Nanoscale Mineral Research Articles

Nanomineralogy of thorite in the supergiant Huayangchuan uranium ore deposit: Revealing a new geochemical behavior of actinide in environment

Thorium (Th) is a naturally occurring radioactive element found in the environment, and recent advancements have been made in identifying and characterizing Th-bearing nanoparticles (NPs). However, the main focus is still on synthesized Th-bearing NPs and knowledge about natural Th-bearing NPs remains limited. Here, high-resolution transmission electron microscopy (HRTEM) observations of thorite from the Huayangchuan uranium ore deposit in Shaanxi Province, Central China, have revealed the nanoscale mineral characteristics of thorite. In this study, thorite NPs ranging from 5–10 nm in size were identified within the uranium ore. A combination of transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS) elemental mapping and corresponding HRTEM images alongside Selected Area Electron Diffraction (SAED) and Fast Fourier Transform (FFT) patterns revealed a complex nanoscale structure in the thorite NPs, consisting of both amorphous and crystalline nanodomains with abundant defects. These nanostructures are associated with a metamictization mechanism in micrometer-sized thorite. Our findings indicate that the metamictization process can generate numerous thorite nanoparticles. Given the high penetrability and mobility of these NPs, the metamictization of thorite poses new challenges for the long-term stability of radioactive substances and the storage containers for radioactive waste. Furthermore, considering the likelihood of environmental release and the chemical toxicity, radioactivity, and nanotoxicity of natural Th-bearing NPs, increased attention should be given to the presence of natural thorite NPs in the ore deposit.

Nanoscale mineral as a novel class enzyme mimic (mineralzyme) with total antioxidant capacity detection: Colorimetric and smartphone-based approaches

Nanozymes, synthetic nano-scale materials with enzyme-like behavior, have shown remarkable advancements and widespread utilization across various applications. However, the majority of nanozymes require precursor of synthetic-chemicals, which are sometimes expensive and undergo complicated preparations and tedious purification procedures. Therefore, it is of utmost significance to find an enzyme mimic that is affordable, abundant, highly efficient, and sustainable for various applications in biomedicine, environmental sciences, and the food industry. We prove the efficient peroxidase-like activities of the earthly available mineral, barunite-II. The braunite-II mineral micro-nanoparticles (NB) were prepared via physical milling. The enzyme mimetic activity of mineral nanoparticles, referred to as “mineralzyme,” could oxidize the chromogenic blue color of TMB (3,3′,5,5′-tetramethylbenzidine) to oxTMB (3,3′,5,5′-tetramethylbenzidine oxide). Michaelis-Menten constant (Km) and maximum velocity (Vmax) were 135 mM and 62.73 mM min−1 for TMB as a substrate, 139.2 mM, and 2.69 mM min−1 for H2O2 as a substrate. The Km values are much lower than those for HRP. We accurately quantified the total antioxidant capacity in seminal fluid samples from infertile patients using the peroxidase activity of the mineral nanoparticles. This investigation will open new avenues to explore the realm of mineralzyme, revealing its significant potential for a wide range of applications involving diverse enzymatic behaviors.

Optimized Nanoscale Mineralization Strategy for Maintaining Bio-enzymatic Stability

Optimized Nanoscale Mineralization Strategy for Maintaining Bio-enzymatic Stability

Myriad Mapping of nanoscale minerals reveals calcium carbonate hemihydrate in forming nacre and coral biominerals

Calcium carbonate (CaCO3) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO2 into solid biominerals. Six crystalline polymorphs of CaCO3 are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO3·6H2O), monohydrocalcite (CaCO3·1H2O, MHC), and calcium carbonate hemihydrate (CaCO3·½H2O, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral. Here, analyzing 200 million spectra with Myriad Mapping (MM) of nanoscale mineral phases, we find CCHH and MHC, along with amorphous precursors, on freshly deposited coral skeleton and nacre surfaces, but not on sea urchin spines. Thus, biomineralization pathways are more complex and diverse than previously understood, opening new questions on isotopes and climate. Crystalline precursors are more accessible than amorphous ones to other spectroscopies and diffraction, in natural and bio-inspired materials.

Controls of Tellurium enrichment in the rare earth elements and yttrium (REY) rich deep-sea sediments from the Central Indian Ocean Basin (CIOB)

As a potential Te reservoir for the global budget, the occurrence, material sources, migration and enrichment mechanism of Te in deep-sea sediments remain unclear. Based on the major and trace elements measurements of bulk sediments, this study proposed a procedure to quantify the contribution of Te by main host minerals, combining with TIMA and LA-ICP-MS in two cores (GC04 and GC11) from the Central Indian Ocean Basin (CIOB) and a core from east of the 90°E Ridge (GC03). Te shows the highest enrichment coefficient of 650 referred to UCC (Upper Continental Crust) in the REY (Rare Earth Elements and Yittrium) rich sediments in GC04, GC11 and GC02 (a core at the south of GC04 and GC11). Clinoptilolite-K and osumilite are indicated as the main host minerals, which correlates Te sources with volcanogenic materials and weathering products of terrigenous rocks. The inter elements correlation, cluster analysis and factors analysis further indicate distinct hydrothermal genetic Te. So, we put forward a hypothesis that Te is mainly sourced from the submarine volcanogenic hydrothermal activities, which are closely associated with local intraplate volcanism episodes from late Miocene with spatial and temporal differences. This study is the first attempt to quantify Te from different minerals and to reveal its geochemical behavior in the deep sea sediments, which will be benefit to the understanding of Te reservoir and cycle in deep sea and the comprehensive utilization of REY-rich deep-sea sediments. However, for the abundant presence of undetectable nanoscale minerals in these sediments, the contribution of Fe-Mn (oxyhydr) oxides and clay minerals of Te need more investigation.

A Cross-Sectional Study of Bone Nanomechanics in Hip Fracture and Aging.

Bone mechanics is well understood at every length scale except the nano-level. We aimed to investigate the relationship between bone nanoscale and tissue-level mechanics experimentally. We tested two hypotheses: (1) nanoscale strains were lower in hip fracture patients versus controls, and (2) nanoscale mineral and fibril strains were inversely correlated with aging and fracture. A cross-sectional sample of trabecular bone sections was prepared from the proximal femora of two human donor groups (aged 44-94 years): an aging non-fracture control group (n = 17) and a hip-fracture group (n = 20). Tissue, fibril, and mineral strain were measured simultaneously using synchrotron X-ray diffraction during tensile load to failure, then compared between groups using unpaired t-tests and correlated with age using Pearson's correlation. Controls exhibited significantly greater peak tissue, mineral, and fibril strains than the hip fracture (all p < 0.05). Age was associated with a decrease in peak tissue (p = 0.099) and mineral (p = 0.004) strain, but not fibril strain (p = 0.260). Overall, hip fracture and aging were associated with changes in the nanoscale strain that are reflected at the tissue level. Data must be interpreted within the limitations of the observational cross-sectional study design, so we propose two new hypotheses on the importance of nanomechanics. (1) Hip fracture risk is increased by low tissue strain, which can be caused by low collagen or mineral strain. (2) Age-related loss of tissue strain is dependent on the loss of mineral but not fibril strain. Novel insights into bone nano- and tissue-level mechanics could provide a platform for the development of bone health diagnostics and interventions based on failure mechanisms from the nanoscale up.

Electrochemical impedance spectroscopy of concrete with nanoscale mineral additives

Electrochemical impedance spectroscopy of concrete with nanoscale mineral additives

Abiotic Factors Influence on Bacillus subtilis IMV B-7023 Phytase Activity

Bacteria of the Bacillus genus can synthesize specific phytase enzymes. This property is especially important for soil bacteria. It helps to mineralize phytin and phytates and to provide these bacteria and plants (in the root zone of which they live) with the available phosphorus. Our previous studies have demonstrated that the Bacillus subtilis IMV B-7023 strain exhibits a phytase activity and can use phytate as a nutrition source. It is a component of the «Azogran» complex bacterial preparation for crop production. As known, abiotic environmental factors can influence the phytase activity of bacteria. In particular, the phytase activity changes significantly under different pH and temperatures. Solid soil particles, including nanosized minerals, can also influence bacteria’s enzymatic activity. The influence of abiotic factors on Bacillus subtilis IMV B-7023 phytase activity has not previously been studied, so this was the aim of our research. Methods. The phytase activity of bacteria was studied by measuring the amount of phosphate released from sodium phytate during the enzymatic reaction, and the nanomaterials’ influence on growth — by cultivation methods. Results. The highest B. subtilis IMV B-7023 phytase activity was observed at 28°C. Also, there was no B. subtilis IMV B-7023 phytase activity at pH 4—6. However, this activity increased at pH 7 and did not change significantly with increasing the buffer system pH to 12. Silicon dioxide influence on the B. subtilis IMV B-7023 growth activity during cultivation in a media with phytate as a phosphorus source depended on the nanomaterial concentration. Thus, at 0.05 and 0.5 g/L of silicon dioxide in the medium, this strain growth activity increased by 8—18%, and at 5.0 g/L of these nanoparticles, bacteria growth inhibition by 19% was observed. At the same time, clay mineral bentonite did not affect the B. subtilis IMV B-7023 growth under the studied cultivation conditions. In addition, silicon dioxide and bentonite stimulated B. subtilis IMV B-7023 phytase activity at all studied concentrations. So, phytase activity increased by 1.82—3.34 times upon adding silicon dioxide and by 2.54—5.83 times upon adding bentonite into the medium. Since the optimal values for phytase activity of most genus Bacillus bacteria are within neutral pH values and temperatures within 50—55°C, a property of B. subtilis IMV B-7023 to show maximum phytase activity at alkaline pH and lower temperatures (28°C) and also stimulation of this activity by soil minerals increases competitiveness of this strain as a component of a bacterial preparation for crop production. Conclusions. Abiotic environmental factors influence the B. subtilis IMV B-7023 supernagrowth and phytase activity. Optimal physicochemical factors for the phytase activity of these bacteria are temperature 28°C and pH 7—12. The concentrations 0.05, 0.5, and 5.0 g/L of silicon dioxide and bentonite increase B. subtilis IMV B-7023 phytase activity. The effect of these nanoscale minerals on the B. subtilis IMV B-7023 growth depends on their type and concentration during cultivation in the medium with phytate as a phosphorus source. The obtained results indicate the potential ability of the B. subtilis IMV B-7023 strain to effectively assimilate phytates in neutral and alkaline soils, especially due to the interaction of these bacteria with bentonite and silicon dioxide nanoparticles. This expands the possibility of using B. subtilis IMV B-7023 in agricultural technologies.

Nanoscale Mineralogical Characterization of Terrestrial and Extraterrestrial Samples by Transmission Electron Microscopy: A Review

Nanoscale minerals (i.e., nanominerals and mineral nanoparticles) in terrestrial and extraterrestrial materials are difficult to characterize because of their small particle sizes, high surface energy, and/or poor crystallization. Transmission electron microscopy (TEM) is a powerful analytical platform for the characterization of minerals at the nano and even atomic scales, and it can determine their morphology through imaging, derive structural information using multiple electron-diffraction techniques, and investigate chemical compositions. Since the 1990s, the application of TEM to the characterization of nanoscale minerals has developed rapidly into a core technique in nanoscale Earth and planetary science (NEPS). This review introduces a brief history and the general principles of TEM, considers detailed methods of preparing specimens for nanoscale mineralogical characterization by TEM, and emphasizes the contributions of TEM to multiple NEPS research fields in recent decades. These contributions are considered from the perspective of nanoscale mineralogical studies of morphology, structure, and chemistry in complex geological materials. Finally, the work provides an outlook on current opportunities to apply TEM methods to nanoscale mineralogical study. This review aims to provide common and practical TEM methods to NEPS researchers and to support the use of TEM for a wide range of applications in nanoscale mineralogy to promote NEPS development.

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth.

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion-mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ∼10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41-92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (∼1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. These roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.

Polyphenol-mediated biomimetic mineralization of sacrificial metal-organic framework nanoparticles for wound healing

Mineralization is a natural process that constructs intricate structures at diverse interfaces, but with poor controllability. Herein, we present an alternative strategy for dynamic control of nano-scale mineralization processes and the subsequent construction of an all-in-one healing agent to meet the requirements of wound healing with complex physiological processes. The key point is the reversible metal-polyphenol coordination, where polyphenol acts as a capping agent to stabilize the mineralized precursor solution. Upon combination with metal-organic frameworks (MOFs) that can competitively capture polyphenol from solution to disrupt the balance of stabilized precursors, the released mineral ions result in fast mineralization on MOF surface. The mineralized metal-phenolic frameworks feature plug-and-play properties. After being loaded into a gelatin-chitosan hydrogel, the composite hydrogel exhibits antibacterial and anti-inflammatory effects while promoting angiogenesis, collagen deposition, and hair follicle regeneration. The mineralization strategy could also be applied to thin film technology for a range of applications.

In-situ U[sbnd]Pb geochronology of vesuvianite in skarn deposits

The timing of hydrothermal activity is a key factor in any predictive genetic model of skarn mineralization, but direct dating is often hindered by the absence of suitable minerals to date. Vesuvianite, a common mineral in skarn deposits, can incorporate U and has a high Pb closure temperature (>650 °C), and consequently may be suitable for dating for skarn deposits. Vesuvianite collected from nine Chinese skarn deposits, including the Jinchuantang SnBi, Shizhuyuan W–Sn–Mo–Bi polymetallic, Jiepai CuW, Dashunlong Sn, Xianghualing Sn, Furong Sn, and Huangshaping W–Sn–Mo–Cu polymetallic deposits in Nanling Range (Southern China), and the Kaerqueka and Saishitang Cu deposits in East Kunlun Orogen (Northwestern China), have high U concentrations (median 66.8 ppm for 460 LA-ICP-MS analysis spots). The flat and stable time-resolved signal spectra for U during LA-ICP-MS analysis, combined with the absence of nanoscale mineral inclusions, porosities, or lattice defects in the JCT vesuvianite, with high and consistent U concentrations, revealed by the HAADF-STEM images, and the marked positive relationships between U and REE collectively suggest that the U incorporation into vesuvianite was primarily controlled by replacement of Ca2+ in eight-fold coordination, confirming that vesuvianite may be a suitable UPb geochronometer. The JCT vesuvianite is characterized by high and consistent U concentrations (260–526 ppm, median 307 ppm) and homogeneous internal texture and elemental distribution, and yields an ID-TIMS UPb concordia age (2σ, 153.9 ± 0.2 Ma, MSWD = 1.6, n = 11), demonstrating that it can be taken as a potential LA-ICP-MS UPb reference material, which can be freely distributed to other laboratories. Using the JCT vesuvianite as a UPb reference material, the Kaerqueka, Saishitang, Jiepai, Dashunlong, Xianghualing, Furong, and Shizhuyuan vesuvianite yielded well-defined LA-ICP-MS UPb ages (239.0–152.1 Ma, 2σ), consistent with previously published age constraints of mineralization and cogenetic igneous rocks. Vesuvianite from the Huangshaping W–Sn–Mo–Cu polymetallic deposit, yielded UPb ages of 157.3 ± 1.4 Ma (2σ, MSWD = 1.8) and 161.0 ± 1.3 Ma (2σ, MSWD = 1.9), providing reliable constraints on the overprinting sequence of the skarn W–Sn–Mo and Cu mineralization events at Huangshaping, which was not previously detectable using other mineralization chronometers. Combined, these ages suggest that vesuvianite is a robust and reliable geochronometer, and offers a new tool for dating skarn deposits.

Nano-scale minerals in-situ supporting CeO2 nanoparticles for off-on colorimetric detection of L–penicillamine and Cu2+ ion

Realizing the high value-added utilization of cheap minerals in environmental catalysis has important practical significance. Herein, four nano-scale minerals, namely halloysite (Hal) nanotubes, palygorskite (Pal) nanorods, and montmorillonite (Mon) and hydrotalcite (LDH) nanosheets, were selected for in-situ supporting CeO2 nanoparticles (NPs) by a facile one-pot hydrothermal method. Among various nanocomposites (NCs), CeO2/Pal behaves the highest peroxidase-like activity, attributing to larger surface area for uniformly dispersing CeO2 NPs and more exposed active oxygen vacancy (Ovac) defects. A novel off-on colorimetric strategy was constructed for detecting toxic L-penicillamine (LPA) and Cu2+ ion with limit of detections (LODs) of 8.37 and 9.80 μM, respectively. Density functional theory (DFT) calculations show that the Ovac defect on CeO2(111) surface can catalyze the heterolytic cleavage of H2O2 into H2O and oxygen radical (•O), instead of being two hydroxyl radicals (•OH) on clean surface. It can also act as trapping site for O2 and H2O adsorption, improving the oxygen affinity and hydrophilicity of CeO2/Pal. This study provides a feasible strategy for designing mineral-based nanozymes and an insight into the possible catalytic mechanism.

Macro- to nanoscale mineral relationships in surficial cobalt-arsenic-bearing mine tailings of the Cobalt Mining Camp, Northeastern Ontario, Canada

ABSTRACT Arsenates, which correspond to the majority of known arsenic (As)-bearing minerals, control the mobilization of As in contaminated soils, sediments, and fluvial environments as well as in tailings and mine waste piles. Additionally, arsenate-bearing Fe-(hydr)oxides are of particular significance for the control of As mobility, as they are among the most thermodynamically stable minerals under near-neutral to alkaline pH conditions. However, in the surficial (upper 30 cm) alkaline mine tailings at the Cobalt Mining Camp in Northeastern Ontario, Canada, these phases only occur in trace amounts. This study attempts to understand this unusual mineralogical feature through an investigation of the relationships between nano- and macroscale mineralogical and geochemical features at two tailings sites (A and B) at the Cobalt Mining Camp. Sixty samples from two depth profiles (0–30 cm; i.e., one sample per centimeter) were collected at the two sites, analyzed for their major and minor chemical elements, and characterized for their mineralogical composition at the nano- to centimeter scale. The tailings material at both sites is predominantly composed of minerals of the amphibole, chlorite, and feldspar groups, as well as carbonates (calcite and dolomite). Minor phases are Co-Fe-Ni-Zn-sulfarsenides and -arsenates. The tailings material at site B contains, on average, higher concentrations of As, Co, Sb, and Zn and lower concentrations of Fe than the material at site A. Secondary (scanning electron microscope) and transmission electron microscopy studies indicate that the alteration of primary sulfarsenides to secondary arsenates may proceed in the following sequence: (1) the formation of Fe-hydroxide and -arsenate mineral surface coatings on sulfarsenides; (2) the downward mobilization of Co-Ni-Zn-arsenate and (FeOHCO3)aq species; (3) replacement of earlier-formed scorodite by Co-Ni-Zn-arsenates; (4) the precipitation of Co-Ni-Zn-arsenates on the surfaces of silicates; and (5) neoformation of Fe-rich hydroxy-interlayered minerals at greater depth, partly replacing earlier-formed Co-Ni-Zn-arsenates. These processes result in layers enriched in As, Co, Sb, and Zn (increase in Co#) and enriched and depleted in Fe (increase and decrease in Fe#) in tailings material at both sites. The TEM studies further indicate that Co-Ni-Zn-arsenates precipitate initially as nanoparticles on the surface of scorodite and detrital silicates and subsequently coarsen through Oswald ripening. The mineralogical-geochemical features depicted in this study provide a better understanding of the geochemical behavior of Co, Fe, and As in alkaline tailings and may assist in the interpretation of mineral-microbial community associations and the development of effective bioleaching strategies for the strategic element cobalt.

Characterization of nano-scale mineral dust aerosols in snow by single particle inductively coupled plasma mass spectrometry

Mineral dust aerosols in snow were analyzed by single particle ICP-MS with machine learning to classify particle groups.

Solubilization of struvite and biorecovery of cerium by Aspergillus niger

Cerium has many modern applications such as in renewable energies and the biosynthesis of nanomaterials. In this research, natural struvite was solubilized by Aspergillus niger and the biomass-free struvite leachate was investigated for its ability to recover cerium. It was shown that struvite was completed solubilized following 2 weeks of fungal growth, which released inorganic phosphate (Pi) from the mineral by the production of oxalic acid. Scanning electron microscopy (SEM) showed that crystals with distinctive morphologies were formed in the natural struvite leachate after mixing with Ce3+. Energy-dispersive X-ray analysis (EDXA), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) confirmed the formation of cerium phosphate hydrate [Ce(PO4)·H2O] at lower Ce concentrations and a mixture of phosphate and cerium oxalate decahydrate [Ce2(C2O4)3·10H2O] at higher Ce concentrations. The formation of these biogenic Ce minerals leads to the removal of > 99% Ce from solution. Thermal decomposition experiments showed that the biogenic Ce phosphates could be transformed into a mixture of CePO4 and CeO2 (cerianite) after heat treatment at 1000 °C. These results provide a new perspective of the fungal biotransformation of soluble REE species using struvite leachate, and also indicate the potential of using the recovered REE as biomaterial precursors with possible applications in the biosynthesis of novel nanomaterials, elemental recycling and biorecovery.Key points• Cerium was recovered using a struvite leachate produced by A. niger.• Oxalic acid played a major role in struvite solubilization and Ce phosphate biorecovery.• Resulting nanoscale mineral products could serve as a precursor for Ce oxide synthesis.

Application of fungal copper carbonate nanoparticles as environmental catalysts: organic dye degradation and chromate removal

Biomineralization is a ubiquitous process in organisms to produce biominerals, and a wide range of metallic nanoscale minerals can be produced as a consequence of the interactions of micro-organisms with metals and minerals. Copper-bearing nanoparticles produced by biomineralization mechanisms have a variety of applications due to their remarkable catalytic efficiency, antibacterial properties and low production cost. In this study, we demonstrate the biotechnological potential of copper carbonate nanoparticles (CuNPs) synthesized using a carbonate-enriched biomass-free ureolytic fungal spent culture supernatant. The efficiency of the CuNPs in pollutant remediation was investigated using a dye (methyl red) and a toxic metal oxyanion, chromate Cr(VI). The biogenic CuNPs exhibited excellent catalytic properties in a Fenton-like reaction to degrade methyl red, and efficiently removed Cr(VI) from solution due to both adsorption and reduction of Cr(VI). X-ray photoelectron spectroscopy (XPS) identified the oxidation of reducing Cu species of the CuNPs during the reaction with Cr(VI). This work shows that urease-positive fungi can play an important role not only in the biorecovery of metals through the production of insoluble nanoscale carbonates, but also provides novel and simple strategies for the preparation of sustainable nanomineral products with catalytic properties applicable to the bioremediation of organic and metallic pollutants, solely and in mixtures.

Metallic-Pb nanospheres in zircon from the Challenger Au deposit, South Australia: probing metamorphic and ore formation histories

AbstractAncient metamorphic processes are recorded by the formation of metallic-Pb nanospheres in zircon, a product of internal Pb mobilisation and thermally driven concentration. Here, metallic-Pb nanospheres formed within an ore deposit are characterised for the first time using high-angle annular dark field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy element-distribution mapping. Exceptional examples from the migmatite-hosted Archean–Paleoproterozoic Challenger Au deposit (Central Gawler Craton, South Australia) support widespread metallic-Pb nanosphere formation in zircon from rocks experiencing granulite-facies metamorphism. We also report new trace-element associations found with metallic-Pb nanospheres and a new mode of occurrence, in which Sc ‘haloes’ form adjacent to metallic-Pb nanospheres within the crystalline zircon lattice. This differs to previously characterised examples of metallic-Pb nanospheres associated with amorphous Si-rich glasses and unidentified Al–Ti, or Fe-bearing phases. Multiple modes of metallic-Pb nanosphere occurrences and trace-element associations suggests multiple modes of formation, probably dependant on zircon composition and metamorphic conditions. Identification of metallic-Pb nanospheres in a growing range of geological settings further highlights the mobility of Pb in zircon and the importance of detailed, nanoscale mineral characterisation, in order to constrain accurate geochronological histories for rocks within high-temperature geological environments.

Nanoscale mineralization of cell-laden methacrylated gelatin hydrogels using calcium carbonate-calcium citrate core-shell microparticles.

Conventional biomaterials developed for bone regeneration fail to fully recapitulate the nanoscale structural organization and complex composition of the native bone microenvironment. Therefore, despite promoting osteogenic differentiation of stem cells, they fall short of providing the structural, biochemical, and mechanical stimuli necessary to drive osteogenesis for bone regeneration and function. To address this, we have recently developed a novel strategy to engineer bone-like tissue using a biomimetic approach to achieve rapid and controlled nanoscale mineralization of a cell-laden matrix in the presence of osteopontin, a non-collagenous protein, and a supersaturated solution of calcium and phosphate medium. Here, we build on this approach to engineer bone regeneration scaffolds comprising methacrylated gelatin (GelMA) hydrogels incorporated with calcium citrate core-shell microparticles as a sustained and reliable source of calcium ions for in situ mineralization. We demonstrate successful biomineralization of GelMA hydrogels by embedded calcium carbonate-calcium citrate core-shell microparticles with the resultant mineral chemistry, structure, and organization reminiscent of that of native bone. The biomimetic mineralization was further shown to promote osteogenic differentiation of encapsulated human mesenchymal stem cells even in the absence of other exogenous osteogenic induction factors. Ultimately, by combining the superior biological response engendered by biomimetic mineralization with the intrinsic tissue engineering advantages offered by GelMA, such as biocompatibility, biodegradability, and printability, we envision that our system offers great potential for bone regeneration efforts.

Super-enrichment mechanisms of precious metals by low-melting point copper-philic element (LMCE) melts

低熔点亲铜元素（LMCE）As、Sb、Bi、Hg、Pb、Se、Te、Tl、Sn等，均具有亲铜性、低熔点、半金属的特性，在成矿过程中可以形成LMCE熔体，并对Au、Ag、PGE等贵金属的高效富集沉淀起到一种重要的桥梁作用。作者对前人研究资料与LMCE热力学相图进行了分析，并结合浅成低温热液型、造山型、卡林-类卡林型、碱性-偏碱性侵入岩型金矿床的研究成果，探讨了LMCE熔体形成、类型及其对Au、Ag、PGE等贵金属富集成矿的机理，并提出了LMCE熔体参与成矿的矿物组合与结构特征标志。LMCE熔体可以在岩浆过程、（岩浆）热液过程及变质过程中形成，是贵金属矿床重要的成矿机制之一。LMCE熔体中存在大量原子团簇，团簇间的聚集生长会使熔体难以达到相平衡，形成许多非平衡矿物组合，如包含LMCE的自然元素、金属互化物及含LMCE的多相矿物。Au在LMCE熔体中也可以团簇存在，金团簇聚集形成球状或片状，并形成巨富的金矿体。LMCE熔体形成的矿物常以浑圆状、近浑圆状、不规则状的单个或群体组合的乳滴、珠滴、气泡的微粒包体产在硫化物、硒化物、碲化物、氧化物和硅酸盐矿物内或沿矿物裂隙线形排列，这些LMCE微粒包体是熔体扰动导致熔-熔或熔-液间发生乳化所致，流体沸腾是引起熔体扰动的主要机制。LMCE熔体不能快速淬火结晶，通常在低温下缓慢冷却达到相平衡，形成复杂的矿物组合，该特点即使在微米到纳米级的矿物微粒中也显著存在。熔体-流体包裹体是LMCE熔体参与成矿作用最为直接的证据。固溶体分解结构、熔体退火结构、矿物-熔体二面角结构、溶解-再沉淀结构等也是LMCE熔体参与成矿的标志性结构。;The low-melting point chalcophile elements (LMCE), including As, Sb, Bi, Hg, Pb, Se, Te, Tl, Sn and so on, have characteristics of chalcophile behavior, low melting point and semi-metallic properties, which can form LMCE melt during mineralization process and play an important role for the efficient enrichment and precipitation of Au, Ag, PGE and other precious metals. In this paper, the previous research data and the LMCE thermodynamic phase diagrams were analyzed. Combining research results of epithermal, orogenic, Carlin to Carlin-like and alkaline to meta-alkaline intrusion-related gold deposits, the authors discussed the formation and type of LMCE melts and their mechanisms for the enrichment of Au, Ag, PGE and other precious metals, and summarized mineral compositions and characteristic textures of mineralization that benefited by LMCE melts. The LMCE melts can be formed during magmatic, (magmatic-) hydrothermal and metamorphic processes, and belong to one of the important metallogenic mechanisms for precious metal deposits. There are many ion clusters in the LMCE melts, and aggregation between the clusters precludes the melt to reach phase equilibrium, which results in many non-equilibrium mineral combinations, including the coexistence of native LMCE, intermetallic compounds and multiphase minerals containing LMCE. Gold could also exist as ion clusters in the LMCE melt that gather to form spherical or flakes native gold, and form the super-rich ore bodies. The minerals formed by LMCE melt often exist as single or group combinations of emulsion droplets, beads, and bubbles in round, nearly round, and irregular particle inclusions in sulfides, selenides, tellurides, oxides and silicates, or distribute along fractures of minerals. These LMCE micro-inclusions are derived from melt disturbance that result in melt-melt or melt-liquid emulsification. Fluid boiling should be the main mechanism that causes the melt disturbance since the LMCE melt cannot be quenched and crystallized quickly at this process. It is usually cooled slowly at low temperature to achieve phase equilibrium and form complex mineral compositions. This feature is significant even in micro-to nano-scale mineral particles. Melt-fluid inclusions are the most direct evidence for the involvement of LMCE melts during mineralization. Solid solution decomposition texture, melt annealing texture, mineral-melt dihedral texture, dissolution-reprecipitation texture are also characteristic textures of LMCE melts involved in mineralization.