Search Results (1,744)

Petrological knowledge on weathering processes controlling the mobility of chemical elements is still limited in the dry tropical zone of Cameroon. This study aims to investigate the mobility of major and trace elements during rhyolite weathering and soil formation in Mobono by understanding the mineralogical and elemental vertical variation. The studied soil was classified as Cambisols containing mainly quartz, K-feldspar, plagioclase, smectite, kaolinite, illite, calcite, lepidocrocite, goethite, sepiolite, and interstratified clay minerals. pH values ranging between 6.11 and 8.77 indicated that hydrolysis, superimposed on oxidation and carbonation, is the main process responsible for the formation of secondary minerals, leading to the formation of iron oxides and calcite. The bedrock was mainly constituted of SiO₂, Al₂O₃, Na₂O, Fe₂O₃, Ba, Zr, Sr, Y, Ga, and Rb. Ce and Eu anomalies, and chondrite-normalized La/Yb ratios were 0.98, 0.67, and 2.86, respectively. SiO₂, Al₂O₃, Fe₂O₃, Na₂O, and K₂O were major elements in soil horizons. Trace elements revealed high levels of Ba (385 to 1320 mg kg⁻¹), Zr (158 to 429 mg kg⁻¹), Zn (61 to 151 mg kg⁻¹), Sr (62 to 243 mg kg⁻¹), Y (55 to 81 mg kg⁻¹), Rb (1102 to 58 mg kg⁻¹), and Ga (17.70 to 35 mg kg⁻¹). LREEs were more abundant than HREEs, with LREE/HREE ratio ranging between 2.60 and 6.24. Ce and Eu anomalies ranged from 1.08 to 1.21 and 0.58 to 1.24 respectively. The rhyolite-normalized La/Yb ratios varied between 0.56 and 0.96. Mass balance revealed the depletion of Si, Ca, Na, Mn, Sr, Ta, W, U, La, Ce, Pr, Nd, Sm, Gd and Lu, and the accumulation of Al, Fe, K, Mg, P, Sc, V, Co, Ni, Cu, Zn, Ga, Ge, Rb, Y, Zr, Nb, Cs, Ba, Hf, Pb, Th, Eu, Tb, Dy, Ho, Er, Tm and Yb during weathering along the soil profile. Full article

To our knowledge, no magnetic B2 phase in the Al–Mn system of near-equiatomic compositions has been reported so far. Here, we investigate the structural and magnetic characteristics of Al₄₅Mn_41.8X_13.2 (X = Fe, Co or Ni) alloys. We demonstrate that adding 13.2 atomic percent magnetic 3d metal to AlMn stabilizes a ferromagnetic B2 structure, where Al and X occupy different sublattices. We employ density functional theory calculations and experimental characterizations to underscore the role of the late 3d metals for the phase stability of the quasi-ordered ternary systems. We show that these alloys possess large local magnetic moments primarily due to Mn atoms partitioned to the Al-free sublattice. The revealed magneto-chemical effect opens alternative routes for tailoring the magnetic properties of B2 intermetallic compounds for various magnetic applications. Full article

This study synthesized FeNiCuAlX high-entropy alloys (HEAs) (where X = Cr, Co, Mn) using arc melting and investigated their high-temperature oxidation behavior in air at 900 °C. The oxidation kinetics of all alloys followed a parabolic rate, with the oxidation rate constants (kp) of FeNiCuAlCr, FeNiCuAlCo, and FeNiCuAlMn being approximately two to three orders of magnitude lower than that of the FeNiCu alloy. Specifically, FeNiCuAlCr exhibited the lowest kp value of 1.72 × 10⁻⁶ mg²·cm⁴/s, which is significantly lower than those of FeNiCuAlCo (3.29 × 10⁻⁶ mg²·cm⁴/s) and FeNiCuAlMn (1.71 × 10⁻⁵ mg²·cm⁴/s). This suggests that the addition of chromium promotes the formation of a dense Al₂O₃/Cr₂O₃ oxide layer, significantly enhancing the oxidation resistance. Furthermore, corrosion resistance was assessed through potentiodynamic polarization and electrochemical impedance spectroscopy in a 3.5% NaCl solution. FeNiCuAlCr demonstrated exceptional resistance to localized corrosion, as indicated by its low corrosion current density (45.7 μA/cm²) and high pitting potential (−0.21 V), highlighting its superior corrosion performance. Full article

South Dongting Lake is an essential aquatic ecosystem that receives substantial water inflows from the Xiangjiang and Zishui Rivers. However, it is significantly impacted by human activities, including mining, smelting, and farming. These activities have led to serious contamination of the lake’s sediments with heavy metals (HMs). This study investigated the distribution, mobility, and influencing factors of HMs at the sediment–water interface. To this end, sediment samples were analyzed from three key regions (Xiangjiang River estuary, Zishui River estuary, and northeastern South Dongting Lake) using traditional sampling methods and Diffusive Gradients in Thin Films (DGT) technology. Analysis of fifteen HMs (Pb, Bi, Ni, As, Se, Cd, Sb, Mn, Zn, V, Cr, Cu, Tl, Co, and Fe) revealed significant spatial heterogeneity. The results showed that Cr, Cu, Pb, Bi, Ni, As, Se, Cd, Sb, Mn, Zn, and Fe exhibited high variability (CV > 0.20), whereas V, Tl, and Co demonstrated stable concentrations (CV < 0.20). Concentrations were found to exceed background values of the upper continental crust of eastern China (UCC), Yangtze River sediments (YZ), and Dongting Lake sediments (DT), particularly at the Xiangjiang estuary (XE) and in the northeastern regions. Speciation analysis revealed that V, Cr, Cu, Ni, and As were predominantly found in the residual fraction (F4), while Pb and Co were concentrated in the oxidizable fraction (F3), Mn and Zn appeared primarily in the exchangeable fractions (F1 and F2), and Cd was notably dominant in the exchangeable fraction (F1), suggesting a high potential for mobility. Additionally, DGT results confirmed a significant potential for the release of Pb, Zn, and Cd. Contamination assessment using the Pollution Load Index (PLI) and Geoaccumulation Index (Igeo) identified Pb, Bi, Ni, As, Se, Cd, and Sb as major pollutants. Among these, Bi and Cd were found to pose the highest risks. Furthermore, the Risk Assessment Code (RAC) and the Potential Ecological Risk Index (PERI) highlighted Cd as the primary ecological risk contributor, especially in the XE. The study identified sediment grain size, pH, electrical conductivity, and nutrient levels as the primary influencing factors. The PMF modeling revealed HM sources as mixed smelting/natural inputs, agricultural activities, natural weathering, and mining/smelting operations, suggesting that remediation should prioritize Cd control in the XE with emphasis on external inputs. Full article

The topic of environmental pollution by petroleum products is highly relevant due to rapid urbanisation, including industrial development, road infrastructure and fuel distribution. Potential threat areas include refineries, fuel stations, pipelines, warehouses and transshipment bases, as well as sites affected by accidents or fuel spills. This study aimed to determine whether organic and mineral materials could mitigate the effects of diesel oil pollution on the soil’s trace element content. The used materials were compost, bentonite and calcium oxide. Diesel oil pollution had the most pronounced effect on the levels of Cd, Ni, Fe and Co. The levels of the first three elements increased, while the level of Co decreased by 53%. Lower doses of diesel oil (2.5 and 5 cm³ per kg of soil) induced an increase in the levels of the other trace elements, while higher doses caused a reduction, especially in Cr. All materials applied to the soil (compost, bentonite and calcium oxide) reduced the content of Ni, Cr and Fe. Compost and calcium oxide also increased Co accumulation in the soil. Bentonite had the strongest reducing effect on the Ni and Cr contents of the soil, reducing them by 42% and 53%, respectively. Meanwhile, calcium oxide had the strongest reducing effect on Fe and Co accumulation, reducing it by 12% and 31%, respectively. Inverse relationships were recorded for Cd (mainly bentonite), Pb (especially compost), Cu (mainly compost), Mn (mainly bentonite) and Zn (only compost) content in the soil. At the most contaminated site, the application of bentonite reduced the accumulation of Pb, Zn and Mn in the soil, while the application of compost reduced the accumulation of Cd. Applying various materials, particularly bentonite and compost, limits the content of certain trace elements in the soil. This has a positive impact on reducing the effect of minor diesel oil pollution on soil properties and can promote the proper growth of plant biomass. Full article

Proper joint function has a significant impact on people’s quality of life. Joints are the point of connection between two or more bones and consist of at least three elements: joint surfaces, the joint capsule, and the joint cavity. Joint diseases are a serious social problem. Risk factors for the development of these diseases include overweight and obesity, gender, and intestinal microbiome disorders. Another factor that is considered to influence joint diseases is trace elements. Under normal conditions, elements such as iron (Fe), copper (Cu), cobalt (Co), iodine (I), manganese (Mn), zinc (Zn), silver (Ag), cadmium (Cd), mercury (Hg), lead (Pb), nickel (Ni) selenium (Se), boron (B), and silicon (Si) are part of enzymes involved in reactions that determine the proper functioning of cells, regulate redox metabolism, and determine the maturation of cells that build joint components. However, when the normal concentration of the above-mentioned elements is disturbed and toxic elements are present, dangerous joint diseases can develop. In this article, we focus on the role of trace elements in joint function. We describe the molecular mechanisms that explain their interaction with chondrocytes, osteocytes, osteoblasts, osteoclasts, and synoviocytes, as well as their proliferation, apoptosis, and extracellular matrix synthesis. We also focus on the role of these trace elements in the pathogenesis of joint diseases: rheumatoid arthritis (RA), osteoarthritis (OA), psoriatic arthritis (PsA), ankylosing spondylitis (AS), and systemic lupus erythematosus (SLE). We describe the roles of increased or decreased concentrations of individual elements in the pathogenesis and development of joint diseases and their impact on inflammation and disease progression, referring to molecular mechanisms. We also discuss their potential application in the treatment of joint diseases. Full article

Graphene quantum dots (GQDs) obtained by microwave-induced pyrolysis of glutamic acid and triethylenetetramine (trien) are fairly stable, emissive, water-soluble, and positively charged nano-systems able to interact with negatively charged meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS₄). The stoichiometric control during the preparation affords a supramolecular adduct, GQDs@TPPS₄, that exhibits a double fluorescence emission from both the GQDs and the TPPS₄ fluorophores. These supramolecular aggregates have an overall negative charge that is responsible for the condensation of cations in the nearby aqueous layer, and a three-fold acceleration of the metalation rates of Cu²⁺ ions has been observed with respect to the parent porphyrin. Addition of various metal ions leads to some changes in the UV/Vis spectra and has a different impact on the fluorescence emission of GQDs and TPPS₄. The quenching efficiency of the TPPS₄ emission follows the order Cu²⁺ > Hg²⁺ > Cd²⁺ > Pb²⁺ ~ Zn²⁺ ~ Co²⁺ ~ Ni²⁺ > Mn²⁺ ~ Cr³⁺ >> Mg²⁺ ~ Ca²⁺ ~ Ba²⁺, and it has been related to literature data and to the sitting-atop mechanism that large transition metal ions (e.g., Hg²⁺ and Cd²⁺) exhibit in their interaction with the macrocyclic nitrogen atoms of the porphyrin, inducing distortion and accelerating the insertion of smaller metal ions, such as Zn²⁺. For the most relevant metal ions, emission quenching of the porphyrin evidences a linear behavior in the micromolar range, with the emission of the GQDs being moderately affected through a filter effect. Deliberate pollution of the samples with Zn²⁺ reveals the ability of the GQDs@TPPS₄ adduct to detect sensitively Cu²⁺, Hg^2+, and Cd²⁺ ions. Full article

Novel high-entropy perovskite oxide powders were synthesized using a sol-gel process. The B-site contained five cations: chromium, cobalt, iron, manganese, and nickel. The B-site cations were present on an equiatomic basis. The A-site cation was lanthanum, with calcium doping. The amount of A-site doping varied from 0 to 30 at%, yielding a composition of La_1−xCa_x(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O_3−δ. The resulting perovskite powders were pressurelessly sintered in air at 1400 °C for 2 h. Sintered densities were measured, and the grain structure was imaged via scanning electron microscopy to investigate the effect of doping. Samples were cut and polished, and their resistance was measured at varying temperatures in air to obtain the electrical conductivity and the mechanism that governs it. Plots of electrical conductivity as a function of composition and temperature indicate that the increased configurational entropy of the perovskite materials has a demonstrable effect. Full article

This study investigates the heavy metal contamination in urban and peri-urban soils of Thessaloniki, Greece, over a two-year period (2023–2024). A total of 208 composite soil samples were systematically collected from 52 sites representing diverse land uses, including high-traffic roadsides, industrial zones, residential neighborhoods, parks, and mixed-use areas, with sampling conducted both after the wet (winter) and dry (summer) seasons. Soil physicochemical properties (pH, electrical conductivity, texture, organic matter, and calcium carbonate content) were analyzed alongside the concentrations of heavy metals such as Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. A pollution assessment employed the Geoaccumulation Index (I_geo), Contamination Factor (Cf), Pollution Load Index (PLI), and Potential Ecological Risk Index (RI), revealing variable contamination levels across the city, with certain hotspots exhibiting a considerable to very high ecological risk. Multivariate statistical analyses (PCA and HCA) identified distinct anthropogenic and geogenic sources of heavy metals. Health risk assessments, based on USEPA models, evaluated non-carcinogenic and carcinogenic risks for both adults and children via ingestion and dermal contact pathways. The results indicate that while most sites present low to moderate health risks, specific locations, particularly near major transport and industrial areas, pose elevated risks, especially for children. The findings underscore the need for targeted monitoring and remediation strategies to mitigate the ecological and human health risks associated with urban soil pollution in Thessaloniki. Full article

The transition to clean and renewable energy sources is critically dependent on efficient hydrogen production technologies. This review surveys recent advances in photocatalytic water splitting, focusing on MNb₂O₆ nanomaterials, which have emerged as promising photocatalysts due to their tunable band structures, chemical robustness, and tailored morphologies. The objectives of this work are to (i) encompass the current synthesis strategies for MNb₂O₆ compounds; (ii) assess their structural, electronic, and optical properties in relation to photocatalytic performance; and (iii) elucidate the mechanisms underpinning enhanced hydrogen evolution. Main data collection methods include a literature review of experimental studies reporting bandgap measurements, structural analyses, and hydrogen production metrics for various MNb₂O₆ compositions—especially those incorporating transition metals such as Mn, Cu, Ni, and Co. Novelty stems from systematically detailing the relationships between synthesis routes (hydrothermal, solvothermal, electrospinning, etc.), crystallographic features, conductivity type, and bandgap tuning in these materials, as well as by benchmarking their performance against more conventional photocatalyst systems. Key findings indicate that MnNb₂O₆, CuNb₂O₆, and certain engineered heterostructures (e.g., with g-C₃N₄ or TiO₂) display significant visible-light-driven hydrogen evolution, achieving hydrogen production rates up to 146 mmol h⁻¹ g⁻¹ in composite systems. The review spotlights trends in heterojunction design, defect engineering, co-catalyst integration, and the extension of light absorption into the visible range, all contributing to improved charge separation and catalytic longevity. However, significant challenges remain in realizing the full potential of the broader MNb₂O₆ family, particularly regarding efficiency, scalability, and long-term stability. The insights synthesized here serve as a guide for future experimental investigations and materials design, advancing the deployment of MNb₂O₆-based photocatalysts for large-scale, sustainable hydrogen production. Full article

Stainless steel dust (SSD) is a by-product generated during the smelting process of stainless steel, which is rich in valuable metals such as Fe, Cr, Ni, and Mn. To optimize the carbothermic reduction process of SSD, this study first conducted the thermodynamic analysis of the carbothermic reduction of SSD and then employed walnut shell biochar as a reductant with non-isothermal thermogravimetric analysis with linear heating rates of 5 °C/min, 10 °C/min, 15 °C/min, and 20 °C/min. The activation energies of the carbothermic reduction reactions were calculated using the FWO method, KAS method, and Friedman method, respectively. Subsequently, the corresponding kinetic models were fitted and matched using the Málek method. The results indicate that before 600 °C, the direct reduction of SSD by carbon plays a dominant role. As the temperature increases, the indirect reduction becomes the main reduction reaction for SSD due to the generation of CO. The activation energies calculated by the Flynn–Wall–Ozawa (FWO) method, Kissinger–Akahira–Sunose (KAS) method, and Friedman method are 412.120 kJ/mol, 416.930 kJ/mol, and 411.778 kJ/mol, respectively, showing close values and a general trend of increasing activation energy as the conversion rate increased from 10% to 90%. Moreover, the reduction reaction is staged. In the conversion range of 10% to 50%, the carbothermic reduction reaction conforms to the shrinking core model within phase boundary reactions, coded as R1/4. In the conversion range of 50% to 60%, it conforms to the shrinking core model within phase boundary reactions, coded as R1/2; in the conversion range of 60% to 90%, the carbothermic reduction reaction follows the second-order chemical reaction model, coded as F2. Full article

Background: Transition metal complexes incorporating fluorinated counter anions represent a significant class of compounds with broad applications in industry, pharmaceuticals, and biomedicine. These fluorinated anions are known to enhance the solubility, stability, and reactivity of the complexes, thereby expanding their functional utility in various chemical and biological contexts. Methods: A set of metal(II) complexes of the general formula [MPy₆][B(C₆F₅)₄]₂ where (Py = pyridine, M = Mn (1), Fe (2), Co (3), Ni (4), Cu (5), Zn (6)) have been synthesized by direct reaction of metal halides and pyridine in the presence of Ag[B(C₆F₅)₄]. The complexes were characterized using different techniques to assure their purity, such as elemental analysis (EA), electron paramagnetic resonance (EPR) spectroscopy, thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, ¹¹B-NMR, ¹H-NMR, and FT-IR spectroscopy. The antimicrobial and antifungal properties against different types of bacteria and fungi were studied for all prepared complexes. Results: The synthesized complexes exhibited broad-spectrum antimicrobial activity, demonstrating variable efficacy compared to the reference antibiotic, oxytetracycline (positive control). Notably, complex 6 displayed exceptional antibacterial activity against Streptococcus pyogenes, with a minimum inhibitory concentration (MIC) of 4 µg/mL, outperforming the control (MIC = 8 µg/mL). Complexes 1, 2, and 4 showed promising activity against Shigella flexneri, Klebsiella pneumoniae, and Streptococcus pyogenes, each with MIC values of 8 µg/mL. Conversely, the lowest activity (MIC = 512 µg/mL) was observed for complexes 3, 5, and 6 against Pseudomonas aeruginosa, Escherichia coli, and Klebsiella pneumoniae, respectively. Regarding antifungal properties, complexes 5 and 6 demonstrated the highest activity against Candida albicans, with MIC values of 8 µg/mL, equivalent to that of the positive control, fluconazole. Density functional theory (DFT) calculations confirmed an overall octahedral coordination geometry for all complexes, with tetragonal distortions identified in complexes 3, 4, and 5. Full article

Lithium-ion batteries (LiBs) are utilized in numerous applications due to advancements in technology, and the recovery of end-of-life (EoL) LiBs is imperative for environmental and economic reasons. Pyrometallurgical and hydrometallurgical methods have been used in the recovery of metals such as Li, Co, and Ni in the EoL LiBs. Hydrometallurgical methods, which have been demonstrated to exhibit higher recovery efficiency and reduced energy consumption, have garnered increased attention in recent research. Inorganic acids, including HCl, HNO₃, and H₂SO₄, as well as organic acids such as acetic acid and citric acid, are employed in the hydrometallurgical recovery of these metals. It is imperative to acknowledge the environmental hazards posed by these acids. Consequently, solvometallurgical processes, which involve the use of organic solvents with minimal or no water, are gaining increasing attention as alternative or complementary techniques to conventional hydrometallurgical processes. In the context of solvent systems that have been examined for a range of solvometallurgical methods, deep eutectic solvents (DESs) have garnered particular interest due to their low toxicity, biodegradable nature, tunable properties, and efficient metal recovery potential. In this study, the leaching process of black mass containing graphite, LCO, NMC, and LMO was carried out in a short time using the ternary DES system. The ternary DES system consists of choline chloride (ChCl), glycolic acid (GLY), and ascorbic acid (AA). As a result of the leaching process of cathode powders in the black mass without any pre-enrichment process, Li, Co, Ni, and Mn elements passed into solution with an efficiency of over 95% at 60 °C and within 1 h. Moreover, the kinetics of the leaching process was investigated, and Density Functional Theory (DFT) calculations were used to explain the leaching mechanism. Full article

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

Unionid mussel populations in a section of the Clinch River in Virginia, USA, has declined substantially, but the causes of the decline remain unknown. To investigate this zone of decline (ZOD), we deployed juvenile freshwater mussels (Villosa iris in 2012 and Lampsilis fasciola in 2013) in both cages and silos at sites within the Clinch River System. We analyzed mussel tissues for trace element and organic contaminant concentrations, shells for trace elements, and environmental media (total water, dissolved water, particulate sediment, and bedload sediment) for both inorganic and organic contaminants. We found a few differences between mussels deployed in cages and those deployed in silos: survival was slightly lower in cages due to periodic sedimentation. Our results identified the ZOD based on the accumulation of trace elements (notably As, Cu, Fe, Mn, Ni, and Sr), polycyclic aromatic hydrocarbons (PAHs), and δ¹⁵N enrichment, with especially high concentrations found in the human-impacted tributaries, Dumps Creek and Guest River. Some correlations were found between environmental media and both mussel tissues and shells. In particular, PAHs and Mn had several significant relationships between bioaccumulated concentrations and environmental concentrations. Finally, Co, Cu, Fe, and V in soft tissues negatively correlated with mussel growth, whereas bioaccumulated PAH concentrations correlated negatively with resident mussel densities. Full article