Phosphate Minerals Research Articles

Rare Earth Element Speciation in Coal and Coal Combustion Byproducts: A XANES and EXAFS Study.

Transitioning to a low-carbon economy, necessary to mitigate the impacts of anthropogenic climate change, will lead to a significant increase in demand for critical minerals such as rare earth elements (REE). Meeting these raw materials requirements will be challenging, so there is increasing interest in new sources of REE including coal combustion byproducts (CCBs). Extraction of REE from CCBs can be advantageous as it involves reusing a waste product, thereby contributing to the circular economy. While a growing body of literature reports on the abundance of REE in CCBs globally, studies examining the key factors which control their recovery, including speciation and mode of occurrence, are lacking. This study employed synchrotron-based X-ray absorption spectroscopy to probe the speciation and local bonding environment of yttrium in coals and their associated CCBs. Linear Combination Fitting identified silicate and phosphate minerals as the dominant REE-bearing phases. Taken together with the results of extended X-ray absorption fine structure (EXAFS) curve fitting, we find there is minimal transformation in the REE host phase during combustion, indicating it is transferred in bulk from the coals to the CCBs. Accordingly, these findings can be incorporated into the development of an efficient, environmentally conscious recovery process.

A billion-year shift in the formation of Earth’s largest ore deposits

Banded iron formations (BIFs) archive the relationship between Earth's lithosphere, hydrosphere, and atmosphere through time. However, constraints on the origin of Earth's largest ore deposits, hosted by BIFs, are limited by the absence of direct geochronology. Without this temporal context, genetic models cannot be correlated with tectono-thermal and atmospheric drivers responsible for BIF upgrading through time. Utilizing in situ iron oxide U-Pb geochronology, we provide a direct timeline of events tracing development of all the giant BIF-hosted hematite deposits of the Hamersley Province (Pilbara Craton, Western Australia). Direct dating demonstrates that the major iron ore deposits in the region formed during 1.4 to 1.1 Ga. This is one billion to hundreds of millions of years later than previous age constraints based upon 1) the presence of hematite ore clasts in conglomerate beds deposited before ~1.84 Ga, and 2) phosphate mineral dating, which placed the onset of iron mineralization in the Province at ~2.2 to 2.0 Ga during the great oxidation event. Dating of the hematite clasts verified the occurrence of a ~2.2 to 2.0 Ga event, reflecting widespread, but now largely eroded iron mineralization occurring when the Pilbara and Kaapvaal cratons were proximal. No existing phosphate mineral dates overlap with obtained hematite dates and therefore cannot be related to hematite crystallization and ore formation. New geochronology conclusively links all major preserved hematite deposits to a far younger (1.4 to 1.1 Ga) formation period, correlated with the amalgamation of Australia following breakup of the Columbia supercontinent.

Donor Sex and Passage Conditions Influence MSC Osteogenic Response in Mineralized Collagen Scaffolds.

Contemporary tissue engineering efforts often seek to use mesenchymal stem cells (MSCs) due to their multi-potent potential and ability to generate a pro-regenerative secretome. While many have reported the influence of matrix environment on MSC osteogenic response, few have investigated the effects of donor and sex. Here, a well-defined mineralized collagen scaffold is used to study the influence of passage number and donor-reported sex on MSC proliferation and osteogenic potential. A library of bone marrow and adipose tissue-derived stem cells from eight donors to examine donor viability in osteogenic capacity in mineralized collagen scaffolds is obtained. MSCs displayed reduced proliferative capacity as a function of passage duration. Further, MSCs showed significant sex-associated variability in osteogenic capacity. Notably, MSCs from male donors displayed significantly higher cell proliferation while MSCs from female donors displayed significantly higher osteogenic response via increased alkaline phosphate activity, osteoprotegerin release, and mineral formation in vitro. The study highlights the essentiality of including donor-reported sex as an experimental variable and reporting culture expansion in future studies of biomaterial regenerative potential.

Chitosan Scaffolds from Crustacean and Fungal Sources: A Comparative Study for Bone-Tissue-Engineering Applications.

Chitosan (CS), a biopolymer, holds significant potential in bone regeneration due to its biocompatibility and biodegradability attributes. While crustacean-derived CS is conventionally used in research, there is growing interest in fungal-derived CS for its equally potent properties in bone regenerative applications. Here, we investigated the physicochemical and biological characteristics of fungal (MDC) and crustacean (ADC)-derived CS scaffolds embedded with different concentrations of tricalcium phosphate minerals (TCP), i.e., 0(wt)%: ADC/MDC-1, 10(wt)%: ADC/MDC-2, 20(wt)%: ADC/MDC-3 and 30(wt)%: ADC/MDC-4. ADC-1 and MDC-1 lyophilised scaffolds lacking TCP minerals presented the highest zeta potentials of 47.3 ± 1.2 mV and 55.1 ± 1.6 mV, respectively. Scanning electron microscopy revealed prominent distinctions whereby MDC scaffolds exhibited striation-like structural microarchitecture in contrast to the porous morphology exhibited by ADC scaffold types. With regard to the 4-week scaffold mass reductions, MDC-1, MDC-2, MDC-3, and MDC-4 indicated declines of 55.98 ± 4.2%, 40.16 ± 3.6%, 27.05 ± 4.7%, and 19.16 ± 5.3%, respectively. Conversely, ADC-1, ADC-2, ADC-3, and ADC-4 presented mass reductions of 35.78 ± 5.1%, 25.19 ± 4.2%, 20.23 ± 6.3%, and 13.68 ± 5.4%, respectively. The biological performance of the scaffolds was assessed through in vitro bone marrow mesenchymal stromal cell (BMMSCs) attachment via indirect and direct cytotoxicity studies, where all scaffold types presented no cytotoxic behaviours. MDC scaffolds indicated results comparable to ADC, where both CS types exhibited similar physiochemical properties. Our data suggest that MDC scaffolds could be a potent alternative to ADC-derived scaffolds for bone regeneration applications, particularly for 10(wt)% TCP concentrations.

Safety of tenofovir alafenamide in people with HIV who experienced proximal renal tubulopathy on tenofovir disoproxil.

Twenty-eight individuals who experienced proximal renal tubulopathy (PRT, Fanconi syndrome) while receiving tenofovir disoproxil initiated tenofovir alafenamide (TAF) and were followed for 5 years. None developed recurrent PRT or experienced significant changes in estimated glomerular filtration rate (by creatinine or cystatin-C), albuminuria, proteinuria, retinol-binding proteinuria, fractional excretion of phosphate, alkaline phosphatase, or bone mineral density at the lumbar spine. These data suggest that TAF is a well tolerated treatment option for individuals vulnerable to developing PRT.

Recombinant human enamelin produced in Escherichia coli promotes mineralization in vitro

BackgroundEnamelin is an enamel matrix protein that plays an essential role in the formation of enamel, the most mineralized tissue in the human body. Previous studies using animal models and proteins from natural sources point to a key role of enamelin in promoting mineralization events during enamel formation. However, natural sources of enamelin are scarce and with the current study we therefore aimed to establish a simple microbial production method for recombinant human enamelin to support its use as a mineralization agent.ResultsIn the study the 32 kDa fragment of human enamelin was successfully expressed in Escherichia coli and could be obtained using immobilized metal ion affinity chromatography purification (IMAC), dialysis, and lyophilization. This workflow resulted in a yield of approximately 10 mg enamelin per liter culture. Optimal conditions for IMAC purification were obtained using Ni2+ as the metal ion, and when including 30 mM imidazole during binding and washing steps. Furthermore, in vitro mineralization assays demonstrated that the recombinant enamelin could promote calcium phosphate mineralization at a concentration of 0.5 mg/ml.ConclusionsThese findings address the scarcity of enamelin by facilitating its accessibility for further investigations into the mechanism of enamel formation and open new avenues for developing enamel-inspired mineralized biomaterials.

(Fe-Ca-Al)-phosphate mineralization enriched with rare earth elements in the sediments of the middle Jurassic paleovalley (Shankinka Occurrence, Moscow Region, central part of the Russian Plate)

(Fe-Ca-Al)-phosphate mineralization enriched with rare earth elements in the sediments of the middle Jurassic paleovalley (Shankinka Occurrence, Moscow Region, central part of the Russian Plate)

Bio-inspired super-wetting coatings constructed from interfacial mineralization of rare earth phosphate for oil/water separation applications

The oil fouling problem of lipophilic polymer matrix causes severe decline of separation performance, becoming one of the most serious challenges for oil/water separation. A chemical-stable and mechanical-strong anti-fouling coating is highly emerged. Herein, to achieve anti-fouling performance on diverse polymer substrates, a biomimic super-wetting coating is fabricated by interfacial mineralization of lanthanum phosphate (LaPO4). The strong interaction between ions makes LaPO4 very stable against acid, base, oil and mechanical impact, while the dense charges on the surface of LaPO4 attract water molecules and create a hydration layer to repulse oil under water. The membranes and meshes modified by such mineralized coating exhibit good separation efficiency (>99 %) and high permeation flux for oil-in-water emulsions and oil/water mixtures, respectively. In addition, notable cyclic flux recovery ability was fulfilled by water rinsing. The fabrication of such mineralized coating is easily operated through solution process and no harmful byproducts will be generated. Basically, the low-cost and eco-friendly mineralized coating is promising for oily water treatment in the practical complicated environment.

Features of Distribution of Rare-Earth Elements in Coals of the Far East

For the first time, the distribution of rare earth elements (REE) has been studied in detail for a number of coal facilities (30 deposits, 650 samples of coal and 210 samples of carbonaceous rocks). The ubiquitous presence of elevated concentrations of REE in coals has been noted. The REE mineral cluster in coals includes the association: ash content of coals – SiO2 – K2O – Al2o3 – TiO2 – Sc – Y – Dy – Ho – Er – Tm – Yb – Lu, and the association La – Ce – Pr – Nd – Sm – Eu – Gd – Tb. The presence of these elements of the mineral part of the coals is preferably in the composition of phosphate minerals – monazite and apatite (according to electron microscopy with microanalysis, the correlation of REE with P2o5). The content of individual REE in humic acids isolated from coals and fractions of coals of different densities has been studied. The specific role of organic matter(s) in the concentration of REE, their presence in the humus component of S and in low-ash coals is shown. Selective accumulation (fractionation) of heavy REE by organic matter has been experimentally established for the first time. Two genetic types of REE mineralization have been identified in coals: mainly terrigenous (hydrogenic) and tufogenic. The increased concentrations of REE in coals are due to the influence of the petrofund. The deposits were ranked according to the degree of prospects for REE based on an assessment of the resource potential of associated REE in the coals of the studied brown coal deposits. REE raw materials (lanthanides in coal ash) differ significantly from traditional types of rare earths ores by an incomparably large relative amount of heavy REE (on average 3–4 times), sometimes reaching 46% of the total REE content. Thus, coal ash is a unique non–traditional source of heavy lanthanides – more rare, valuable and expensive. The coals of the studied deposits should be considered as associated raw materials for rare earths.

Inoculation with Bacillus megaterium CNPMS B119 and Bacillus subtilis CNPMS B2084 improve P-acquisition and maize yield in Brazil.

Phosphorus (P) is a critical nutrient for plant growth, yet its uptake is often hindered by soil factors like clay minerals and metal oxides such as aluminum (Al), iron (Fe), and calcium (Ca), which bind P and limit its availability. Phosphate-solubilizing bacteria (PSB) have the unique ability to convert insoluble P into a soluble form, thereby fostering plant growth. This study aimed to assess the efficacy of inoculation of Bacillus megaterium B119 (rhizospheric) and B. subtilis B2084 (endophytic) via seed treatment in enhancing maize yield, grain P content, and enzyme activities across two distinct soil types in field conditions. Additionally, we investigated various mechanisms contributing to plant growth promotion, compatibility with commercial inoculants, and the maize root adhesion profile of these strains. During five crop seasons in two experimental areas in Brazil, Sete Lagoas-MG and Santo Antônio de Goiás-GO, single inoculations with either B119 or B2084 were implemented in three seasons, while a co-inoculation with both strains was applied in two seasons. All treatments received P fertilizer according to plot recommendations, except for control. Both the Bacillus strains exhibited plant growth-promoting properties relevant to P dynamics, including phosphate solubilization and mineralization, production of indole-3-acetic acid (IAA)-like molecules, siderophores, exopolysaccharides (EPS), biofilms, and phosphatases, with no antagonism observed with Azospirillum and Bradyrizhobium. Strain B2084 displayed superior maize root adhesion compared to B119. In field trials, single inoculations with either B119 or B2084 resulted in increased maize grain yield, with relative average productivities of 22 and 16% in Sete Lagoas and 6 and 3% in Santo Antônio de Goiás, respectively. Co-inoculation proved more effective, with an average yield increase of 24% in Sete Lagoas and 11% in Santo Antônio de Goiás compared to the non-inoculated control. Across all seasons, accumulated grain P content correlated with yield, and soil P availability in the rhizosphere increased after co-inoculation in Santo Antônio de Goiás. These findings complement previous research efforts and have led to the validation and registration of the first Brazilian inoculant formulated with Bacillus strains for maize, effectively enhancing and P grain content.

Increasing control over biomineralization in conodont evolution

Vertebrates use the phosphate mineral apatite in their skeletons, which allowed them to develop tissues such as enamel, characterized by an outstanding combination of hardness and elasticity. It has been hypothesized that the evolution of the earliest vertebrate skeletal tissues, found in the teeth of the extinct group of conodonts, was driven by adaptation to dental function. We test this hypothesis quantitatively and demonstrate that the crystallographic order increased throughout the early evolution of conodont teeth in parallel with morphological adaptation to food processing. With the c-axes of apatite crystals oriented perpendicular to the functional feeding surfaces, the strongest resistance to uniaxial compressional stress is conferred along the long axes of denticles. Our results support increasing control over biomineralization in the first skeletonized vertebrates and allow us to test models of functional morphology and material properties across conodont dental diversity.

Contribution of Saharan dust to chemical weathering fluxes and associated phosphate release in West Africa

Huge amounts of mineral dust are produced in northern Africa, representing the largest source of aerosols worldwide. Transatlantic dust transport is known to fertilize soils as far as in the Amazon Basin. Yet, the influence of Saharan dust on chemical weathering fluxes and associated nutrient release in West Africa remains largely overlooked. To address this issue, we analysed clay fractions (<2 µm) of river sediments (n = 37) from across the Niger River basin - the largest river system in West Africa - using neodymium and hafnium isotope compositions as proxies for provenance (εNd) and chemical weathering (ΔεHf CLAY).Compared to previously published data for corresponding sand fractions, measured εNd values indicate significant size-dependent decoupling for Nd isotopes in most samples, with εNd differences between clay and sand fractions yielding values as great as ∼26 ε-units. Using mixing models, we show that this discrepancy reflects the overwhelming presence in the studied clay fractions of Harmattan dust blown from the Bodélé Depression in Chad, which we estimate to account for about 40 % of the fine-grained sediment load exported to the Gulf of Guinea. Additionally, significant ΔεHf CLAY variability occurs across the Niger catchment, partly explained by the presence of zircon in clay-size fractions, but also by preferential alteration of dust-borne accessory phosphate minerals in the subtropical regions of the watershed.Based on these results, we propose that Saharan dust plays a major role in controlling regional patterns of chemical weathering in West Africa, suggesting that enhanced wet deposition of mineral dust in shield areas dominated by transport-limited weathering regime can result in a large increase in weatherability and associated release of phosphorus. These findings have general implications for the importance of mineral aerosols in controlling sediment yield and the supply of weathering-derived nutrients to continental areas bordering large subtropical deserts worldwide.

A novel multi-model estimation of phosphorus in coal and its ash using FTIR spectroscopy

The level of phosphorus must be carefully monitored for proper and effective utilization of coal and coal ash. The phosphorus content needs to be assessed to optimize combustion efficiency and maintenance costs of power plants, ensure quality, and minimize the environmental impact of coal and coal ash. The detection of low levels of phosphorus in coal and coal ash is a significant challenge due to its complex chemical composition and low concentration levels. Effective monitoring requires accurate and sensitive equipment for the detection of phosphorus in coal and coal ash. X-ray fluorescence (XRF) is a commonly used analytical technique for the determination of phosphorus content in coal and coal ash samples but proves challenging due to their comparatively weak fluorescence intensity. Fourier Transform Infrared spectroscopy (FTIR) emerges as a promising alternative that is simple, rapid, and cost-effective. However, research in this area has been limited. Until now, only a limited number of research studies have outlined the estimation of major elements in coal, predominantly relying on FTIR spectroscopy. In this article, we explore the potential of FTIR spectroscopy combined with machine learning models (piecewise linear regression—PLR, partial least square regression—PLSR, random forest—RF, and support vector regression—SVR) for quantifying the phosphorus content in coal and coal ash. For model development, the methodology employs the mid-infrared absorption peak intensity levels of phosphorus-specific functional groups and anionic groups of phosphate minerals at various working concentration ranges of coal and coal ash. This paper proposes a multi-model estimation (using PLR, PLSR, and RF) approach based on FTIR spectral data to detect and rapidly estimate low levels of phosphorus in coal and its ash (R2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^2$$\\end{document} of 0.836, RMSE of 0.735 ppm, RMSE (%) of 34.801, MBE of − 0.077 ppm, MBE (%) of 5.499, and MAE of 0.528 ppm in coal samples and R2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^2$$\\end{document} of 0.803, RMSE of 0.676 ppm, RMSE (%) of 38.050, MBE of − 0.118 ppm, MBE (%) of 4.501, and MAE of 0.474 ppm in coal ash samples). Our findings suggest that FTIR combined with the multi-model approach combining PLR, PLSR, and RF regression models is a reliable tool for rapid and near-real-time measurement of phosphorus in coal and coal ash and can be suitably modified to model phosphorus content in other natural samples such as soil, shale, etc.

Naturally occurring radioactive material (NORM) in Saudi Arabia: A Review

Saudi Arabia, the world's largest crude oil exporter, also possesses rich deposits of natural resources like phosphate, bauxite, copper, and various minerals. Extracting and processing these resources can concentrate naturally occurring radionuclides in the resulting products, byproducts, residues, and wastes. This can sometimes elevate their activity concentrations above original levels, potentially increasing exposure risks for workers and the public, and contaminating the environment.This review provided a comprehensive overview of naturally occurring radioactive materials (NORM) across various industries in Saudi Arabia. It outlines the regulatory framework established by the country's authority for NORM management. By reviewing current literature, the article presents activity concentrations of key radionuclides of interest - 40K and those from the 238U and 232Th decay series-within different industries. The review highlights the need for further research to assess the impact of industrial processes on the activity concentrations of natural radionuclides. It concludes by calling for additional studies to address the significant knowledge gap on NORM in specific industries, particularly phosphate, bauxite, water treatment plant and oil and gas, which have the potential to generate radioactive waste. The importance of characterizing industries involving NORM is emphasized for evaluating radiological impact and implementing appropriate safety measures.

A Fusion-Growth Protocell Model Based on Vesicle Interactions with Pyrite Particles.

Protocell models play a pivotal role in the exploration of the origin of life. Vesicles are one type of protocell model that have attracted much attention. Simple single-chain amphiphiles (SACs) and organic small molecules (OSMs) possess primitive relevance and were most likely the building blocks of protocells on the early Earth. OSM@SAC vesicles have been considered to be plausible protocell models. Pyrite (FeS2), a mineral with primitive relevance, is ubiquitous in nature and plays a crucial role in the exploration of the origin of life in the mineral-water interface scenario. "How do protocell models based on OSM@SAC vesicles interact with a mineral-water interface scenario that simulates a primitive Earth environment" remains an unresolved question. Hence, we select primitive relevant sodium monododecyl phosphate (SDP), isopentenol (IPN) and pyrite (FeS2) mineral particles to build a protocell model. The model investigates the basic physical and chemical properties of FeS2 particles and reveals the effects of the size, content and duration of interaction of FeS2 particles on IPN@SDP vesicles. This deepens the understanding of protocell growth mechanisms in scenarios of mineral-water interfaces in primitive Earth environments and provides new information for the exploration of the origin of life.

Phosphates on Mars and Their Importance as Igneous, Aqueous, and Astrobiological Indicators

This paper reviews the phosphate phases in meteorites and those measured by landed spacecraft, what they reveal about past igneous and aqueous conditions on Mars, and important implications for potential prebiotic chemistry, past habitability, and potential biosignatures that could be detected in samples returned from Mars. A review of the 378 martian meteorites as of 2023 indicate that of the two most common phosphate minerals in Mars meteorites, merrillite and apatites, the apatite composition is largely F- and Cl-rich, with shergottites containing more OH. The phosphate concentrations examined across multiple missions show a relatively narrow range of phosphate, with higher concentrations observed in the Mount Sharp Group in Gale crater and Wishstone at Gusev crater and lower concentrations observed at Jezero crater floor and Jezero fan. Possible secondary phosphates detected on Mars, including Fe phosphates at Jezero crater and Gusev crater and Ca- and Al-bearing secondary phosphates, temperatures of formation of secondary phases and their dissolution rates and solubilities are reviewed and summarized. Despite this wealth of information about phosphates on Mars, due to their fine scale and relatively low concentrations, Mars Sample Return is needed to better understand phosphate and its implications for the igneous, aqueous, and astrobiological history of Mars.

Alendronate as Bioactive Coating on Titanium Surfaces: An Investigation of CaP-Alendronate Interactions.

The surface modification of dental implants plays an important role in establishing a successful interaction of the implant with the surrounding tissue, as the bioactivity and osseointegration properties are strongly dependent on the physicochemical properties of the implant surface. A surface coating with bioactive molecules that stimulate the formation of a mineral calcium phosphate (CaP) layer has a positive effect on the bone bonding process, as biomineralization is crucial for improving the osseointegration process and rapid bone ingrowth. In this work, the spontaneous deposition of calcium phosphate on the titanium surface covered with chemically stable and covalently bound alendronate molecules was investigated using an integrated experimental and theoretical approach. The initial nucleation of CaP was investigated using quantum chemical calculations at the density functional theory (DFT) level. Negative Gibbs free energies show a spontaneous nucleation of CaP on the biomolecule-covered titanium oxide surface. The deposition of calcium and phosphate ions on the alendronate-modified titanium oxide surface is governed by Ca2+-phosphonate (-PO3H) interactions and supported by hydrogen bonding between the phosphate group of CaP and the amino group of the alendronate molecule. The morphological and structural properties of CaP deposit were investigated using scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and attenuated total reflectance Fourier transform infrared spectroscopy. This integrated experimental-theoretical study highlights the spontaneous formation of CaP on the alendronate-coated titanium surface, confirming the bioactivity ability of the alendronate coating. The results provide valuable guidance for the promising forthcoming advancements in the development of biomaterials and surface modification of dental implants.

Evaluation of vitamin D deficiency and low bone mass in children with asthma in fars province: A case-control study.

Asthma is a chronic inflammatory pulmonary disease which affects 10%-20% of children and adolescents. Inhaled corticosteroids (ICS) is one of its most effective therapies. The effect of systemic corticosteroids on decreasing bone mineral density (BMD) was investigated and proved in children; however, the influence of ICSs on bone density has still remained unclear. This study evaluates the bone mineral density of children and adolescents with asthma in southern Iran and the associated factors, for example, amount of used inhaled steroid. This case-control study enrolled 41 children and adolescents (aged 8-18 years) with asthma and their age and gender-matched controls in 2019-2020. Serum Calcium, phosphate, vitamin D, and bone mineral density were measured. Their physical activity, sun exposure, and fracture history were evaluated subjectively. Lumbar BMD and BMD Z-score in patients showed no significant difference with controls (p = 0.23, p = 0.73). Also, it showed that there was no significant difference in biochemical studies, growth, and bone densitometry parameters between patients who used ICSs for less than 3 months/year corticosteroid therapy compared to those with equal or more than 3 months/year usage. Prevalence of vitamin D deficiency was 28% and 8% in the controls and patients, respectively (p = 0.005). The present study showed that 9.46% of children and adolescents with asthma had low bone mass for chronological age, and it is not significantly higher than normal population. Dosage of inhaled steroid did not associate with osteoporosis in these patients. Prevalence of vitamin D deficiency in patients was lower than normal population, probably due to receiving vitamin D in their routine follow-ups.

Clam Shell-Derived Hydroxyapatite: A Green Approach for the Photocatalytic Degradation of a Model Pollutant from the Textile Industry.

This work aims to evaluate the potential use of natural wastes (in particular, clam shells) to synthesize one of the most well-known and versatile materials from the phosphate mineral group, hydroxyapatite (HAP). The obtained material was characterized in terms of morphology and composition using several analytical methods (scanning electron microscopy-SEM, X-ray diffraction-XRD, X-ray fluorescence-XRF, Fourier transform infrared spectroscopy-FTIR, thermal analysis-TGA, and evaluation of the porosity and specific surface characteristics by the Brunauer-Emmett-Teller-BET method) in order to confirm the successful synthesis of the material and to evaluate the presence of potential secondary phases. The developed material was further doped with iron oxide (HAP-Fe) using a microwave-assisted method, and both materials were evaluated in terms of photocatalytic activity determined by the photodecomposition of methylene blue (MB) which served as a contaminant model. The best results (approx. 33% MB degradation efficiency, after 120 min. of exposure) were obtained for the hydroxyapatite material, superior to the HAP-Fe composite (approx. 27%). The utilization of hydroxyapatite obtained from clam shells underscores the importance of sustainable and eco-friendly practices in materials syntheses. By repurposing waste materials from the seafood industry, we not only reduce environmental impact, but also create a valuable resource with diverse applications, contributing to advancements in both healthcare and environmental protection.

Deciphering the U-Pb dates of sedimentary phosphates: A complex example from the Upper Cretaceous-Lower Paleogene series in northwestern Morocco

Uranium‑lead geochronology rapidly generates dates of rock deposition/formation with reasonable precision and accuracy using laser ablation inductively coupled plasma mass spectrometry, which is needed for bracketing stratigraphy. However, previous radiometric U-Pb dating of biogenic (i.e., bones and teeth) and sedimentary phosphate minerals have had limited success, probably because of the nanometric to micrometric crystallites that generate open system behavior. Sediment lithification inhibiting trace element exchange between minerals and porewaters and thus forcing phosphorus-rich crystallites to adopt a closed system behavior has been suggested for interpreting U-Pb dating of carbonate fluorapatite (CFA). Despite these insights, what remains lacking is extensive U-Pb CFA dating at the regional scale to test whether several processes influence the timing of U-Pb system closure by inhibiting U and Pb exchanges. Here, we report U-Pb CFA dating from four sampling sites in northwestern Morocco to understand better the meaning of U-Pb dates in CFA. The Upper Cretaceous-Lower Paleogene phosphate series yields anomalously low 207Pb/206Pb initial ratios and young dates ranging from 37.3 ± 2.4 Ma to 22.7 ± 0.7 Ma, which does not agree with the terrestrial lead model composition for Paleogene ages and the known biostratigraphic ages, respectively. We argue that ancient radiogenic Pb from leached polymetallic mineralizations of the regional environment have been incorporated into CFA and that a 25 to 40 Ma-long widespread resetting of the U-Pb system has affected the northwestern Moroccan phosphates. Neither CFA-hosted CO32− concentrations nor rare earth element and yttrium contents indicate post-depositional modifications of the chemical nature of phosphate-bearing rocks. Burial diagenesis promoting sediment lithification is one of the mechanisms that have triggered final closure of the U-Pb system of CFA minerals and, interestingly, the sedimentation rate was probably not a controlling factor. Unexpectedly, U-Pb dates of ∼23 Ma from three stratigraphic levels separated by several million years seem to be concomitant with the regional emersion and generalized continentalization of northwestern Morocco, allowing CFA to behave as a closed system. We conclude that the laser ablation inductively coupled mass spectrometry U-Pb dating of biogenic and sedimentary CFA minerals must be carefully employed to date the timing of fossilization or sediment deposition.