Search Results (30)

Enhanced Geothermal Systems (EGS) require thermochemically stable proppant materials capable of sustaining fracture conductivity under harsh subsurface conditions. This study systematically investigates the response of commercial proppants to coupled thermo-hydro-chemical (THC) effects, focusing on chemical stability and microstructural evolution. Four proppant types were evaluated: an ultra-low-density ceramic (ULD), a resin-coated sand (RCS), and two quartz-based silica sands. Experiments were conducted under simulated EGS conditions at 130 °C with daily thermal cycling over a 25-day period, using diluted site-specific Utah FORGE geothermal fluids. Static batch reactions were followed by comprehensive multi-modal characterization, including scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and micro-computed tomography (micro-CT). Proppants were tested in both granular and powdered forms to evaluate surface area effects and potential long-term reactivity. Results indicate that ULD proppants experienced notable resin degradation and secondary mineral precipitation within internal pore networks, evidenced by a 30.4% reduction in intragranular porosity (from CT analysis) and diminished amorphous peaks in the XRD spectra. RCS proppants exhibited a significant loss of surface carbon content from 72.98% to 53.05%, consistent with resin breakdown observed via SEM imaging. While the quartz-based sand proppants remained morphologically intact at the macro-scale, SEM-EDS revealed localized surface alteration and mineral precipitation. The brown sand proppant, in particular, showed the most extensive surface precipitation, with a 15.2% increase in newly detected mineral phases. These findings advance understanding of proppant–fluid interactions under low-temperature EGS conditions and underscore the importance of selecting proppants based on thermo-chemical compatibility. The results also highlight the need for continued development of chemically resilient proppant formulations tailored for long-term geothermal applications. Full article

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

The Boda Claystone Formation (BCF) is considered to serve as a natural barrier to the potential high-level radioactive waste repository in Hungary. In order to evaluate the radionuclide retention capacity of the albitic claystone of the BCF, the adsorption and diffusion properties of the rock for Ni²⁺ and Co²⁺ cations (activation products) were investigated separately and in competitive conditions when the two ions were simultaneously added. Batch sorption experiments were performed with powdered and conditioned albitic claystone samples in synthetic pore water to obtain adsorption isotherms. In addition, adsorption tests were performed on petrographic thin sections to check the transferability between dispersed and compact systems. Correlation analysis of microscopic X-ray fluorescence elemental maps recorded on thin sections suggested that nickel is primarily bound to clay minerals (mainly illite and chlorite), which was confirmed by (scanning) transmission electron microscopy measurements. Around illite particles, a newly formed nickel-rich few atomic layer thick phyllosilicate phase was identified. The discrepancy between the experimental and modeled adsorption isotherm at high concentrations could be explained with this nickel-rich new phase. Apart from C_in = 10⁻³ M and only Ni²⁺ or Co²⁺ in the source, the apparent diffusion coefficients of Ni²⁺ and Co²⁺ (C_in = 10⁻³–10⁻² M) were found to be similar. Overall, the BCF shows promising capabilities to retain the studied radionuclides. Full article

Sweet potatoes (Ipomoea batatas) are highly profitable, contribute to food security, and their leaves rich in phytonutrients. This study examined the optimal leaf harvesting stage by harvesting newly formed leaves (leaves 1 to 5) to achieve the highest concentration of carotenoids, phenolic compounds, antioxidant properties and mineral content. Leaves of five purple-fleshed sweet potato genotypes ‘2019-11-2’ and ‘2019-1-1’, ‘Purple-purple’, and from the USA ‘08-21P’ and ‘16-283P’ were harvested based on tuber life cycle [vegetative 8 weeks after planting (VS-8WAP), tuber initiation (TIS-12WAP), and tuber maturation phases (TMS-16WAP)]. At the 8WAP stage, leaves of genotype ‘2019-11-2’ had the highest concentrations of cyanidin-caffeoyl-sophoroside-glucoside (17.64 mg/kg), cyanidin-caffeoyl-feruloyl-sophoroside-glucoside (41.51 mg/kg), peonidin-caffeoyl-hydroxybenzoyl-sophoriside-glucoside (45.25 mg/kg), and peonidin caffeoyl-feruloyl-sophoriside-glucoside (24.47 mg/kg), as well as antioxidant scavenging activity. In contrast, ‘Purple-purple’ harvested at TIS-12WAP showed the highest concentration of caffeoylquinic acid derivatives. Zeaxanthin, lutein, all trans-β-carotene, and cis-β-carotene are the most abundant carotenoids in genotype ‘08-21P’ at VS-8WAP. As a result, local genotypes ‘2019-11-2’ harvested at 8WAP and ‘Purple-purple’ harvested at 12WAP are potential sources of anthocyanins and caffeoylquinic acid derivatives. Conversely, USA’s genotype ‘08-21P’ at the VS-8WAP stage is an excellent source of carotenoids. The leaves of USA’s ‘08-21P’ genotype and the local ‘2019-11-2’ genotype at TMS-16WAP exhibited the highest content of Fe and Mn, respectively. The study identified the optimal leaf stage for consumption of leaves and for use as a functional ingredient. Full article

Biomacromolecules control mineral formation during the biomineralization process, but the effects of the organic components’ functionality on the type of mineral phase is still unclear. The biomimetic precipitation of calcium phosphates in a physiological medium containing either polycarboxybetaine (PCB) or polysulfobetaine (PSB) was investigated in this study. Amorphous calcium phosphate (ACP) or a mixture of octacalcium phosphate (OCP) and dicalcium phosphate dihydrate (DCPD) in different ratios were identified depending on the sequence of initial solution mixing and on the type of the negative functional group of the polymer used. The more acidic character of the sulfo group in PSB than the carboxy one in PCB determines the dominance of the acidic solid phases, namely, an acidic amorphous phase or DCPD. In the presence of PCB, the formation of ACP with acicular particles arranged in bundles with the same orientation was observed. A preliminary study on the remineralization potential of the hybrid material with the participation of PSB and a mixture of OCP and DCPD did not show an increase in enamel density, contrary to the materials based on PCB and ACP. Moreover, the latter showed the creation of a newly formed crystal layer similar to that of the underlying enamel. This defines PCB/ACP as a promising material for enamel remineralization. Full article

The Lower Urgen molybdenum deposit (44,856 t Mo @ 0.141%), situated in the northern Great Xing’an Range, is a newly discovered porphyry molybdenum deposit. Mineralization is characterized by veinlet-disseminated- and vein-type quartz–sulfide orebodies primarily occurring in the cupola of the Early Cretaceous granite porphyry stock. In this study, we present a detailed description of the ore geology, molybdenite Re-Os dating, H-O-S-Pb isotopic compositions, and fluid inclusion (FI) analyses including petrography, laser Raman, and microthermometry to precisely constrain the timing of ore formation, the origin of ore-forming fluids and materials, as well as the metal precipitation mechanism. Molybdenite Re-Os dating yielded two model ages of 141.2 ± 1.5 and 147.7 ± 1.7 Ma, coeval with the regional Late Jurassic–Early Cretaceous molybdenum metallogenesis. The hydrothermal process can be divided into three stages: the quartz–molybdenite(–pyrite) stage, quartz–polymetallic sulfide stage, and quartz–carbonate stage. Four types of FIs were distinguished for quartz, including two-phase liquid-rich (L-type), saline (S-type), CO₂-rich (C1-type), and CO₂-bearing (C2-type) FIs. Microthermometric data showed that the homogenization temperatures and salinities from the early to late stages were 240–430 °C, 5.0–11.9, and 30.1–50.8 wt% NaCl equiv.; 180–280 °C and 3.0–9.1 wt% NaCl equiv.; and 120–220 °C and 0.2–7.9 wt% NaCl equiv., respectively, suggesting a decreasing trend. H-O isotopic compositions indicate that the ore-forming fluids were initially of magmatic origin with the increasing incorporation of meteoric water. S-Pb isotopic compositions indicate that the ore-forming materials originated from granitic magmas, and the mineralization is genetically related to the ore-bearing granite porphyry stock in the deposit. Fluid immiscibility and fluid–rock interaction are collectively responsible for the massive deposition of molybdenite in stage 1, whereas fluid mixing and immiscibility played a critical role in the deposition of polymetallic sulfide in stage 2. Full article

Rocks and minerals buried in the earth’s surface usually undergo weathering processes and change color in the burying environment. A kind of yellow Chinese stamp stone named “Lumu stone”, which is buried in a yellowish weathering crust (yellowish soil), was selected to investigate its color changes in the weathering processes. In this study, the appearance features, mineral components, micromorphology, spectroscopy characteristics, and color causation of the “Lumu stone” were studied by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), an electron probe microanalyzer (EPMA), a laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS), and a UV-Visible (UV-Vis) spectrum. The “Lumu stone” usually exhibits a darker yellow outer layer and a lighter yellow core, suggesting that yellow color permeated into the stone from the surface to the core gradually and the color is secondary forming. The results from XRD and SEM show the studied samples are mainly composed of dickite and illite. The individual particles of the dickite and illite are about 2–5 μm, randomly distributing in the three-dimensional space and constituting voids among the particles. The acid pickling experiments using HCl coupled with KSCN confirmed that the mineral phases that caused the yellow color of the matrix are iron oxide and hydroxide. On the other hand, goethite and hematite were observed gathering in the yellow and brown-red cracks on the “Lumu stone” by SEM study. However, iron oxide and hydroxide in the matrix were difficult to observe and detect among the dickite and illite aggregates by SEM and XRD methods. It indicates that they may be nanoscale in size and very low in content. According to the calculation of the second derivative of Kubelka-Munk (K-M) transformed diffuse reflection spectroscopy (DRS) curves obtained from UV-Vis, the characteristic peaks of goethite and hematite were found in the yellow matrix, and their contributions to the color were confirmed. The concentrations of goethite and hematite were calculated to be 0.32 to 1.87 g/kg and 0.22 to 0.93 g/kg in the studied samples, respectively. In this study, a series of methods were employed to detect very low levels of goethite and hematite in the samples undergoing weathering processes. Additionally, nanoscale goethite and hematite were considered newly formed minerals when buried in the weathering processes and may gradually move into the voids among phyllosilicate particles. Therefore, they turned the “Lumu stone” yellow. Full article

Concentrated growth factors (CGF) is the newest generation platelet concentrate product, which has been reported to promote the proliferation and differentiation of human dental pulp cells (hDPCs). However, the effect of liquid phase of CGF (LPCGF) has not been reported. This study was aimed to evaluate the influence of LPCGF on the biological properties of hDPCs, and to explore the in vivo mechanism of dental pulp regeneration based on the hDPCs-LPCGF complex transplantation. It was found that LPCGF could promote the proliferation, migration and odontogenic differentiation of hDPCs, and 25% LPCGF induced the most mineralization nodule formation and the highest DSPP gene expression. The heterotopic transplantation of the hDPCs-LPCGF complex resulted in the formation of regenerative pulp tissue with newly formed dentin, neovascularization and nerve-like tissue. Together, these findings provide key data on the effect of LPCGF on the proliferation, migration, odontogenic/osteogenic differentiation of hDPCs, and the in vivo mechanism of hDPCs-LPCGF complex autologous transplantation in pulp regeneration therapy. Full article

The solid phase of a commercial calcium phosphate (Graftys^® HBS) was combined with ovine or human blood stabilized either with sodium citrate or sodium heparin. The presence of blood delayed the setting reaction of the cement by ca. 7–15 h, depending on the nature of the blood and blood stabilizer. This phenomenon was found to be directly related to the particle size of the HBS solid phase, since prolonged grinding of the latter resulted in a shortened setting time (10–30 min). Even though ca. 10 h were necessary for the HBS blood composite to harden, its cohesion right after injection was improved when compared to the HBS reference as well as its injectability. A fibrin-based material was gradually formed in the HBS blood composite to end-up, after ca. 100 h, with a dense 3D organic network present in the intergranular space, thus affecting the microstructure of the composite. Indeed, SEM analyses of polished cross-sections showed areas of low mineral density (over 10–20 µm) spread in the whole volume of the HBS blood composite. Most importantly, when the two cement formulations were injected in the tibial subchondral cancellous bone in a bone marrow lesion ovine model, quantitative SEM analyses showed a highly significant difference between the HBS reference versus its analogue combined with blood. After a 4-month implantation, histological analyses clearly showed that the HBS blood composite underwent high resorption (remaining cement: ca. 13.1 ± 7.3%) and new bone formation (newly formed bone: 41.8 ± 14.7%). This was in sharp contrast with the case of the HBS reference for which a low resorption rate was observed (remaining cement: 79.0 ± 6.9%; newly formed bone: 8.6 ± 4.8%). This study suggested that the particular microstructure, induced by the use of blood as the HBS liquid phase, favored quicker colonization of the implant and acceleration of its replacement by newly formed bone. For this reason, the HBS blood composite might be worth considering as a potentially suitable material for subchondroplasty. Full article

The super-large Baerzhe Be–Nb–Zr–REE deposit in NE China is hosted in the Early Cretaceous peralkaline granites. In this work, the newly discovered granitic dikes developed around the Baerzhe deposit were studied for the first time, focusing on their genesis and genetic relationships with the Baerzhe peralkaline granites. Zircon U-Pb dating of these granitic rocks (including the granite porphyry, rhyolite and miarolitic granite) yielded Early Cretaceous ages of 125–121 Ma. Their mineral assemblages and geochemical features suggest that they share similar features with the peralkaline A-type granites. Their geochemical data and zircon Hf isotopic compositions (ε_Hf(t) = +3.4 to +10.5) indicate that the peralkaline granitic rocks were formed by the partial melting of dehydrated charnockite with extensive plagioclase crystal fractionation, which resulted in a peralkaline affinity. There are two types of distinct zircons in the studied samples: the type I zircon with a bright rim and dark core, which may represent a cumulate mineral phase captured together with aggregates during eruption, and the type II zircon with a higher evolution degree crystallized in the residual melts. Combined with the simulation results using whole-rock trace elements, we proposed that the peralkaline granitic dikes represent more evolved interstitial melts than the Baerzhe granitic magma. In the Early Cretaceous extensional tectonic settings, mantle-derived magma upwelled, which induced the melting of the lower crust and prolonged the evolutionary process of the magma crystal mush. Full article

Class C fly ash has been receiving increasing attention due to the gradual transition of thermal power plants all over the world to the fluidized bed combustion technology with sulfur dioxide emissions capture. This research investigates the utilization of class C fly ash in fired ceramic materials with simultaneous efficient and novel containment of sulfur dioxide emissions in the flue gas during firing. A number of experiments were conducted by addition of sodium water glass with different molar ratios of SiO₂:Na₂O, sodium carbonate, and different ratios of sodium carbonate to water glass to the class C fly ash to examine the optimal combination and quantity for the creation and formation of the mineral phase haüyne which resulted in reduction and containment of SO₂ emissions. Results revealed that a 12% dose of sodium water glass with a low molar ratio of 1.7 (SiO₂:Na₂O) combined with class C fly ash was more effective in the formation of haüyne and the resulting decrease of SO₂ in the flue gas was more substantial. The newly formed mineral phase haüyne was identified by an X-ray diffraction analysis and scanning electron microscopy with energy dispersive X-ray spectroscopy. Outcomes reveal a potential for utilization of class C fly ash in the fired materials by containment of sulfur dioxide into their structure. Full article

We provide results of a comprehensive mineralogical and microstructural study of relict lherzolites of the main ore field and fresh rocks from a deep structural borehole drilled in the south-eastern part of the Kempirsay massif. Olivine and orthopyroxene from lherzolites contain numerous pieces of evidence of material redistribution at different scales caused mainly by solid-state processes, such as plastic flow of mantle, syntectonic recrystallization, and annealing. The results of deformation-induced processes at the submicron scale are recorded by optical and electronic microscopy. In olivine, the plastic deformation caused segregation of impurities at structural defects. As a result, abundant tiny rods of newly formed Cr-spinels occurred inside its grains. Moreover, in enstatite, deformation caused partial or complete chemical decomposition with exsolution of diopside, pargasite and spinel lamellae up to the formation of a “fibrous” structure. In other cases, it provided partial or complete recrystallization to form new phases of enstatite-2, forsterite, diopside, pargasite, and spinel. Petrographic observations are validated by geochemical data, i.e., regularly decreasing concentrations of minor elements in neoblasts compared to large grains (porphyroclasts). Further redistribution of spinel grains with the formation of chromitite bodies is witnessed by their permanent association with the most mobile phase of the upper mantle, i.e., olivine, which is the only mineral that remains stable under the intense plastic flow. An increased concentration of Cr-spinel grains during formation of massive chromitites could appear under conditions close to pressure sintering, as evidenced by stressed textures of ores and an increased grain size compared to disseminated chromitites. The formation of unique chromitite deposits is associated with integration of numerous disparate podiform bodies into “ore bunches” due to the tectonic impact in the shear-compression regime. This was most likely associated with transition of the rifting (spreading) regime to that of the upper mantle of the fore-arc basin. Full article

This study investigates the capability of the Southeast Mesohellenic Trough (SE MHT) sandstone formations to serve as a potential reservoir for CO₂ storage in response to the emerging climate change issues by promoting environmentally friendly mineral sequestration applications. Sandstone samples, for the first time, were evaluated for their petrographic characteristics, mineral chemistry, geochemical properties, as well as their petrophysical and gas adsorption properties through tests. The sandstones were tested and classified into distinct groups. The most promising site to be considered for pilot CO₂ storage testing is the Pentalofos Formation locality since its sandstones display specific mineral phases with the proper modal composition to conceivably react with injected CO₂, leading to the development of newly formed and stable secondary mineral phases. The gas adsorption results are also more encouraging for sandstones from this sedimentary formation. All the measured UCS (uniaxial compressive strength), Ei (bending stiffness), and ν (Poisson’s ratio) results are above those dictated by international standards to perform CO₂ storage practices safely. Furthermore, the specified targeted locality from the Pentalofos Formation holds the geological advantage of being overlaid by an impermeable cap-rock formation, making it suitable for deploying CO₂ mineralization practices. The demarcated area could permanently store a calculated amount of ~50 × 10⁵ tons of CO₂ within the geological reservoir by reacting with the specified mineral phases, as specified through the proposed petrographic PrP index (potential reactive phases). Full article

Casein is a micellar protein rich in glutamic and aspartic acids as well as in phosphoserine. Considering its native affinity for calcium and the connection of sub-micelles through calcium phosphate nanoclusters, this protein holds promise for stimulating biomimetic mineralisation phenomena and direct binding with the mineral phase of hard tissues. In this work we prepared new hybrids based on casein embedded in a poly(2-hydroxyethyl methacrylate)-polyethyleneglycol diacrylate (PHEMA-PEGDA) hydrogel. The resulting materials were investigated structurally by Fourier transform infrared (FT-IR). Casein modified the water affinity and the rheological properties of the hybrids. The microstructure was explored by scanning electron microscopy (SEM) and the distribution of the protein was established by combined SEM micrographs and elemental mapping considering the casein-specific elements (P, N and S) not contained by the synthetic hydrogel matrix. The effect of casein on the mineralisation potential and stability of the mineral phase was investigated by FT-IR and SEM when alternating incubation in Ca/P solutions is performed. Increasing casein content in the hybrids leads to improved mineralisation, with localised formation of nanoapatite phase on the protein areas in the richest sample in protein. This behaviour was proved microstructurally by SEM and through overlapping elemental distribution of Ca and P from the newly formed mineral and P, S and N from the protein. This study indicates that nanoapatite-casein-PHEMA-PEGDA nanocomposites may be developed for potential use in bone repair and regeneration. Full article

Paper-ash is used for remediation of heavily contaminated soils with metals, but remediation efficiency after longer periods has not been reported. To gain insights into the mechanisms of immobilization of cadmium (Cd), lead (Pb), and znic (Zn), a study was performed in the laboratory experiment in uncontaminated, artificially contaminated, and remediated soils, and these soils treated with sulfate, to mimic conditions in contaminated soil from zinc smelter site. Remediation was performed by mixing contaminated soil with paper-ash to immobilize Cd, Pb, and Zn in the geotechnical composite. Partitioning of Cd, Pb, and Zn was studied over one year in seven-time intervals applying the sequential extraction procedure and complementary X-ray diffraction analyses. This methodological approach enabled us to follow the redistribution of Cd, Pb, and Zn over time, thus, to studying immobilization mechanisms and assessing the remediation efficiency and stability of newly formed mineral phases. Cd, Pb, and Zn were effectively immobilized by precipitation of insoluble hydroxides after the addition of paper-ash and by the carbonization process in insoluble carbonate minerals. After remediation, Cd, Pb, and Zn concentrations in the water-soluble fraction were well below the limiting values for inertness: Cd by 100 times, Pb by 125 times, and Zn by 10 times. Sulfate treatment did not influence the remediation efficiency. Experimental data confirmed the high remediation efficiency and stability of insoluble Cd, Pb, and Zn mineral phases in geotechnical composites. Full article