Search Results (127)

The chemical compositions and formation temperatures of magnesian calcite and dolomite were estimated by using the combination of chemical analysis, crystallographic parameters, and a plethora of various diagrams and mathematical calculations. This study presents an example of the calculated crystallo-chemical formula (Ca_0.960Mg_0.039Fe_0.001)CO₃, obtained from chemical analysis on a representative marble sample from the Bukulja–Venčac area in central Serbia. Substituting CaCO₃ with MgCO₃ and FeCO₃ in dolomite adds approximately 3–5 mol. %, enhancing the classification and indicating that it is more accurately identified as magnesium-excess dolomite. The estimated formation temperature of magnesian calcite (1) is approximately 528 °C, whereas magnesian calcite (2) forms at about 341 °C. The ~187 °C difference corresponds to ~3.28 mol. % MgCO₃ (~7.18% dolomite), reflecting the distinction between magnesian calcite (1) and magnesian calcite (2). Considering the presence of the submicroscopic intergrowth and exsolution of dolomite within magnesian calcite (1), which are further subdivided in magnesian calcite (2), the estimated formation temperature of ~341 °C appears to be more realistic. The synthesis of the results suggests that this combined method could be helpful in the geothermometry of marble samples after the treatment with acetic acid. However, despite the promising results, additional experiments are necessary to validate the proposed modified geothermometry approach. Full article

Sulfides are essential tracers for understanding the redox conditions, diffusion processes, and thermal mechanisms involved in the formation of ordinary chondrites. Their mineralogical and textural evolution provides valuable constraints on the metamorphic history of parent bodies. In this context, the Ksar El Goraane meteorite, which fell in Morocco in 2018 and is classified as an H5 ordinary chondrite, represents a particularly instructive case for investigating sulfur behavior during thermal metamorphism. Petrographic observations combined with geochemical data obtained by electron probe microanalysis (EPMA) and energy-dispersive X-ray spectroscopy (EDS) were used to characterize the main silicate and sulfide phases and to evaluate their degree of chemical equilibration. The compositions of olivine (Fa_18–20), Mg-Rich orthopyroxene, and sodic plagioclase (An_10–15) display limited analytical dispersion and well-recrystallized textures, confirming that Ksar El Goraane experienced an equilibrated metamorphic grade consistent with an H5 ordinary chondrite. The sulfide assemblage is dominated by troilite (FeS), iron-rich pyrrhotite (Fe_1−xS), and pentlandite ((Fe,Ni)₉S₈), with minor occurrences of pyrite (FeS₂). Textural relationships and chemical homogeneity observed in backscattered electron images and elemental maps indicate progressive re-equilibration during thermal metamorphism. Formation and transformation temperatures of the sulfide phases are inferred through comparison with experimental and empirical constraints reported in the literature. These results suggest early high-temperature crystallization of troilite, followed by sulfur depletion leading to pyrrhotite formation, subsequent low-temperature exsolution of pentlandite, and localized late-stage pyrite crystallization. Full article

Pt-Fe alloys with abundant inclusions are from the Camumbi River placer deposit, Ecuador. They are derived from unknown Alaskan–Uralian-type intrusion(s) within the Late Cretaceous Naranjal accreted terrane. Compositions of our previously documented chilled silicate glass inclusions are increasingly fractioned from hydrous ferrobasalt to rhyolite in terms of TAS (total alkalis vs. silica). Their liquid lines of descent change from tholeiitic to the calc-alkaline magma series. Here, we document seven rare composite inclusion parageneses of Cu–PGM (platinum-group mineral) sulfides, each coexisting with and exsolved from related fractionated silicate glass (melt). Differentiation is dominated by fractional crystallization in PGM bulk compositions from tholeiitic silicate melts at the highest T (temperature): ~1018 °C. Silicate glass inclusions following the lower T calc-alkaline trend coexist with sulfide PGM parageneses that were likely differentiated, in terms of Pt-Rh-Pd and BMs (base metals), by incongruent melting due to decompression and S-degassing at ~983–830 °C. S-saturated sulfide melts become S-undersaturated below 845 °C. The calculated temperatures are for silicate glass. Pt-rich braggite shows increasing fractionation towards Pd-rich vysotskite within one inclusion paragenesis. A late braggite–vysotskite fractionation trend shows decreasing minor base metals (BMs). Thiospinels are dominated by cuprorhodsite. Minor thiospinels indicate Fe and then strong Ni enrichment at the lowest T. Decompression exsolutions, deflation, and the partial melting of some sulfide inclusion parageneses support rapid ascent to higher crustal levels within a deep-sourced cumulate intrusion. Full article

Experimental and theoretical techniques have been developed to quantify foamy oil behaviour of solvent-heavy oil systems at bubble level during a gas exsolution process. During constant composition expansion (CCE) tests, we artificially induced foamy oil dynamics for solvent-heavy oil systems by gradually reducing pressure and recorded the changed pressures and volumes in an isolated PVT setup at a given temperature. By discretizing gas bubbles on the basis of the classical nucleation theory, we theoretically integrated the population balance equation (PBE), Fick’s law, and the Peng–Robinson equation of state (PR EOS) to reproduce the experimental measurements. Pseudo-bubblepoint pressure for a given solvent-heavy oil system can be increased with either a lower pressure depletion rate or a higher temperature, during which gas bubble growth is facilitated with a reduction in viscosity and/or an increase in solvent concentration, but gas bubble nucleation and mitigation is hindered with an increase in solvent concentration. Compared to CO₂, CH₄ is found to yield stronger and more stable foamy oil, indicating that foamy oil is more stable with a larger amount of dispersed gas bubbles at lower temperatures. Using the PR EOS together with the modified alpha functions at T_r = 0.7 and T_r = 0.6, the absolute average relative deviation (AARD) is reduced from 4.58% to 2.24% with respect to the predicted pseudo-bubblepoint pressures. Full article

The lack of ultra-high temperature and ultra-high pressure (U-HTHP) experimental devices makes the data of CO₂-CH₄ solubility and exsolution insufficient under U-HTHP conditions, which leads to an unclear competitive solubility-exsolution mechanism of CH₄-CO₂ miscible natural gas. This study systematically investigates fluid-phase characteristics in the LD10-X gas field, the impacts of mixing ratio, sequence, temperature, and pressure on CO₂/CH₄ solubility, and the CO₂/CH₄ exsolution patterns. Mixing ratio experiments showed that CH₄ does not appear in the mixed solution when CO₂ mole fraction exceeds 7%. Solubility sequence tests revealed that CH₄ is no longer dissolved when CO₂ reaches solubility equilibrium. However, CO₂ continues to dissolve when CH₄ reaches the solubility equilibrium. Solubility with temperature and pressure experiments showed that solubility of both CO₂ and CH₄ increased with rising temperature and pressure. In addition, the exsolution amount increased slowly and then increased rapidly with the increase in the pressure difference for the CO₂ in the CO₂ and CH₄ phase. In addition, these laws were employed to explain the changes in CH₄ and CO₂ concentrations during the drill steam testing of wells LD10-X-10 and LD10-X-12, mainly because the extraction capacity of CO₂ decreased after pressure reduction. Additionally, CO₂ produced by chemical equilibrium movements extracted excess CH₄ again. This study provides guidelines for the design of CO₂ storage schemes and enhanced CH₄ recovery. Full article

Natural hydrogen is generated by fairly deep processes and/or in low-permeability rocks. In such contexts, fluids circulate mainly through the network of faults and fractures. However, hydrogen flows from these hydrogen-generating layers can reach sedimentary rocks with more typical permeability and porosity, allowing H₂ flows to spread out rather than be concentrated in fractures. In that case, three different H₂ transport modes exist: advection (displacement of water carrying dissolved gas), diffusion, and free gas Darcy flow. Numerical models have been run to compare the efficiency of these different modes and the pathway they imply for the H₂ in a sedimentary basin with active aquifers. The results show the key roles of these aquifers but also the competition between free gas flow and the dissolved gas displacement which can go in opposite directions. Even with a conservative hypothesis on the H₂ charge, a gaseous phase exists at few kilometers deep as well as free gas accumulation. Gaseous phase displacement could be the faster and diffusion is neglectable. The modeling also allows us to predict where H₂ is expected in the soil: in fault zones, eventually above accumulations, and, more likely, due to exsolution, above shallow aquifers. Full article

The Bundelkhand granite (BG) constitutes the bulk of the granitoid complex in the Bundelkhand Craton and preserves imprints of its evolution from the magmatic to a protracted hydrothermal stage as deduced from the petrography. In order to reconstruct such a path of evolution in this study, thermobarometric calculations were attempted on the mineral chemistry of the major (hornblende, plagioclase, biotite) and minor (epidote, apatite) magmatic phases. They yielded magmatic temperatures and pressures (in excess of 700 °C and ~5 kbar), although not consistently, and indicate mid-crustal conditions at the onset of crystallization. Temperatures in the hydrothermal regime within the BG are better constrained by the chemistry of the chlorite and epidote minerals (340 to 160 °C) that conform with the ranges of homogenization temperatures of aqueous–biphase inclusions in matrix quartz in the BG and subordinate quartz veins. These reconstructions indicate that fluid within the BG evolved down to lower temperatures and towards the deposition of quartz and, more importantly, bears a striking similarity to the temperature–salinity characteristics of fluid in the giant quartz reef system. Scanty mixed aqueous–carbonic inclusions in the BG are indicative of the CO₂-poor nature of the BG magma and the exsolution of CO₂ at lower pressure (~2.6 kbar). The dominant mechanism of fluid evolution in the BG appears to be the incursion of meteoric fluid, which caused fluid dilution. Laser Raman microspectrometry reveals many types of solid phases in aqueous–carbonic inclusions in the BG domain. The occurrence of unusual, effervescent-type inclusions, though infrequent, bears a striking similarity to that reported in the giant quartz reef domain. Thus, the highlight of the present work is the convincing fluid inclusion evidence that genetically links the BG with the giant quartz reef system, although many cited discrepancies arise from the radiometric dates. We visualize the episodic release of silica-transporting fluid to the major fracture system (now occupied by the giant reef) from the BG, thus making the fluid in the two domains virtually indistinguishable. Full article

This study investigates pegmatites with exceptionally rare mineralogical and chemical signatures, hosted by the 1.8 Ga peralkaline albite-enriched granite, which corresponds to the renowned Madeira Sn-Nb-Ta-F (REE, Th, U) deposit in Pitinga, Brazil. Four distinct pegmatite types are identified: border pegmatites, pegmatitic albite-enriched granite, miarolitic pegmatite, and pegmatite veins. The host rock itself has served as the source for the fluids that gave rise to all these pegmatites. Their mineral assemblages mirror the rare-metal-rich paragenesis of the host rock, including pyrochlore, cassiterite, riebeckite, polylithionite, zircon, thorite, xenotime, gagarinite-(Y), genthelvite, and cryolite. These pegmatites formed at the same crustal level as the host granite and record a progressive magmatic–hydrothermal evolution driven by various physicochemical processes, including tectonic decompressing, extreme fractionation, melt–melt immiscibility, and internal fluid exsolution. Border pegmatites crystallized early from a F-poor, K-Ca-Sr-Zr-Y-HREE-rich fluid exsolved during solidification of the pluton’s border and were emplaced in contraction fractures between the pluton and country rocks. Continued crystallization toward the pluton’s core produced a highly fractionated melt enriched in Sn, Nb, Ta, Rb, HREE, U, Th, and other HFSE, forming pegmatitic albite-enriched granite within centimetric fractures. A subsequent pressure quench—likely induced by reverse faulting—triggered the separation of a supercritical melt, further enriched in rare metals, which migrated into fractures and cavities to form amphibole-rich pegmatite veins and miarolitic pegmatites. A key process in this evolution was melt–melt immiscibility, which led to the partitioning of alkalis between two phases: a K-F-rich aluminosilicate melt (low in H₂O), enriched in Y, Li, Be, and Zn; and a Na-F-rich aqueous melt (low in SiO₂). These immiscible melts crystallized polylithionite-rich and cryolite-rich pegmatite veins, respectively. The magmatic–hydrothermal transition occurred independently in each pegmatite body upon H₂O saturation, with the hydrothermal fluid composition controlled by the local degree of melt fractionation. These highly F-rich exsolved fluids caused intense autometasomatic alteration and secondary mineralization. The exceptional F content (up to 35 wt.% F in pegmatite veins), played a central role in concentrating strategic and critical metals such as Nb, Ta, REEs (notably HREE), Li, and Be. These findings establish the Madeira system as a reference for rare-metal magmatic–hydrothermal evolution in peralkaline granites. Full article

The current work records for the first time the rare-metal pegmatites with mixed NYF-LCT located at Wadi Sikait, south Eastern Desert of the Egyptian Nubian Shield. Most of the Sikait pegmatites are associated with sheared granite and are surrounded by an alteration zone cross-cutting through greisen bodies. Sikait pegmatites show zoned and complex types, where the outer wall zones are highly mineralized (Nb, Ta, Y, Th, Hf, REE, U) than the barren cores. They consist essentially of K-feldspar, quartz, micas (muscovite, lepidolite, and zinnwaldite), and less albite. They contain a wide range of accessory minerals, including garnet, columbite, fergusonite-(Y), cassiterite, allanite, monazite, bastnaesite (Y, Ce, Nd), thorite, zircon, beryl, topaz, apatite, and Fe-Ti oxides. In the present work, the discovery of Li-bearing minerals for the first time in the Wadi Sikait pegmatite is highly significant. Sikait pegmatites are highly mineralized and yield higher maximum concentrations of several metals than the associated sheared granite. They are strongly enriched in Li (900–1791 ppm), Nb (1181–1771 ppm), Ta (138–191 ppm), Y (626–998 ppm), Hf (201–303 ppm), Th (413–685 ppm), Zr (2592–4429 ppm), U (224–699 ppm), and ∑REE (830–1711 ppm). The pegmatites and associated sheared granite represent highly differentiated peraluminous rocks that are typical of post-collisional rare-metal bearing granites. They show parallel chondrite-normalized REE patterns, enriched in HREE relative to LREE [(La/Lu)_n = 0.04–0.12] and strongly negative Eu anomalies [(Eu/Eu*) = 0.03–0.10]. The REE patterns show an M-type tetrad effect, usually observed in granites that are strongly differentiated and ascribed to hydrothermal fluid exchange. The pegmatite has mineralogical and geochemical characteristics of the mixed NYF-LCT family and shows non-CHARAC behavior due to a hydrothermal effect. Late-stage metasomatism processes caused redistribution, concentrated on the primary rare metals, and drove the development of greisen and quartz veins along the fracture systems. The genetic relationship between the Sikait pegmatite and the surrounding sheared granite was demonstrated by the similarities in their geochemical properties. The source magmas were mostly derived from the juvenile continental crust of the Nubian Shield through partial melting and subsequently subjected to a high fractional crystallization degree. During the late hydrothermal stage, the exsolution of F-rich fluids transported some elements and locally increased their concentrations to the economic grades. The investigated pegmatite and sheared granite should be considered as a potential resource to warrant exploration for REEs and other rare metals. Full article

Solid oxide cells (SOCs) are highly efficient and versatile devices capable of utilizing a variety of fuels, presenting promising solutions for energy conversion and renewable resource utilization. There is an urgent need for the strategic design of robust and high-efficiency materials to enhance both conversion and energy efficiencies before SOCs can be applied for large-scale industrial production. Nanocomposite electrodes, especially those fabricated through infiltration and metal nanoparticle exsolution, have emerged as highly active electrocatalytic materials that significantly improve the performance and durability of SOCs. This review systematically summarizes and analyzes recent advances in the nanoscale architecture of electrode materials fabricated via common nanoengineering strategies, including infiltration and in situ exsolution, with applications in CO₂/H₂O reduction, hydrocarbon electrochemical oxidation, solid oxide fuel cells, and reversible operation. Finally, this review highlights existing bottlenecks and promising breakthroughs in common nanotechnologies, aiming to provide useful references for the rational design of nanomaterials for SOCs. Full article

CuCrO₂ (mcconnellite) was synthesized using both the solid-state method and microwave dielectric firing. It was characterized as a novel black ceramic pigment for use in various industrial glazes. For the first time, the application of mcconnellite (CuCrO₂) and its coloured glazes as selective solar absorbers (SSA) for integral ceramic solar collectors has been reported. The addition of quartz or anatase as colour modifiers was investigated to prevent the bluing of the pigment in Zn-containing glazes, a phenomenon associated with the exsolution of copper. Furthermore, doping with lanthanide oxides was explored to address two key challenges: controlling the formation of pinhole defects in porcelain glazes, which are linked to the destabilization of Cu⁺, and adjusting the IR cut-off wavelength to improve its performance as SSA. Full article

Solid oxide cells (SOCs) can operate efficiently in solid oxide fuel cell (SOFC) and/or solid oxide electrolysis cell (SOEC) modes, and are one of the most promising electrochemical devices for energy conversion and storage, facilitating the integration of renewable energies with the electric grid. However, the SOC electrodes suffer performance and stability issues, especially in the case of fuel electrodes when SOCs are fueled by cheaper and more available fuels such as methane and natural gas. Typical Ni-YSZ cermet fuel electrodes suffer problems of coarsening, carbon deposition, and sulfur poisoning. Therefore, developing new electrodes using novel design strategies for SOCs is crucial. In this review work, the fuel electrode development strategies including the in situ exsolution of nanoparticles, multi-elemental nanocatalysts, and nanofiber materials have been reviewed and summarized for the design of new electrodes for SOCs. Nanofiber electrodes with in situ exsolved nanoparticles, which combine the advantages of a unique nanofiber microstructure and stable and active exsolved nanoparticles, are of great interest and significantly contribute to the development of high-performance fuel electrodes for SOCs. Full article

This study investigates the effect of the exsolution behavior of alumina-rich spinel on the formation and distribution of CA₆ (CaAl₁₂O₁₉) in corundum castables bonded with calcium aluminate cement. In this study, alumina-rich spinel is substituted for tabular corundum in the same proportions and grain size. The matrices after curing were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The phase composition and microstructure of the matrices containing alumina-rich spinel were analyzed after firing at 1600 °C. These results showed that the addition of alumina-rich spinel significantly improved the mechanical strength of the castables. This improvement was attributed to the alumina produced by spinel exsolution during firing at 1600 °C, which reacted in situ with CA₂ (CaAl₄O₇) to form CA₆. CA₆ connects the different particles and forms an interspersed interlocking structure within the spinel. The CA₆-MA interspersed interlocking structure replaces part of the CA₆-Al₂O₃ structure and significantly improves the mechanical strength of the castables. Full article

The Neoarchean diorite- and tonalite-dominated Chibougamau pluton (Canada) is ideal for case studies dedicated to the petrogenesis and timing of emplacement of fertile magmatic systems and associated Cu-Au porphyry systems. Using whole-rock analyses, geochronology, and zircon chemistry, it is determined that an early magmatic phase (pre-2714 Ma) is derived from a dioritic magma with a moderate ƒO₂ (ΔFMQ 0 to +1), which is optimal for transporting Au and Cu, and that diorite is a potentially fertile magma. Field descriptions indicate that the main mineralizing style consists of sulfide-filled hairline fractures and quartz–carbonate veins. This is likely the consequence of fluid circulation facilitated by a well-developed diaclase network formed following the intrusion of magma at about 4–7 km depth in a competent hosting material. The petrographic features of fluid inclusions (FIs), considered with their microthermometric data and evaporate mound chemistry, suggest the exsolution of early CO₂-rich fluids followed by the unmixing of later aqueous saline fluids characterized by a magmatic signature (i.e., Na-, Ca-, Fe-, Mn-, Ba-, and Cl-F). The type of magmatism and its oxidation state, age relationships, the nature of mineralization, and fluid chemistry together support a model whereby metalliferous fluids are derived from an intermediate hydrous magma. This therefore enforces a porphyry-type metallogenic model for this Archean setting. Full article

Solid Oxide Electrolysis Cells (SOECs) can electro-reduce carbon dioxide to carbon monoxide, which not only effectively utilizes greenhouse gases, but also converts excess electrical energy into chemical energy. Perovskite-based oxides with exsolved metal nanoparticles are promising cathode materials for direct electrocatalytic reduction of CO₂ through SOECs, and have thus received increasing attention. In this work, we doped Pr_0.7Ba_0.3MnO_3−δ at the B site, and after reduction treatment, metal nanoparticles exsolved and precipitated on the surface of the cathode material, thereby establishing a stable metal–oxide interface structure and significantly improving the electrocatalytic activity of the SOEC cathode materials. Through research, among the Pr_0.7Ba_0.3Mn_1−xNi_xO_3−δ (PBMN_x = 0–1) cathode materials, it has been found that the Pr_0.7Ba_0.3Mn_0.9Ni_0.1O_3−δ (PBMN_0.1) electrode material exhibits greater catalytic activity, with a CO yield of 5.36 mL min⁻¹ cm⁻² and a Faraday current efficiency of ~99%. After 100 h of long-term testing, the current can still remain stable and there is no significant change in performance. Therefore, the design of this interface has increasing potential for development. Full article