly understood. In this study, we document high-Mg olivines (81–91 mol.% forsterite) with extremely low Ni concentrations (mostly <600 ppm), which occur in host dacites recovered from the southwestern Okinawa Trough (SWOT). The temperature–pressure of crystallization had a negligible effect on the Ni contents of the olivines, and reactions between primary basaltic magmas and the lithospheric mantle were also insignificant. Small sulphide droplets are present in the olivines, which suggest that sulphide–silicate melt immiscibility occurred during the early stages of magmatic evolution. Although early segregation of sulphide melts could reduce the Ni contents of the primitive magmas, our forward modelling suggests that sulphide segregation cannot solely explain the low Ni contents. Therefore, the most likely explanation for low Ni concentrations is the interaction between Ca-rich carbonate melts and the mantle wedge, forming an olivine-rich mantle source by consumption of orthopyroxene, as indicated by the extremely low Ni/Mg and high Ca/Fe ratios of magmatic olivines. Given that the SWOT is located just ~100 km above the Wadati–Benioff zone, our results provide rare evidence for carbonate recycling at sub-arc depths in an active subduction zone.