Search Results (78)

Zoharite (IMA 2017-049), (Ba,K)₆ (Fe,Cu,Ni)₂₅S₂₇, and gmalimite (IMA 2019-007), ideally K₆□Fe²⁺₂₄S₂₇, are two new sulfides of the djerfisherite group. They were discovered in an unusual gehlenite–wollastonite paralava with pyrrhotite nodules located in the Hatrurim pyrometamorphic complex, Negev Desert, Israel. Zoharite and gmalimite build grained aggregates confined to the peripheric parts of pyrrhotite nodules, where they associate with pentlandite, chalcopyrite, chalcocite, digenite, covellite, millerite, heazlewoodite, pyrite and rudashevskyite. The occurrence and associated minerals indicate that zoharite and gmalimite were formed at temperatures below 800 °C, when sulfides formed on external zones of the nodules have been reacting with residual silicate melt (paralava) locally enriched in Ba and K. Macroscopically, both minerals are bronze in color and have a dark-gray streak and metallic luster. They are brittle and have a conchoidal fracture. In reflected light, both minerals are optically isotropic and exhibit gray color with an olive tinge. The reflectance values for zoharite and gmalimite, respectively, at the standard COM wavelengths are: 22.2% and 21.5% at 470 nm, 25.1% and 24.6% at 546 nm, 26.3% and 25.9% at 589 nm, as well as 27.7% and 26.3% at 650 nm. The average hardness for zoharite and for gmalimite is approximately 3.5 of the Mohs hardness. Both minerals are isostructural with owensite, (Ba,Pb)₆(Cu,Fe,Ni)₂₅S₂₇. They crystallize in cubic space group Pm$\overline{3}$m with the unit-cell parameters a = 10.3137(1) Å for zoharite and a = 10.3486(1) Å for gmalimite. The calculated densities are 4.49 g·cm⁻³ for the zoharite and 3.79 g·cm⁻³ for the gmalimite. The primary structural units of these minerals are M₈S₁₄ clusters, composed of MS₄ tetrahedra surrounding a central MS₆ octahedron. The M site is occupied by transition metals such as Fe, Cu, and Ni. These clusters are further connected via the edges of the MS₄ tetrahedra, forming a close-packed cubic framework. The channels within this framework are filled by anion-centered polyhedra: SBa₉ in zoharite and SK₉ in gmalimite, respectively. In the M₈S₁₄ clusters, the M atoms are positioned so closely that their d orbitals can overlap, allowing the formation of metal–metal bonds. As a result, the transition metals in these clusters often adopt electron configurations that reflect additional electron density from their local bonding environment, similar to what is observed in pentlandite. Due to the presence of shared electrons in these metal–metal bonds, assigning fixed oxidation states—such as Fe²⁺/Fe³⁺ or Cu⁺/Cu²⁺—becomes challenging. Moreover, modeling the distribution of mixed-valence cations (Fe²⁺/³⁺, Cu⁺/²⁺, and Ni²⁺) across the two distinct M sites—one located in the MS₆ octahedron and the other in the MS₄ tetrahedra—often results in ambiguous outcomes. Consequently, it is difficult to define an idealized end-member formula for these minerals. Full article

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

Understanding pollution levels, ecological health risks, and sources of potentially toxic metals (PTMs) in the soil from university campuses is critical for assessing environmental safety. Soil samples were collected from 12 locations across urban parks and green areas at Sohag University in Egypt. The samples were processed and analysed for heavy metals, including iron (Fe), manganese (Mn), cobalt (Co), nickel (Ni), chromium (Cr), lead (Pb), zinc (Zn), copper (Cu), and cadmium (Cd). Pollution levels were evaluated using indices such as the pollution index (PI), pollution load index (PLI), geo-accumulation index (I_geo), and enrichment factors (EFs). Among the pollution indices, the EFs showed the highest sensitivity in detecting anthropogenic contributions, particularly for Cd, Pb, and Cr. Spatial distribution maps and multivariate statistical analyses, including correlation matrix (CM), principal component analysis (PCA), and cluster analysis (CA), were applied to identify the relationships between PTMs and soil properties, and source apportionment was performed using positive matrix factorisation (PMF). The results indicated that Mn, Ni, and Co were primarily geogenic, whereas Pb, Zn, Cr, and Cd showed higher concentrations, suggesting moderate-to-significant anthropogenic pollution. Pb and Cd pose considerable ecological risks, whereas other metals such as Cr and Cu exhibit moderate ecological threats. The non-carcinogenic and carcinogenic risks to the students were within safe limits, as defined by United States Environmental Protection Agency (USEPA) threshold values. Source apportionment using PMF identified five main sources of PTMs: industrial and anthropogenic activities (30.0%), traffic emissions (25.0%), natural soil processes (20.0%), agricultural practices (15.0%), and mixed industrial traffic sources (10.0%). These findings emphasise the importance of controlling anthropogenic activities to ensure a safer campus environment. Full article

Sub-nano metal clusters have important physicochemical features that lead to a wide range of applications. Herein, we point out an unfailing reproducible protocol to synthesize ruthenium single-atom catalysts and ultra-small clusters supported on various silica–alumina mixed oxides. The catalysts were synthesized via a dendrimer-free, sonication-assisted route, with ruthenium loadings up to 2 wt%. Raman spectroscopy mapping revealed a wide coverage of the materials’ surfaces by ruthenium, while HAADF-STEM evidenced that 100% of the ruthenium was at the sub-nano scale, with up to 74% of the single atoms and metal clusters having an average size between 0.3 and 0.7 nm, independently of the support or the metal’s loading. These materials exhibited highly selective size-dependent catalytic performances in upgrading biomass-derived furfural into transportation biofuel additive 2,2′-difurfurylether, with turnover frequencies up to 1148 h⁻¹. Ruthenium single atoms and sub-nano clusters showed an exceptional resistance to sintering, with a size variation of ±0.1 nm before and after reaction, and no metal leaching was observed. Full article

This study explores the chemical composition of different macrophyte species and infers their potential in extracting nutrients and some heavy metals from water as well as the use of macrophytes’ biomass as natural fertilizers. It used a dataset obtained from a previous study composed of 445 samples of chemical concentrations in the dried biomass of 16 macrophyte species collected from the Santana Reservoir in Rio de Janeiro, Brazil. Correlation tests, analysis of variance, and factor analysis of mixed data were performed to infer correspondences between the macrophyte species. The results showed that the macrophyte species can be grouped into three different clusters with significantly different profiles of chemical element concentrations (N, P, K⁺, Ca²⁺, Mg²⁺, S, B, Cu²⁺, Fe²⁺, Mn²⁺, Zn²⁺, Cr³⁺, Cd²⁺, Ni²⁺, Pb²⁺) in their biomass (factorial map from PCA). Most marginal macrophytes have a lower concentration of chemical elements (ANOVA p-value < 0.05). Submerged and floating macrophyte species presented a higher concentration of metallic and non-metallic chemical elements in their biomass (ANOVA p-value < 0.05), revealing their potential in phytoremediation and the removal of toxic compounds (such as heavy metal molecules) from water. A cluster of macrophyte species also exhibited high concentrations of macronutrients and micronutrients (ANOVA p-value < 0.05), indicating their potential for use as soil fertilizers. These results reveal that the plant’s location in the reservoir (marginal, floating, or submerged) is a relevant feature associated with macrophytes’ ability to remove chemical components from the water. The obtained results can contribute to planning the management of macrophyte species in large water reservoirs. Full article

Exchange bias (EB) materials, whose magnetization curve can shift along the field axis after field cooling, have attracted tremendous attention and play a crucial role in the development of fundamental physics as well as practical applications of magnetization storage. In this work, the N-, P-, and Q-type ferrimagnets of Néel’s notation were realized in mixed valence metal formates [CH₃NH₂CH₃]_n[Cr^III_1−xFe^III_xFe^II(HCO₂)₆]_n by altering x, respectively. The positive and negative EB was found in N- and P-type ferrimagnets. The exchange anisotropy originates from the antiferromagnetic exchange interaction between the uncompensated spin of the host ferrimagnetic lattice and the pinned compensated spin of the antiferromagnetic clusters as a guest, which is rooted in the valence disorder of the iron ions. Full article

The oxime group is important in organic and inorganic chemistry. In most cases, this group is part of an organic molecule possessing one or more donor sites capable of forming bonds to metal ions. One family of such compounds is the group of 2-pyridyl (aldo)ketoximes. Metal complexes of 2-pyridyl oximes continue to attract the intense interest of many inorganic chemistry groups around the world for a variety of reasons, including their interesting structures, physical and biological properties, and applications. A unique member of 2-pyridyl ketoximes is di-2-pyridyl ketoxime (dpkoxH), which contains two 2-pyridyl groups and an oxime functionality that can be easily deprotonated giving the deprotonated ligand (dpkox⁻). The extra 2-pyridyl site confers a remarkable flexibility resulting in metal complexes with exciting structural and reactivity features. Our and other research groups have prepared and characterized many metal complexes of dpkoxH and dpkox⁻ over the past 30 years or so. This work is an attempt to build a “periodic table” of dpkoxH, which is near completion. The filled spaces of this “periodic table” contain metal ions whose dpkoxH/dpkox⁻ complexes have been structurally characterized. This work reviews comprehensively the to-date published coordination chemistry of dpkoxH with emphasis on the syntheses, reactivity, relationship to metallacrown chemistry, structures, and properties of the metal complexes; selected unpublished results from our group are also reported. The sixteen coordination modes adopted by dpkoxH and dpkox⁻ have provided access to monomeric and dimeric complexes, trinuclear, tetranuclear, pentanuclear, hexanuclear, heptanuclear, enneanuclear, and decanuclear clusters, as well as to a small number of 1D coordination polymers. With few exceptions ({M^IILn^III₂} and {Ni^II₂Mn^III₂}; M = Ni, Cu, Pd, and Ln = lanthanoid), most complexes are homometallic. The metals whose ions have yielded complexes with dpkoxH and dpkox⁻ are Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Re, Os, Ir, Au, Hg, lanthanoids (mainly Pr and Nd), and U. Most metal complexes are homovalent, but some mixed-valence Mn, Fe, and Co compounds have been studied. Metal ion-assisted/promoted transformations of dpkoxH, i.e., reactivity patterns of the coordinated ligand, are also critically discussed. Some perspectives concerning the coordination chemistry of dpkoxH and research work for the future are outlined. Full article

This study aims to investigate the impact of indoor sources and outdoor air on indoor PM_2.5-bound benzo(a)pyrene, with a focus on identifying emission sources and understanding the influence of environmental variables. For this purpose, we collected indoor and outdoor data on PM_2.5-bound PAHs, inorganic gaseous pollutants, trace metals, ions, radon, and meteorological parameters, resulting in a comprehensive dataset of 100 variables from an urban site in Belgrade, Serbia. We applied seven regression tree ensemble algorithms to interrelate the variables alongside six metaheuristic optimization algorithms to refine model accuracy and robustness. Subsequently, we explained the best-performing model locally using Shapley additive explanations and clustered variables with similar impacts into distinct groups. These groups were systematically characterized, defining them as environmental settings that shape benzo(a)pyrene dynamics. The setting resulting in the highest indoor benzo(a)pyrene concentrations (197% to 297% relative to the expected value) was dominated by outdoor emissions associated with residential heating and traffic (up to 140%) and indoor source identified as cooking. This integrated approach uniquely enables a quantitative assessment of the contributions from both indoor and outdoor emission sources to pollutant concentrations in indoor spaces, underscoring the importance of both in shaping indoor air quality. Unlike traditional source apportionment methods that assume linear source mixing, our approach integrates nonlinear interactions and contextual variables, such as meteorological conditions and outdoor pollutants, to better capture indoor air quality dynamics. The results also highlight the need for further studies to explore broader contextual factors and refine source attribution in complex urban settings. Full article

The energy sector is the sector that generates the highest amount of environmental contamination, especially in water sources, mostly in the case of coal-based energy production. The aim of this study was to examine a significant contamination source, heavy metal contamination, in coal mining effluents. The current investigation introduces an MOF platform based on zirconium clusters and isophthalic acid with NH₂-MIP-SO₃H mixed amine and sulfonic acid functional groups in order to remove the most common heavy metal ions in coal mining effluents, including Hg, Cd, Pb, and Cu ions. The water matrix and the operational conditions were identified to be very influential in the removal process, such as the pH of water, the initial metal concentration and operating time. NH₂-MIP-SO₃H offers a great removal efficiency of metals starting from 745.83 mg/g for Cd, 673.67 mg/g for Cu, 589.85 mg/g for Hg, and 481.66 mg/g for Pb ions, with the Langmuir equation for equilibrium and pseudo-second-order equation for kinetics being the ideal models to express the equilibrium and kinetic data, respectively. A significant impact of water pH was found to occur, with the NH₂-MIP-SO₃H platform performing best at pH 6. Reuse of NH₂-MIP-SO₃H demonstrates excellent reusability, sustaining 90% of initial performance over eight regeneration cycles. The interaction of functional group-functional metal was the dominant mechanism in the removal process. The NH₂-MIP-SO₃H unique approach to heavy metal removal provides a very hopeful outlook for additional investigations in larger-scale studies. Full article

The features for assessing the authenticity of wines by region of origin are studied, based on the relationship between the mineral composition of the wine, the grapes, and the soil profile (0 to 160 cm) from the place of growth of Cabernet Sauvignon grapes. Soil, grape, and wine samples were taken from the territories of six vineyards in the Anapa district of Krasnodar Territory, Russia. Using the methods of ICP-OES, thermal, and X-ray phase analysis, the soils were differentiated into three groups, differing in mineralogical and mineral compositions. The soil samples of the first group contained up to 31% quartz, the second group up to 25% quartz and 19% mixed calcite, and the third group up to 32% calcite and 15% quartz. The formation of the elemental image of the grapes was studied, taking into account the total content and mobile forms of metals in the soil. The territorial proximity of the vineyards did not affect the extraction of elements from the soil into the grape berry, and the migration of metals for each territory was selective. According to the values of the biological absorption coefficient, the degree of transition of metals from the soil to a berry was estimated. For K, Ti, Zn, Rb, Cu, and Fe in all berries, the coefficient was higher than 1.00, which means that the berry extracts contained not only mobile-form, but also difficult-to-dissolve metal compounds. The migration of macro-components from the soil to the berry was low, and amounted to 6–7% for Ca, 0.8–3.0% for Na, and 25–70% for Mg of the concentration of their mobile forms. For all territories, the maximum correlation between metal concentrations in grapes and soil was observed for samples from a depth of 0–40 cm. The discriminant model based on concentrations of Rb, Al, K, Sr, Co, Na, Pb, Ca, and Ni showed the formation of clusters in the territories of vineyard cultivation. The developed model allow the problems of identifying wines by region to be solved with high accuracy, using their elemental image. Full article

Developing high−efficiency membrane materials for the rapid removal of organic dyes is crucial but remains a challenge. Polyoxometalates (POMs) clusters with anionic structures are promising candidates for the removal of cationic dyes via electrostatic interactions. However, their shortcomings, such as their solubility and inability to be mass−produced, hinder their application in water pollution treatment. Here, we propose a simple and green strategy utilizing the room temperature stirring method to mass produce nanoscale polyoxometalate−based metal−organic frameworks (POMOFs) with porous rhomboid−shaped dodecahedral and hexagonal prism structures. The products were labeled as POMOF1 (POMOF-PW₁₂) and POMOF2 (POMOF-PMo₁₂). Subsequently, a series of x wt% POMOF1/PAN (x = 0, 3, 5, and 10) nanofiber membranes (NFMs) were prepared using electrospinning technology, where polyacrylonitrile (PAN) acts as a “glue” molecule facilitating the bonding of POMOF1 nanoparticles. The as−prepared samples were comprehensively characterized and exhibited obvious water stability, as well as rapid selective adsorption filtration performance towards cationic dyes. The 5 wt% POMOF1/PAN NFM possessed the highest removal efficiency of 96.7% for RhB, 95.8% for MB, and 86.4% for CV dyes, which realized the selective separation over 95% of positively charged dyes from the mixed solution. The adsorption mechanism was explained using FT−IR, SEM, Zeta potential, and adsorption kinetics model, which proved that separation was determined via electrostatic interaction, hydrogen bonding, and π–π interactions. Moreover, the POMOF1/PAN membrane presented an outstanding recoverable and stable removal rate after four cycles. This study provides a new direction for the systematic design and manufacture of membrane separation materials with outstanding properties for contaminant removal. Full article

Eddavidite is a new mineral species (IMA2018-010) with ideal formula, Cu₁₂Pb₂O₁₅Br₂, and cubic Fm$\overline{3}$m symmetry: a = 9.2407(9) Å; V = 789.1(2) ų; Z = 2. Eddavidite is the bromine analog of murdochite, Cu₁₂Pb₂O₁₅Cl₂, with which it forms a solid solution series. The type locality is the Southwest mine, Bisbee, Cochise County, Arizona, U.S.A. Eddavidite also occurs in the Ojuela mine, Mapimí, Durango, Mexico. Eddavidite occurs as domains within mixed murdochite–eddavidite crystals. The empirical formula, normalized to 12 Cu apfu, is Cu₁₂(Pb_1.92Fe_0.06Si_0.06)(O_15.08F_0.02)-(Br_0.99Cl_0.89☐_0.12). Type locality samples contain up to 67% eddavidite component, while Ojuela mine samples contain up to 62%. Mixed eddavidite–murdochite crystals show forms {100} and {111}; the habit grades from cubic through cuboctahedral to octahedral. Mixed eddavidite–-murdochite crystals exhibit good cleavage on {111}. Eddavidite is black, opaque with submetallic luster, and visually indistinguishable from intergrown murdochite. Its Mohs hardness is 4; d_meas. = 6.33 g/cm³, d_calc. = 6.45 g/cm³. The crystal structure, refined to R = 0.0112, consists of corner-sharing square planar CuO₄ units, arranged in Cu₁₂O₂₄ metal oxide clusters, which encapsulate Br atoms. PbO₈ cubes share edges with Cu₁₂O₂₄ clusters in a continuous framework. Eddavidite incorporates bromine remaining after desiccation of paleo-seawater at its two known localities, which were both once situated along the Western Interior Seaway. Full article

Background and Objectives: Enzymes involved with acetylation capacity affects the metabolization of several xenobiotics that can be deposited in adipose tissue and hinder weight loss, leading to obesity. Our aim was to identify single nucleotide polymorphisms (SNPs) related to the xenobiotic’s metabolism and to associate such with the serum levels of heavy metals in an individual with excess body weight. Methods: The sample was selected at the Ribeirão Preto Medical School at the University of São Paulo, Brazil. Genotyping arrays were performed with 23 SNPs. Quality control and imputation steps were applied using the functions in the package ‘snpReady’ (CRAN) and ‘imput’ (Bioconductor). Results: This study selected 189 individuals of mixed ethnicity of both sexes, with a mean age of 42.2 ± 12.9 years and a mean BMI of 45.1 ± 11.4 kg/cm². From the cluster of 23 evaluated SNPs, we observed a higher frequency of SNP 1799930 in the NAT2 gene (N-acetyltraferase). The genotypes were correlated to the serum levels of different metals. We observed that individuals homozygous for the mutant allele (AA), called fast metabolizers, had lower levels of aluminum (Al) (51.4 ± 18.9 µg/L) compared to those considered slow metabolizers (GG) (64.0 ± 37.2 µg/L; p = 0.02). No difference was observed when compared with heterozygosity (AG). Furthermore, the BMI of fast metabolizers (48.7 ± 12.8 kg/cm²) was higher than the slow metabolizer individuals (45.9 ± 10.4 kg/cm²; p < 0.05). Discussion: Fast metabolizers seem to have a greater Al metabolization only in homozygosis, that is, the dose-dependent gene, to exert its effect. Interestingly, the presence of the AA genotype is associated with a higher BMI, suggesting that larger studies should be carried out investigating the deposition of metals in adipose tissue. Full article

Two types of isostructural iron-cobalt/nickel-antimony-oxo tartrate cluster-based compounds, namely (H₃O)(Me₂NH₂)[M(H₂O)₆]₂[Fe^II₂Sb^III₁₂(μ₄-O)₃(μ₃-O)₈(tta)₆]·6H₂O (M = Co (1); Ni (3)), H_5/3[Co_2.5Fe^II_4/3Fe^III₃(H₂O)₁₃Sb^V_1/3Fe^III_2/3(μ₄-O)₂(μ₃-O)₄Sb^III₆(μ₃-O)₂(tta)₆]·2H₂O (2) and H₂[Ni_2.25Fe^II_1.5Fe^III₃(H₂O)₁₄Sb^V_0.25Fe^III_0.75(μ₄-O)₂(μ₃-O)₄Sb^III₆(μ₃-O)₂(tta)₆]·2H₂O (4) (H₄tta = tartaric acid) were synthesized via simple solvothermal reactions. All the clusters in the structures adopt sandwich configurations, that is, bilayer sandwich configuration in 1 and 3 and monolayer sandwich configuration in 2 and 4. Interestingly, the monolayer sandwiched compounds 2 and 4 represent rare examples of cluster-based compounds containing mixed-valence Sb(III, V), whose center of the intermediate layer is the co-occupied [Fe_xSb^V_1−x]. This is different from that of previously reported sandwich-type antimony-oxo clusters in which the center position is either occupied by a transition metal ion or a Sb(V) alone. Thus, the discovery of title compounds 2 and 4 makes the evolution of center metal ion more complete, that is, from M, M_xSb^V_1−x to Sb^V. All the title compounds were fully characterized, and the photocatalysis, proton conduction and magnetism of compounds 2 and 4 were studied. Full article

Converting superfluous CO₂ into value-added chemicals is regarded as a practical approach for alleviating the global warming problem. Powered by renewable electricity, CO₂ reduction reactions (CO₂RR) have attracted intense interest owing to their favorable efficiency. Metal catalysts exhibit high catalytic efficiency for CO₂ reduction. However, the reaction mechanisms have yet to be investigated. In this study, CO₂RR to CH₃OH catalyzed by CuAg bimetal is theoretically investigated. The configurations and stability of the catalysts and the reaction pathway are studied. The results unveil the mechanisms of the catalysis process and prove the feasibility of CuAg clusters as efficient CO₂RR catalysts, serving as guidance for further experimental exploration. This study provides guidance and a reference for future work in the design of mixed-metal catalysts with high CO₂RR performance. Full article