Electron Microprobe Research Articles

Leveraging Ligand Steric Demand to Control Ligand Exchange and Domain Composition in Stratified Metal-Organic Frameworks.

Incorporatingdiversecomponentsintometal-organic frameworks (MOFs) can expand their scope of properties and applications.Stratified MOFs (sMOFs) consist of compositionally unique concentric domains (strata), offering unprecedentedcomplexity through partitioning of structural and functional components. However, the labile nature ofmetal-ligand coordination handicapsachieving compositionally-distinct domainsdue toligand exchange reactions occurring concurrentlywithsecondary strata growth. To achieve complex sMOF compositions, characterizingand controllingthe competing processes of new strata growth and ligand exchangeare vital. This work systematicallyexaminescontrolling ligand exchangein UiO-67 sMOFs by tuning ligandsterics. We present quantitative methodsfor assessing and visualizing the outcomes of strata growth and ligand exchange that relyon high-angle annular dark-field images and elemental mapping via scanning transmission electron microscopy-energy dispersive X-ray spectroscopy. In addition, weleverageligand stericsto create 'blocking layers'that minimizeligand exchange between strata which are particularly susceptible to ligand exchange and inter-strata ligand mixing. Finally,we evaluatestrata compositional integrity in various solvents and find that sMOFs can maintain their compositions for >12 months in some cases.Collectively, these studies and methodsenhanceunderstanding and control overligandplacement in multi-domain MOFs,factors that underscore careful tunning of properties and function.

Gold occurrence in the footwall of the Lappberget Deposit, Garpenberg Mine, Sweden: Implications for recovery efficiency

By-product metals have a significant potential to bring additional economic benefits to mines. However, a detailed characterization of their distribution is generally required to fulfill this potential and should preferably be integrated into a geometallurgical assessment. This contribution presents a detailed mineralogical and textural investigation of gold-bearing phases at the footwall of the Zn–Pb–Ag–(Cu–Au) Lappberget Deposit, Garpenberg Mine, Sweden, using optical microscopy, scanning electron microscope with energy dispersive spectroscopy (SEM-EDS), electron probe microanalysis (EPMA), laser ablation-inductively coupled plasma mass spectrometer (LA-ICPMS), and bulk chemical analysis applied to drill core and Knelson concentrator samples. Gold is a by-product at the Garpenberg mine, but it is unclear how the mineralogy, occurrence, and distribution of gold-bearing phases impact on gold recoveries during mineral processing. Our results show that Au-dominant electrum is the most abundant gold-bearing phase in the footwall of the Lappberget deposit, occurring strongly associated to sulfides in a variety of textures and grain sizes. Electrum grains commonly occur within sulfide borders, as inclusions, intergrowth and overgrowths of chalcopyrite, pyrite, galena, sphalerite, and pyrrhotite. Gangue minerals may also contain disseminated electrum and inclusions. Electrum grain sizes range from ∼5 µm to 300 µm, predominantly below 100 µm. The potential of sulfide lattice-bound invisible gold in the form of solid-solution gold and colloidal gold was also investigated, showing Au depletion within the analyzed sulfide carriers. The analysis of the concentrate samples from the Knelson gravity concentrator showed 584 and 431 ppm of gold content. High degree of liberation is observed among the gold-bearing phases in the concentrate, and gold recovery is highest among fractions coarser than 106 µm mesh. Pyrite and galena are the most abundant minerals in the concentrate samples. The gold-bearing phases were categorized based on its mineralogy, texture, grain size, and association and their influence on gold processing, especially textures and grain size, which implicates its liberation in milling and recovery by the gravity separator.

Investigating the impact of palaeoclimatic conditions and diagenesis on the genesis of Permian Continental Red Beds: A case study from the Bohemian Massif, Czechia

The processes responsible for reddening of Continental Red Beds (CRBs) and the relationship between colour variation and paleoenvironmental conditions are presented focusing on a comprehensive multi-proxy study of Permian sediments in the Bohemian Massif, Czechia. The investigation incorporates facies analysis, quantitative colour assessment using diffuse Vis-spectral reflectance (DRS), optical and electron microprobe microscopy, bulk-rock (XRF and XRD), and in-situ geochemistry (laser-ablation ICP-MS). Results indicate a progressive drying trend from the Cisuralian to Guadalupian series in studied continental red sediments. Different facies indicate the change of the sedimentary environment from a deep lacustrine environment (lower part of Rudník Member, Cisuralian) to a fluvial floodplain and eolian environment (Trutnov Formation, Guadalupian). Examination of the three major categories (white, grey-green and red sediments) identified in the studied continental red beds indicate that diagenetic alteration of clay minerals and biotite were the main source of iron fuelling the growth of hematite responsible for their red colour. Early diagenetic processes and paleoenvironmental conditions, particularly the oxidizing or reducing conditions play a key role in the red sediment formation. It is suggested that later diagenetic stages are incapable of colouring non-red, iron-rich sediments formed in deep anoxic lacustrine environments. Microbial activities and reducing fluids have been identified as the main factors in the formation of grey-green sediments forming distinct reduction zones. The reduction spots formed during the early stages of diagenesis (eodiagenesis), and they were likely never red. In contrast, reduction strips, initially exhibiting a red hue, underwent a colour change during more advanced stages of diagenesis (mesodiagenesis).

One-Pot Phyto-Mediated Synthesis of Fe2O3/Fe3O4 Binary Mixed Nanocomposite Efficiently Applied in Wastewater Remediation by Photo-Fenton Reaction

A binary Fe2O3/Fe3O4 mixed nanocomposite was prepared by phyto-mediated avenue to be suited in the photo-Fenton photodegradation of methylene blue (MB) in the presence of H2O2. XRD and SEM analyses illustrated that Fe2O3 nanoparticles of average crystallite size 8.43 nm were successfully mixed with plate-like aggregates of Fe3O4 with a 15.1 nm average crystallite size. Moreover, SEM images showed a porous morphology for the binary Fe2O3/Fe3O4 mixed nanocomposite that is favorable for a photocatalyst. EDX and elemental mapping showed intense iron and oxygen peaks, confirming composite purity and symmetrical distribution. FTIR analysis displayed the distinct Fe-O assignments. Moreover, the isotherm of the developed nanocomposite showed slit-shaped pores in loose particulates within plate-like aggregates and a mesoporous pore-size distribution. Thermal gravimetric analysis (TGA) indicated the high thermal stability of the prepared Fe2O3/Fe3O4 binary nanocomposite. The optical properties illustrated a narrowing in the band gab (Eg = 2.92 eV) that enabled considerable absorption in the visible region of solar light. Suiting the developed binary Fe2O3/Fe3O4 nanocomposite in the photo-Fenton reaction along with H2O2 supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. The solar-driven photodegradation reactions were conducted and the estimated rate constants were 0.002, 0.0047, and 0.0143 min−1 when using the Fe2O3/Fe3O4 nanocomposite, pure H2O2, and the Fe2O3/Fe3O4/H2O2 hybrid catalyst, respectively. Therefore, suiting the developed binary Fe2O3/Fe3O4 nanocomposite and H2O2 in photo-Fenton reaction supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. After being subjected to four photo-Fenton degradation cycles, the Fe2O3/Fe3O4 nanocomposite catalyst still functioned admirably. Further evaluation of Fe2O3/Fe3O4 nanocomposite in photocatalytic remediation of contaminated water using a mixture of MB and pyronine Y (PY) dyestuffs revealed substantial dye photodegradation efficiencies.

Phase equilibria of CaO–Al2O3–CaO·TiO2 system at 1500 °C in hydrogen atmosphere

The phase diagram of CaO–Al2O3-TiOx system is of great importance in guiding the design of metallurgical slag systems for Al–Ti alloy steel, controlling Ti-bearing inclusions in molten steel, and regulating the mineral phase of vanadium-titanium magnetite. In the present work, the high temperature equilibration-quench technique was adopted, and the types and compositions of equilibrium phases were identified by Electron Probe Micro Analysis (EPMA) and X-ray diffraction (XRD). The isothermal section of CaO–Al2O3–CaO·TiO2 system at 1500 °C in H2 atmosphere was constructed for the first time. There are 7 three-phase fields, 10 two-phase fields, and a single liquid phase field. On this basis, according to the theoretical analysis of the crystal structure, the formation energy analysis based on first-principles calculations, and the related theories of defect chemistry, the formation mechanisms of CaTiO3 and Ca3Ti2O7 solid solution with were determined, respectively. Additionally, the experimental phase diagram was utilized to discuss the dissolution type and the equilibrium solubility of typical inclusions (Al2O3, Ti3O5, and CaO·TiO2) in Al–Ti alloy steel.

PdRuO2/PVP nanomaterial as a highly selective, stable, and applicable potentiometric sensor for the detection of Cr3+

PdRuO2/PVP nanomaterial was synthesized using a straightforward method and characterized using advanced analytical methods such as TEM, XRD, XPS, elemental mapping and SEM. The synthesized PdRuO2/PVP nanomaterial was used as an ionophore in potentiometric sensor electrodes and successfully adapted to Cr3+ ion detection in a large number of aqueous samples. Several experimental parameters of the PdRuO2/PVP sensor such as potentiometric behavior, selectivity, repeatability, response time, pH, titration, and recovery in real samples were investigated. Potentiometric behavioral characteristics were performed in the concentration range 1 × 10−6–1.0 × 10−1 M. The repeated experiments performed six times showed that there was no deviation in the measurements. The limit of detection of the PdRuO2/PVP potentiometric sensor was very low with a value of 8.6 × 10−8 M. The potentiometric measurements showed that the synthesized PdRuO2/PVP ionophore was highly effective in detecting Cr3+ in a wide pH range of 2.0–8.0 and was found to have a shelf life of over 1 year. As a result, the synthesized PdRuO2/PVP electrode material was found to be highly selective, stable, and applicable for Cr3+ detection.Graphical

Fabrication of TiO2 Nanoparticle Coating on Stainless Steel 316L and Its Assessment for Orthopaedic Applications

The study aims to investigate the efficacy of titanium dioxide (TiO2) nanoparticle coating on stainless steel 316L (SS 316L) orthopaedic implants to enhance their biocompatibility, osseointegration, and durability. The TiO2 nanoparticles were synthesized via the hydrothermal method and extensively characterized for composition, crystallinity, and morphology using techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), corroborated by elemental mapping. SEM and XRD analyses revealed the synthesized nanoparticles have a spherical shape and an average size of approximately 23 nanometres. The synthesized TiO2 nanoparticles were uniformly coated on SS 316L substrates using the spin coating technique, as confirmed by SEM images. Cell viability of the synthesized TiO2 nanoparticles, as well as uncoated and TiO2 nanoparticle-coated SS 316L substrates, was evaluated using the MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay against the NIH-3T3 mouse embryonic fibroblast cell line. The results demonstrated that the TiO2 nanoparticle-coated SS 316L substrate showed a significant increase of 22.87% in cell viability as compared to the uncoated SS 316L substrate. A ball-on-disc tribometer was employed to assess wear and friction resistance at various speeds, viz., 150 rpm, 300 rpm, and 450 rpm, under 30N load conditions for five minutes. The results collectively indicate a substantial improvement in the performance of TiO2 nanoparticle-coated SS 316L substrates for orthopaedic applications.

Effect of gamma irradiation on properties of the synthesized PANI-Cu nanoparticles assimilated into PS polymer for electromagnetic interference shielding application

Conductive polymer nanocomposites for electromagnetic interference (EMI) shielding are important materials that can be combat the increasingly dangerous radiation pollution arising from electronic equipment and our surrounding environment. In this work, we have synthesized polyaniline-copper nanoparticles (PANI-Cu NPs) by the copper salt based oxidative polymerization method at room temperature and then added with different concentration (0, 1, 3 and 5 wt%) in polystyrene polymer forming PS/ PANI-Cu nanocomposites films by means of the traditional solution casting technique. The formed PANI-Cu NPs were investigated by UV/Vis spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM) and SEM/EDX elemental mapping techniques. On the other hand, the prepared PS/PANI-Cu nanocomposites films were evaluated by UV and SEM, the mechanical properties of the nanocomposites films were evaluated and showed an improvement by added PANI-Cu NPs up to 3 wt% and 50 kGy gamma exposure dose. The PS/PANI-Cu nanocomposites films were examined as electromagnetic interference shielding material. Electromagnetic shielding effectiveness of the produced nanocomposites were tested in the X-band of the radio frequency range namely from 8 to 12 GHz using the vector network analyzer (VNA) and a proper wave guide. All samples were studied before and after 50 kGy gamma-ray irradiation under the same condition of pressure and temperature. The results showed that the nanocomposites have improved shielding properties.

In Operando Study of Microsupercapacitors with Gel Electrolytes Using Nano‐Beam Synchrotron X‐ray Diffraction

AbstractSynchrotron radiation X‐ray diffraction (XRD) with nanoscale beam size was used here for in situ and in operando study of micro‐supercapacitors (MSC) with gel electrolyte and MXene Ti3C2Tx electrodes. The electrode structure was characterized as a function of applied voltage and distance from the gap separating electrodes using microscopic cells with cylindrical shape designed for transmission mode XRD. The devices with gel electrolytes based on H2SO4 (with H2O/PVA and DMSO/PVA) showed stable performance with no changes in MXene structure under voltage swaps between positive and negative values. Experiments with KI‐based electrolytes demonstrated changes of MXene structure correlated with decrease of energy storage parameters under conditions of increased operation voltage starting from 0.8 V. The optimal performance of the MSCs was observed when the MXene structure remained unchanged upon switching the applied voltage polarity. The changes of inter‐layer distance of MXene upon swap of applied voltage correlate with decrease of device performance and are undesirable for stable operation of MSC's. We also tested feasibility of X‐ray fluorescence (XRF) for characterization of electrolyte ion migration in MSCs using 2D element mapping. Irreversible sorption of iodine by MXene was found using XRF mapping of charged electrodes using standard in‐plane MSC device and KI electrolyte.

Industrial Deportment of Minor and Trace Elements in Direct Nickel Matte Smelting

AbstractA sampling campaign was carried out at an industrial nickel flash smelter with the aim of evaluating the trace element distributions along the smelting line from raw materials to high-grade nickel matte and discard slag. The industrial technology was direct-to-nickel matte smelting without conventional Peirce–Smith converters, thus having two different nickel mattes as smelting products and feeds in the refinery: the sulfidic low-iron nickel matte from smelting furnace and the low-sulfur electric furnace matte from slag cleaning. Major and trace element concentrations were obtained from the solidified samples by electron probe microanalysis and laser ablation–inductively coupled plasma–mass spectrometry. Due to the industrial sampling environment, i.e., the slow cooling rate of the samples, not all the trace element concentrations were able to be measured at the lowest detection limits of the techniques used in some of the phases formed after cooling. However, the obtained results and element distribution coefficients were in good agreement with equilibrium values published in the literature.

Understanding engagement in intensive learning: From fuzzy chaotic indigestion to eupeptic clarity

This paper is framed by Nick Zepke’s, Vicki Trowler’s, and Paul Trowler’s concept of student engagement being “chaotic”, suffering from “indigestion” and “fuzziness”. This study was conducted at a UK higher education institution that recently moved to a “block and blend” delivery approach. We investigated what students and staff think engagement looks like in an intensive block and blend learning context. Data were gathered from students and staff via an online survey, which consisted of both scaled and open-ended questions. Findings are synthesised in an elemental map, providing a comparison of students and staff perceptions of engagement. Specifically, students and staff thought engagement in an intensive block and blend context entailed participation and active learning; a mindset that included enthusiasm, interest, focus, and enjoyment; timely completion of assessments; relationships with peers and tutors; doing more than required, such as completing extra readings; and accessing help and support. Participants also identified attendance as an indicator of student engagement and determined that the university has a responsibility to create learning environments to foster student engagement. Overall, the study findings point to elements of student engagement that may be designed into intensive block and blend learning environments. These approaches are also relevant to other similar intensive learning contexts.

Green synthesis of novel Zn0.5Ni0.5FeCrO4 spinel magnetic nanoparticles: Photodegradation of 4-nitrophenol and aniline under visible light irradiation

This study explores novel nanoparticles used in environmental remediation of 4-nitrophenol and aniline from wastewater bodies. The Zn0.5Ni0.5FeCrO4 magnetic nanoparticles (MNPs) were synthesized using tragacanth gel as a green, low-cost, and easy sol-gel method. The MNPs were characterized by XRD, XPS, FT-IR, VSM, TEM, EDX, FESEM, BET, DRS, and elemental mapping. The analysis demonstrated that nanoparticles have a spinel cubic structure, spatial distribution of the elements, ferromagnetic activity, narrow bandgap, and uniform morphology. Furthermore, effectiveness of the developed MNPs to degrade recalcitrant organic pollutants such as 4-nitrophenol (4-NP) and aniline under visible light exposure were studied. The results indicated 95% aniline and 80% of 4-NP were successfully degraded in 180 and 150 min, respectively. The total organic carbon (TOC) analysis revealed 65% and 54% removal of aniline and 4-NP. LC-MS was employed to elucidate the photodegradation mechanism and to identify the degradation products, including small fragmented molecules.

Impact of particle size and associated minerals on rare earth desorption and incorporation mechanisms in a South American ion-adsorption clay

This research delves into the intricate nexus of particle size, mineralogical composition, surface attributes, elemental mapping, and rare earth element (REE) adsorption mechanisms within an ion-adsorption clay sample from South America. The investigation entails the fractionation of the ion-adsorption clay into three size categories: S1 (< 0.25 mm), S2 (0.25–0.5 mm), and S3 (0.5–2 mm). Each fraction undergoes meticulous characterization to unveil its elemental composition, mineralogical composition, surface area, morphological characteristics, elemental mapping, and the mechanisms governing REE incorporation. The results indicate that S1 has 31% physiosorbed, 8% chemisorbed, and 61% mineralized REEs, while S2 has 40% physiosorbed, 5% chemisorbed, and 55% mineralized REEs, and S3 has 24% physiosorbed, 5% chemisorbed, and 71% mineralized REEs. The physisorbed REEs are attributed to the presence of kaolinite, conducive to mostly physisorption. In terms of grain size and REE content/type relationship, the results show that REE content decreases with increasing grain size; however, there is not a clear trend in terms of REE occurrence modes with grain size. Heavy rare earth elements (HREEs) are discernibly favored in adsorption over light rare earth elements (LREEs). This preference is underpinned by the weathering processes that led to the formation of ion-adsorption clay, which facilitated the transport and accumulation of HREEs. Notably, the ion-adsorption clay encompasses a substantial content of mineralized REEs, necessitating more demanding extraction methodologies, such as acid baking followed by water leaching if complete extraction of all REEs is desired. Among the desorbable REEs, physisorption dominates, encompassing over 80% of the total. Chemisorbed REEs exhibit versatility in association with various minerals, encompassing kaolinite, quartz, and goethite. In essence, this study unveils the intricate interplay between particle dimensions, mineralogical constitution, surface attributes, and REE adsorption modes within this ion-adsorption clay sample. The ion-adsorption clay in this study contains a significant portion of mineralized REEs that cannot be extracted using the mild conditions typically employed for the desorption process. Additionally, the REE concentration in this ion-adsorption clay is notably higher than the average found in clay deposits worldwide, reaching levels comparable to those of regolith deposits in China, which are a major global source of REEs. This remarkable concentration of REEs, along with the unique modes of their occurrence in this deposit, presents a significant interest to the scientific community.

Efficient synthesis of some [1,3]-oxazine derivatives in the presence of solid acid nano catalyst based on ferrierite and study on their activity against breast cancer through molecular docking calculation

In this research, the magnetic solid acid nanocatalyst based on ferrierite has been prepared and used as catalyst for the green synthesis of some [1,3]-oxazine derivatives in water at room temperature. The synthesized compounds were obtained in high to excellent yields after short reaction times and the structure of synthesized products were investigated by spectroscopic methods such as: FT-IR, 1H NMR and 13C NMR. The prepared magnetic solid acid catalyst was characterized using XRD, FT-IR, FE-SEM, EDX, elemental mapping, TGA and VSM analysis methods. Magnetic catalyst has easy separation ability, which leads to better and easier recycling. The preparation and synthesis of [1,3]-oxazine derivatives were carried out at room temperature in the presence of M-FER/TEPA/SO3H. Easy workup, green solvent (water) and also short reaction times with high to excellent yield of products, are some of advantageous of presented method. Docking calculations on the structure of the synthesized compounds proved their medicinal properties against breast cancer cells.

Study on hydrogen reduction mechanism of MoO3 using Ti–Mo core–shell powder

In this study, the hydrogen reduction mechanism of MoO3 was analyzed in detail using Ti–Mo core–shell powder manufactured through a milling and reduction process. MoO3 and Ti powders were ball-milled to refine the MoO3 powder and coat it onto the Ti powder to fabricated core-shell structure. Subsequently, the milled powder was heat-treated at 600°C in a hydrogen atmosphere to reduce MoO3 to nano-sized Mo. In addition, the reduction behavior of MoO3 was analyzed by varing the reduction times to 1, 10, 30 min and 1, 3, 5 h. Phase analysis was conducted using X-ray diffraction, and oxidation state analysis was conducted using X-ray photoelectron spectroscopy. Morphology analysis was performed using scanning electron microscopy, and elemental analysis was conducted using electron probe micro-analysis. It was confirmed that Mo9O26 and Mo4O11 intermediate phases were formed sequentially as MoO3 was reduced to MoO2, and Mo9O26 had a plate shape with a thickness of sub-70 nm, and Mo4O11 exhibited a thickness of sub-300 nm. Especially, the Mo2O3 intermediate phase, previously studied only theoretically, was experimentally confirmed for the first time in the reduction process from MoO2 to Mo. Furthermore, the analysis of Mo-oxide intermediate phases was explained by the structural characteristics of the core–shell. The shell of Mo oxide was thick and dense, making it difficult for the vapor phase necessary for CVT reduction to penetrate and diffuse into the shell. As a result, the rapid CVT reduction occurred outside the shell, while relatively slower reduction occurred inside the shell where intermediate phases were observed.

New data and insights on the secondary glass workshop of Comacchio (Italy): MgO contents, steatite crucibles and alternatives to recycling

This study introduces a collection of 33 glass samples, encompassing production indicators (blocks, fluidity tests, drops, cuts and wastes) and finished products (mainly goblets and probably a lamp) dating to the second half of the 7th century, except for a single more recent specimen (12th-14th). Additionally, a fragment was taken from a crucible bearing a thin layer of glass inside it. This new collection complements the investigation of glass materials from the Comacchio workshop previously analysed by Bertini et al. (2020).Measurements were performed using scanning electron microscopy, electron microprobe, laser ablation inductively coupled plasma mass spectroscopy on all samples and Sr–Nd isotopic analyses on 5 blocks.The results showed how the entire collection can be classified as natron-based silica-soda-lime glass and that the high MgO contents frequently observed are due to contamination with the steatite crucible. Contextually, the hypothesis of using plant ash-based glass mixed with natron-based glass formulated in the previous literature seems to have run out, along with the use of plant ash-based glass itself, further weakened by the very low representativeness of this latter type of glass on the site.The technological investigation further elucidated that recycling may not singularly account for the Comacchio glass technology. Discernible correlations may suggest the introduction of different types of metals, indicating a specialised control over the production process. Notably, the preference for green–blue glass emerges as a distinctive hallmark, underscoring the deliberate pursuit of a specific aesthetic taste.Lastly, the provenance analysis showed that over three-quarters of production was based on semi-finished products from Egypt, while only the remaining quarter came from the Levantine coast.

New data and insights on the secondary glass workshop of Comacchio (Italy): MgO contents, steatite crucibles and alternatives to recycling

This study introduces a collection of 33 glass samples, encompassing production indicators (blocks, fluidity tests, drops, cuts and wastes) and finished products (mainly goblets and probably a lamp) dating to the second half of the 7th century, except for a single more recent specimen (12th-14th). Additionally, a fragment was taken from a crucible bearing a thin layer of glass inside it. This new collection complements the investigation of glass materials from the Comacchio workshop previously analysed by Bertini et al. (2020).Measurements were performed using scanning electron microscopy, electron microprobe, laser ablation inductively coupled plasma mass spectroscopy on all samples and Sr–Nd isotopic analyses on 5 blocks.The results showed how the entire collection can be classified as natron-based silica-soda-lime glass and that the high MgO contents frequently observed are due to contamination with the steatite crucible. Contextually, the hypothesis of using plant ash-based glass mixed with natron-based glass formulated in the previous literature seems to have run out, along with the use of plant ash-based glass itself, further weakened by the very low representativeness of this latter type of glass on the site.The technological investigation further elucidated that recycling may not singularly account for the Comacchio glass technology. Discernible correlations may suggest the introduction of different types of metals, indicating a specialised control over the production process. Notably, the preference for green–blue glass emerges as a distinctive hallmark, underscoring the deliberate pursuit of a specific aesthetic taste.Lastly, the provenance analysis showed that over three-quarters of production was based on semi-finished products from Egypt, while only the remaining quarter came from the Levantine coast.

Gemological Characteristics of Blue-Violet Cordierite

Cordierite is a violet-blue gem mineral primarily composed of magnesium aluminum silicate. This study employed three samples of Mg-cordierite and conducted tests on their gemological characteristics, spectroscopic features, and chemical composition using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet spectrophotometry, X-ray photoelectron spectroscopy (XPS), and electron microprobe. The study also explored and analyzed the polychroism and coloration mechanisms of the samples. The results indicate that the lattice vibrations of the Mg-cordierite samples differ along the directions parallel to the a, b, and c crystallographic axes, leading to certain variations in spectral characteristics among these directions. The article provides experimental evidence for the reasons for the polychroism of cordierite in different crystal axes, which is of great significance in the quality evaluation of cordierite.

Crystallization of Calcium Carbonate and Calcium Phosphate Phases in Silica Hydrogel: Morphological and Compositional Characterization

The present study showcases a series of crystallization experiments using a specially designed double diffusion system to grow crystals belonging to the calcium carbonate–phosphate system. The experimental U-shaped device comprised two vertical solution containers, separated by a horizontal column of silica hydrogel. Each container was filled with 0.5 M CaCl2 and 0.5 M Na2CO3 solutions, which diffused through the gel column over time. Na3PO4 solutions, with 50 and 500 ppm concentrations, were incorporated into the gel in different experiments, resulting in a homogeneous distribution of phosphate concentrations within the diffusion column. After 15- and 30-day incubation periods post-nucleation, the crystals formed in different sections of the gel were carefully extracted and studied with scanning electron microscopy and electron microprobe. Additionally, Raman spectra were collected from the samples using a confocal Raman microscope, providing further insights into their molecular composition and structural properties. The obtained results show that under the induced experimental conditions (i) phosphate incorporates into calcite’s structure, and (ii) the growth of calcium phosphates in the presence of carbonate ions involves the sequential, heterogeneous nucleation of CO3-bearing OCP/HAP-like phases, with Raman spectral characteristics very similar to those of bioapatites.

Crystallization Sequence of the Spodumene-Rich Alijó Pegmatite (Northern Portugal) and Related Metasomatism on Its Host Rock

The Barroso–Alvão region is an excellent setting for studying Li mineralization associated with granitic pegmatites and developing Li exploration techniques. Among the distinguished pegmatite types in this pegmatite field, the spodumene-bearing dyke from Alijó is a representative example of an Iberian Li–Cs–Ta (LCT) pegmatite currently under exploitation. In this work, we examine the internal evolution of the Alijó dyke and its external metasomatic effect on the surrounding metasediments, contributing to lithium exploration techniques. Electron microprobe analyses provided clues about the crystallization conditions and the degree of differentiation of the pegmatitic melt, whereas the external metasomatism induced by the spodumene-bearing pegmatite was studied through whole-rock geochemistry. The obtained results indicate that the primary crystallization of the studied dyke likely occurred at temperatures between 450–500 °C, with emplacement at shallow crustal levels of about 2–3 kbar. The high concentrations of trace elements such as Li, Cs, Rb, Be, Sn, Nb, Ta, Ge, U, and Tl in the pegmatitic melt suggests high availability of these elements, allowing their partitioning into an early exsolved fluid phase. The exsolution of this fluid phase, subtracting components such as F and B, from the pegmatitic melt would cause a significant undercooling of the melt. Moreover, the interaction of this expelled fluid with the country rock generated a metasomatic overprint in the surrounding metasedimentary host rocks. The metasomatic effect in Alijó is strongly influenced by the nature of the host metasediments, with a significantly higher grade of metasomatism observed in pelitic (mica-rich) samples compared to psammitic (mica-poor) samples collected at same distances from the dyke. The greisen developed close to the pegmatite contact reflects this metasomatic signature, characterized by the mobilization of at least B, F, Li, Rb, Cs, Sn, Be, Nb, Ta, and Tl. We cautiously suggest that whole rock Li concentrations greater than 300 ppm, combined with a minimum value of 1000 ppm for the sum of B, F, Li, Rb, Cs, and Sn in pelitic metasediments of Barroso–Alvão, may be indicative of a mineralized pegmatite in this region.