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A mining tailing dam rupture in Brazil in November 2015 released millions of tons of mining waste into the Rio Doce ecosystem, leading to long-term aquatic ecosystem impacts. Although multiple lines of evidence indicate tailings associations with potentially toxic elements in estuarine sediments and biological impact and bioaccumulation pathways in fishes, the extent of contamination in base benthic species is still largely unknown. Moreover, Rare Earth Elements (REE) have not received any attention in this regard. This study assessed REE in fiddler crabs (Minuca rapax) sampled from the Rio Doce estuary in 2017, nearly 2 years after the disaster. The ΣREE in crab hepatopancreas and muscle were high (327.83 mg kg-1 w.w. and 33.84 mg kg-1 w.w., respectively, compared to other assessments in crabs, indicating a preference for REE bioaccumulation in the hepatopancreas compared to muscle. Neodimium, La, and Ce were detected at the highest concentrations. The REE from the Rio Doce Basin were, thus, transported and deposited in the estuary with the mine tailings slurry, leading to bioaccumulation in crabs. This may lead to trophic effects and other ecological impacts not readily measured by typical impact assessment studies, revealing an invisible and not typically acknowledged damage to the Rio Doce estuary.

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In this work, bioaccessibility tests for rare earth elements (REEs), Th, and U in marine sediment were carried out, in addition to complementary tests for cytotoxicity and bioaccumulation for the elements La, Ce, Eu, and Gd. The evaluation of human health risk through dermal absorption and oral ingestion was performed using the hazard quotient (HQ). According to the gastric digestion simulation (SBET), it was observed that the elements Ce and Nd exhibited higher absorption capacities in the human body (> 2 µg g-1). La and Sc presented intermediate concentrations (close to 1 µg g-1), while the remaining elements displayed concentrations below 0.5 µg g-1. In the gastrointestinal digestion extraction stage (PBET), all the elements maintained a similar absorption capacity to that observed in SBET, except for the absorption of Y which increased. The results of the bioaccumulation test conducted with fibroblast cells (L929) indicated that La and Eu had a 25% probability of intracellular accumulation. The cell viability test, with exposure to a standard REEs, Th, and U solution in 2% v v-1 HNO3 medium (until 100 µg mL-1) and an aqueous solution of La2O3, Gd(NO3)3, Ce(NO3)3, and Eu2O3 (until 1000 µg mL-1), did not demonstrate cytotoxic effects on fibroblast cells. Considering the ingestion hazard quotient (HQing) and dermal hazard quotient (HQderm) obtained, it was suggested that there is no significant risk of non-carcinogenic effects (< 1). However, they had higher HQing values compared to HQderm, indicating that REEs pose more significant risk to human health through oral ingestion absorption than dermal absorption.

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We present a study on the green synthesis of undoped and Er-doped ZnO compounds using Mangifera indica gum (MI). A set of tests were conducted to assess the structure of the material. The tests included X-ray diffraction, Raman, and Fourier-transform infrared spectroscopy. Optical properties were studied using diffuse reflectance and photoluminescence. Morphological and textural investigations were done using SEM images and N2 adsorption/desorption. Furthermore, photocatalytic tests were performed with methylene blue (MB), yellow eosin (EY), and the pharmaceutical drug ibuprofen (IBU) under UV irradiation. The study demonstrated that replacing the stabilizing agent with Mangifera indica gum is an effective method for obtaining ZnO nanoparticles. Additionally, the energy gap of the nanoparticles exhibits a slight reduction in value. Photoluminescence studies showed the presence of zinc vacancies and other defects in both samples. In the photocatalytic test, the sample containing Er3+ exhibited a degradation of 99.7% for methylene blue, 81.2% for yellow eosin, and 52.3% for ibuprofen over 120 min. In the presence of methyl alcohol, the degradation of MB and EY dyes is 16.7% and 55.7%, respectively. This suggests that hydroxyl radicals are responsible for the direct degradation of both dyes. In addition, after the second reuse, the degradation rate for MB was 94.08%, and for EY, it was 82.35%. For the third reuse, the degradation rate for MB was 97.15%, and for EY, it was 17%. These results indicate the significant potential of the new semiconductor in environmental remediation applications from an ecological synthesis.

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Iron ore tailings are stored in large dams and pose risks to the environment around the world. In Brazil, the rupture of these dams has become frequent and has generated environmental and social concern. Rare earth elements are good tracers of sediment sources and our results indicated chronic contamination of the seabed sediment from the marine region affected by the Fundão Dam tailings since 2015, including areas of environmental protection. This research, carried out between November 2018 and September 2021, with a database of 575 samples, showed a greater amount of contaminated material in the marine region adjacent to the Doce River mouth. Although data suggest prior mining contamination of the Doce River basin, the Fundão episode was an empirical and massive example of the environmental damage caused by these human activities over the centuries, showing that the impact remains in the shallow marine environments for years. Integr Environ Assess Manag 2024;20:179-188. © 2023 SETAC.

Os rejeitos de minério de ferro são armazenados em grandes barragens que trazem riscos ao meio ambiente em todo o mundo. No Brasil, o rompimento dessas barragens tem se tornado frequente e gerado preocupação ambiental e social. Elementos terras raras são bons marcadores de fontes sedimentares e nossos resultados indicaram uma contaminação crônica da região marinha afetada pelos rejeitos da barragem de Fundão, incluindo áreas de proteção ambiental. Esta pesquisa teve com 575 amostras analisadas entre os meses de novembro de 2018 e outubro de 2021, com a região marinha adjacente a foz do Rio Doce apresentando o maior grau de impacto. Embora os dados ressaltem a contaminação histórica da mineração na bacia do Rio Doce, o episódio do Fundão foi um exemplo empírico e massivo dos danos ambientais causados por essas atividades ao longo dos séculos, mostrando que o impacto permanece nos ambientes marinhos rasos por anos. Integr Environ Assess Manag 2024;20:179-188.

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TbxPr1-xAl2are ferrimagnetic materials exhibiting magnetocaloric effect that have gained considerable attention due to their potential use as an alternative in refrigeration, magnetic sensors and in information storage technology. Here using the mean field approach numerical simulations were conducted forx= 0.1, 0.2, 0.3, 0.4, 0.5, and 0.75, to analyze selected physical properties, such as x-ray and neutron powder diffraction, magnetization and heat capacity. The simulations successfully reproduced the experimental data providing a comprehensive characterization and improved understanding of this family of compound.

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The present research aimed to evaluate the use of grape stalk in the adsorption of lanthanum and cerium to identify the best operating conditions enabling the application of the bioadsorbent in REEs leached from phosphogypsum. The grape stalk was characterized and showed an amorphous structure with a heterogeneous and very porous surface. Also, it was possible to identify the groups corresponding to carboxylic acids, phenols, alcohols, aliphatic acids, and aromatic rings. The pH effect study showed that the adsorption process of La3+ and Ce3+ ions was favored at pH 5.0. The adsorption kinetics followed the pseudo-second-order model. In just 20 min, 80% saturation was reached, while equilibrium was reached after 120 min. The adsorption isotherms were appropriately adjusted to the Langmuir model, and the maximum adsorption capacities were obtained at 298 K, which were 35.22 mg g-1 for La3+ and 37.99 mg g-1 for Ce3+. Furthermore, the adsorption process was favorable, spontaneous, and exothermic. In the study's second phase, phosphogypsum was leached with a sulfuric acid solution. Then, the adsorption of REEs was carried out under the experimental conditions of pH after leaching and pH 5.0 (adjustment carried out with sodium hydroxide solution) at 298 K for 120 min and with adsorbent dosages of 1 and 5 g L-1. This process resulted in removal percentages above 95% for the most abundant REEs, such as neodymium, lanthanum, and cerium, at pH 5.0 and a dosage of 5 g L-1, demonstrating the effectiveness of the bioadsorbent used. These results indicate the potential of using grape residue as a promising bioadsorbent in recovering rare earth elements from phosphogypsum leachate.

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This study introduces a novel method for producing Ag nanoclusters (NCs) within GeO2-PbO glasses doped with Tm3+ ions. Sample preparation involved the melt-quenching method, employing adequate heat treatment to facilitate Ag NC formation. Absorption spectroscopy confirmed trivalent rare-earth ion incorporation. Ag NC identification and the amorphous structure were observed using transmission electron microscopy. A tunable visible emission from blue to the yellow region was observed. The energy transfer mechanism from Ag NCs to Tm3+ ions was demonstrated by enhanced 800 nm emission under 380 and 400 nm excitations, mainly for samples with a higher concentration of Ag NCs; moreover, the long lifetime decrease of Ag NCs at 600 nm (excited at 380 and 400 nm) and the lifetime increase of Tm3+ ions at 800 nm (excitation of 405 nm) corroborated the energy transfer between those species. Therefore, we attribute this energy transfer mechanism to the decay processes from S1→T1 and T1→S0 levels of Ag NCs to the 3H4 level of Tm3+ ions serving as the primary path of energy transfer in this system. GeO2-PbO glasses demonstrated potential as materials to host Ag NCs with applications for photonics as solar cell coatings, wideband light sources, and continuous-wave tunable lasers in the visible spectrum, among others.

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In this study, we emphasize the critical role of sample pretreatment. We report on the behavior of NdFeB magnet samples exposed to four different acid media for digestion. NdFeB magnets are becoming a significant source of neodymium, a rare-earth element critical to many technologies and a potential substitute for traditional mining of the element. To address this, we meticulously tested nitric acid, hydrochloric acid, acetic acid, and citric acid, all at a concentration of 1.6 M, as economical and environmentally friendly alternatives to the concentrated mineral acids commonly used in the leaching of these materials. The pivotal stage involves the initial characterization of samples in the solid state using SEM-EDX and XPS analysis to obtain their initial composition. Subsequently, the samples are dissolved in the four aforementioned acids. Finally, neodymium is quantified using ICP-OES. Throughout our investigation, we evaluated some analytical parameters to determine the best candidate for performing the digestion, including time, limits of detection and quantification, accuracy, recovery of spike samples, and robustness. After careful consideration, we unequivocally conclude that 1.6 M nitric acid stands out as the optimal choice for dissolving NdFeB magnet samples, with the pretreatment of the samples being the critical aspect of this report.

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YMnO3 is a P-type semiconductor with a perovskite-type structure (ABO3). It presents two crystalline systems: rhombohedral and hexagonal, the latter being the most stable and studied. In the hexagonal system, Mn3+ ions are coordinated by five oxygen ions forming a trigonal bipyramid, and the Y3+ ions are coordinated by five oxygen ions. This arrangement favors its ferroelectric and ferromagnetic properties, which have been widely studied since 1963. However, applications based on their optical properties have yet to be explored. This work evaluates the photoelectric response and the photocatalytic activity of yttrium manganite in visible spectrum wavelengths. To conduct this, a rod-obelisk-shaped yttrium manganite with a reduced indirect bandgap value of 1.43 eV in its hexagonal phase was synthesized through the precipitation method. The synthesized yttrium manganite was elucidated by solid-state techniques, such as DRX, XPS, and UV-vis. It was non-toxic as shown by the 100% leukocyte viability of mice BALB/c.

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Rare earth elements (REE) have unique chemical properties, which allow their use as geochemical tracers. In this context, the present study aims to assess the role of Funil Reservoir on REE biogeochemical behavior. We collected water samples upstream of the reservoir (P-01) in the city of Queluz, inside the reservoir (P-02), and downstream of Funil Reservoir (P-03) in the city of Itatiaia, RJ. In the field, physicochemical parameters were measured using a probe (pH, temperature, electrical conductivity, and dissolved oxygen). In the laboratory, water samples were filtered (0.45 µm) and properly packed until chemical analysis. Chlorophyll a concentrations were determined by a spectrophotometric method and suspended particulate matter (SPM) by a gravimetric method. Ionic concentrations were determined by ion chromatography technique and REE concentrations were determined by ICP-MS. Chlorophyll a concentrations were higher in Funil Reservoir. Ionic concentrations in Queluz (P-01) suggest anthropic contamination. The sum of REE in the dissolved fraction ranged from 2.12 to 12.22 µg L-1. A positive anomaly of La in Queluz indicates anthropic contamination. The observed patterns indicate that Funil Reservoir acts as a biogeochemical barrier, modifying the fluvial transport of REE. Nonetheless, another factor that probably influences REE behavior is the algal bloom that occurs in reservoirs during the rainy season. The seasonal behavior of algae can influence REE biogeochemistry through the incorporation and release of trace metals.

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Coal has been a valuable natural resource for Mexico not just for its relative abundance but for its critical role in the development of the steel and energy industries. It has been also important in the socioeconomic context of the northeast of the country. However, since years ago, coal mining is facing a transition due to the emergence of new energy sources and the public concern about global warming. A brief review on coal reserves, production and possible non-power uses was carried out to provide insight on the reserves in a global context, extraction patterns and alternatives that the Mexican coal industry has to evolve. For this purpose, Mexican coal reserves were overviewed and contextualized at a global level and total coal production figures from 1970 to 2021 were analyzed to identify fluctuations and differences in the amounts produced between coking and non-coking coal. Further, rare earth elements, carbon fiber and humic acid from coal were briefly reviewed with the aim of initiating a debate on the high value-added products that can be obtained and the technologies that can be adopted to develop the coal industry of Mexico. Coal proven reserves in Mexico are of 1211 million tonnes and, from 1970 to 2021, 428.11 million tonnes have been produced. Of the total cumulative production, 68.8% corresponds to non-coking coal and 31.2% to coking coal.

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Rare earth elements have played a key role in technological advancement, attracting great visibility in the global commodity market. Xenotime, a heavy rare earth resource (YPO4), can be found associated with granitic rocks, as in the Pitinga deposit, located in the Brazilian Amazon region, where the main gangue minerals are quartz, microcline and albite. This research investigates the application of a new collector produced from pracaxi oil, an Amazon oil abundant in Brazil, in the selective flotation between xenotime and its main gangue minerals. The study conducted the synthesis and characterization of the collector, the chemical, mineralogical and surface characterization of minerals, as well as the evaluation of collector adsorption and flotability via microflotation tests, zeta potential measurements, surface tension determination and XRD, WDXRF, ICP-MS, FTIR and XPS analyses. The pracaxi collector was found to be mainly composed of oleic acid (56.2%), linoleic acid (14.1%) and behenic acid (10.6%), in addition to exhibiting a critical micelle concentration (CMC) of approximately 150 mg/L. Microflotation tests indicated that the best condition for selective recovery of xenotime occur at alkaline condition (pH 9.0), presenting selectivity of approximately 90% with collector concentration of 10.0 mg/L. The zeta potential data confirmed a selective adsorption of pracaxi collector onto xenotime, with an increase in the surface charge from -30 mV to -68 mV, whereas no significant changes were detected in the silicates. The FTIR spectra showed the appearance of a band at 1545 cm-1 on the surface of the xenotime after collector adsorption, which indicates, along with the zeta potential data, the chemical nature of the adsorption. The presence of small amounts of iron in the lattice structure of silicate gangues can act as an activator, and therefore, may be responsible for the small flotability of these minerals. The performance of the pracaxi oil collector presented in this study indicates the great potential of this Amazonian oil for application in the selective flotation of xenotime ores found in the region.

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After more than a decade since smartphones became consolidated in the market, many recycling solutions have been proposed to deal with them. To continue developing useful solutions and enable adjustment of routes, this mini-review aims to analyse the current research scenario, presenting relevant gaps, trends and opportunities. From a structured searching and screening procedure, a vast source of data was arranged and is available to extract useful information (43 studies on composition and 93 studies on recycling). The study provides discussions about the history of smartphone development, constituent materials and recycling methods for different components, comparisons between feature phones and smartphones and others. Among some conclusions, the authors highlight the lack of studies on pre-extractive methods, green chemistry, recovery of critical and precious metals, determination of priority materials for recovery and solutions for entire devices. In the end, a list containing six research gaps for composition studies and seven research gaps for recycling studies is provided and may be seen as opportunities for future research.

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Currently, SEM-EDS is used to detect gunshot residue (GSR) from the presence of Ba, Pb, and Sb in the sample. However, the development of new nontoxic ammunition (NTA) has prevented conventional metals from being found. In this work, we aim to determine the presence of an inorganic luminescent chemical marker based on rare earth in gunshot residues using the technique of squarewave voltammetry (SWV). After firing, the luminescent complex [(Eu2 Zr)(btc)3 (Hbtc)0.5 .6H2 O], which is used as a chemical marker, can be detected under a UV lamp. An aqueous solution with 0.1 mol L-1 KCl as supporting electrolyte can be easily collected on carbon paste electrode surfaces for SWV analysis A = 100 mV, f = 10 Hz, and step potential of 5 mV are required. The luminescent marker incorporated into the carbon paste electrode showed two anodic peak currents in the region of 0.4 V (vs Ag/AgCl) and at 0.75 V (vs Ag/AgCl) and also a cathodic one in 0.4 V (vs Ag/AgCl). SEM-EDS was able to analyze the same voltammetric results for conventional and nontoxic ammunition containing the luminescent marker. Therefore, voltammetry and SEM-EDS are valid for detecting the new residue marker in GSR. Despite this, the electrochemical method is still more advantageous because of its low cost and lack of expensive equipment and supplies in forensic laboratories.

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In this work, a ZnO hemisphere-like structure co-doped with Er and Cr was obtained by the co-precipitation method for photocatalytic applications. The dopant's effect on the ZnO lattice was investigated using X-ray diffraction, Raman, photoluminescence, UV-Vis and scanning electron microscopy/energy dispersive spectroscopy techniques. The photocatalytic response of the material was analyzed using methylene blue (MB) as the model pollutant under UV irradiation. The wurtzite structure of the Zn0.94Er0.02Cr0.04O compound presented distortions in the lattice due to the difference between the ionic radii of the Cr3+, Er3+ and Zn2+ cations. Oxygen vacancy defects were predominant, and the energy competition of the dopants interfered in the band gap energy of the material. In the photocatalytic test, the MB degradation rate was 42.3%. However, using optimized H2O2 concentration, the dye removal capacity reached 90.1%. Inhibitor tests showed that •OH radicals were the main species involved in MB degradation that occurred without the formation of toxic intermediates, as demonstrated in the ecotoxicity assays in Artemia salina. In short, the co-doping with Er and Cr proved to be an efficient strategy to obtain new materials for environmental remediation.

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The use of environmental tracers brings comprehensive benefits to the management of water resources since it helps to prevent their pollution, minimize public health risks, and thus reduce the impact of urbanization. In Brazil, the Guarani Aquifer System (GAS) has strategic and environmental importance, making its preservation and sustainable exploitation mandatory. The present study aimed at evaluating sources of contamination in the GAS using the combination of geochemical data and two environmental tracers: nitrate isotopes (15NNO3 and 18ONO3) and one rare earth element (Gadolinium-Gd). For that, five wells-four exploiting the GAS and one the Bauru Aquifer System (BAS)-were selected to discuss the human inputs in groundwater used for public supply in an urban area. Traditional physicochemical analyses were conducted for six campaign samplings and nitrate monitoring for this period was evaluated on a time scale, also considering the accumulated rainfall. Besides that, the double isotopic method (DIM), e.g., δ18ONO3 e δ15NNO3, was applied to identify the fractionation and enable the distinction of the nitrate contamination source. In addition, the determination of anomalies of Gd, a wastewater-derived contaminant, was also performed to verify recent human inputs in groundwater. The results show that the local existence of nitrate in the GAS and BAS-even at low concentrations (values from 0.26 to 6.68 mg L-1)-originated from anthropogenic inputs (septic waste), as indicates the typical isotopic signals ratio in the isotopic approach. Associated with that, the evaluation of Gd permitted the separation of groundwater samples into older or more recent leakages. The use of environmental tracers to assess anthropogenic inputs in groundwater reiterates the importance of adopting more effective protection strategies for water resources management systems, in order to prevent contamination.

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The rare-earth-free MnAlC alloy is currently considered a very promising candidate for permanent magnet applications due to its high anisotropy field and relatively high saturation magnetization and Curie temperature, besides being a low-cost material. In this work, we presented a simple fabrication route that allows for obtaining a magnetically enhanced bulk τ-MnAlC magnet. In the fabrication process, an electric arc-melting method was carried out to melt ingots of MnAlC alloys. A two-step solution treatment at 1200 °C and 1100 °C allowed us to synthesize a pure room-temperature ε-MnAlC ingot that completely transformed into τ-MnAlC alloy, free of secondary phases, after an annealing treatment at 550 °C for 30 min. The Rietveld refinements and magnetization measurements demonstrated that the quenched process produces a phase-segregated ε-MnAlC alloy that is formed by two types of ε-phases due to local fluctuation of the Mn. Room-temperature hysteresis loops showed that our improved τ-MnAlC alloy exhibited a remanent magnetization of 42 Am2/kg, a coercive field of 0.2 T and a maximum energy product, (BH)max, of 6.07 kJ/m3, which is higher than those reported in previous works using a similar preparation route. Experimental evidence demonstrated that the synthesis of a pure room-temperature ε-MnAlC played an important role in the suppression of undesirable phases that deteriorate the permanent magnet properties of the τ-MnAlC. Finally, magnetic images recorded by Lorentz microscopy allowed us to observe the microstructure and magnetic domain walls of the optimized τ-MnAlC. The presence of magnetic contrasts in all the observed grains allowed us to confirm the high-quality ferromagnetic behavior of the system.

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Light-based therapies and diagnoses including photodynamic therapy (PDT) have been used in many fields of medicine, including the treatment of non-oncological diseases and many types of cancer. PDT require a light source and a light-sensitive compound, called photosensitizer (PS), to detect and destroy cancer cells. After absorption of the photon, PS molecule gets excited from its singlet ground state to a higher electronically excited state which, among several photophysical processes, can emit light (fluorescence) and/or generate reactive oxygen species (ROS). Moreover, the biological responses are activated only in specific areas of the tissue that have been submitted to exposure to light. The success of the PDT depends on many parameters, such as deep light penetration on tissue, higher PS uptake by undesired cells as well as its photophysical and photochemical characteristics. One of the challenges of PDT is the depth of penetration of light into biological tissues. Because photon absorption and scattering occur simultaneously, these processes depend directly on the light wavelength. Using PS that absorbs photons on "optical transparency windows" of biological tissues promises deeper penetration and less attenuation during the irradiation process. The traditional PS normally is excited by a higher energy photon (UV-Vis light) which has become the Achilles' heel in photodiagnosis and phototreatment of deep-seated tumors below the skin. Thus, the need to have an effective upconverter sensitizer agent is the property in which it absorbs light in the near-infrared (NIR) region and emits in the visible and NIR spectral regions. The red emission can contribute to the therapy and the green and NIR emission to obtain the image, for example. The absorption of NIR light by the material is very interesting because it allows greater penetration depth for in vivo bioimaging and can efficiently suppress autofluorescence and light scattering. Consequently, the penetration of NIR radiation is greater, activating the biophotoluminescent material within the cell. Thus, materials containing Rare Earth (RE) elements have a great advantage for these applications due to their attractive optical and physicochemical properties, such as several possibilities of excitation wavelengths - from UV to NIR, strong photoluminescence emissions, relatively long luminescence decay lifetimes (µs to ms), and high sensitivity and easy preparation. In resume, the relentless search for new systems continues. The contribution and understanding of the mechanisms of the various physicochemical properties presented by this system is critical to finding a suitable system for cancer treatment via PDT.

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The development of X-ray-absorbing scintillating nanoparticles is of high interest for solving the short penetration depth problem of visible and infrared light in photodynamic therapy (PDT). Thus, these nanoparticles are considered a promising treatment for several types of cancer. Herein, gadolinium oxide nanoparticles doped with europium ions (Gd2O3:Eu3+) were obtained by using polyvinyl alcohol as a capping agent. Hybrid silica nanoparticles decorated with europium-doped gadolinium oxide (SiO2-Gd2O3:Eu3+) were also prepared through the impregnation method. The synthesized nanoparticles were structurally characterized and tested to analyze their biocompatibility. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy confirmed the high crystallinity and purity of the Gd2O3:Eu3+ particles and the homogeneous distribution of nanostructured rare earth oxides throughout the fumed silica matrix for SiO2-Gd2O3:Eu3+. Both nanoparticles displayed stable negative ζ-potentials. The photoluminescence properties of the materials were obtained using a Xe lamp as an excitation source, and they exhibited characteristic Eu3+ bands, including at 610 nm, which is the most intense transition band of this ion. Cytotoxicity studies on mouse glioblastoma GL261 cells indicated that these materials appear to be nontoxic from 10 to 500 µg·mL-1 and show a small reduction in viability in non-tumor cell lines. All these findings demonstrate their possible use as alternative materials in PDT.