Search Results (12)

Rhabdophane, CePO₄∙H₂O, nanoparticles were prepared by mechanochemical synthesis with different durations and thoroughly characterized by various characterization techniques. X-ray diffraction analysis showed that the optimal synthesis duration was 15 min, since, in this case, pure rhabdophane is obtained, without traces of contamination by the vessel material. The size of the obtained nanoparticles, as determined from high-resolution transmission electron microscopy images, was around 5 nm. According to UV-Vis diffuse reflectance spectroscopy results, rhabdophane nanoparticles show transparency to visible light and high absorption in the UV region, with a direct bandgap of 3.1 eV. The photocatalytic activity in the Castor oil degradation process and the cytotoxicity for human skin cells were determined and compared to commercial TiO₂ nanoparticles, with rhabdophane nanoparticles exhibiting superior properties. Small particle size, purity, absorption in the UV range, transparency to visible light, low photocatalytic activity, and low cytotoxicity indicated the possibility of prepared rhabdophane application as an inorganic UV filter in photoprotective formulations. Full article

Rare Earth Elements (REE) phosphates (monazite, xenotime, and rhabdophane) are critical REE-bearing minerals typically formed in hydrothermal and magmatic ore deposits. The thermodynamic properties of those REE minerals are crucial to understanding the solubility, speciation, and transport of REE complexes. However, the standard-state Gibbs free energy of formation (∆G°_f) values reported for these minerals in the literature vary by up to 25 kJ mol⁻¹. Here, we present linear free energy relationships that allow the evaluation and estimation of the ∆G°_f values at 25 °C and 1 bar for the three minerals from the ionic radius (r_REE³⁺) and the non-solvation Gibbs free energy contribution to the REE³⁺ aqua ion (∆G°_{n, REE}³⁺): ∆G°_f,monazite − 399.71 r_REE³⁺ = 1.0059 ∆G°_n,REE³⁺ − 2522.51; ∆G°_f,xenotime − 344.08 r_REE³⁺ = 0.9909 ∆G°_n,REE³⁺ − 2451.53; and ∆G°_{f,rhabdophane} − 416.17 r_REE³⁺ = 1.0067 ∆G°_{n, REE}³⁺ − 2688.86. Moreover, based on the new dataset derived for REE end-members, we re-fitted the binary Margules parameter (W) from previous theoretical calculations into linear correlations: W + 0.00204 ∆G°^’_n,monazite = 39.3549 ∆V + 0.0641; W + 0.00255 ∆G°^’_n,xenotime = 25.4885 ∆V − 0.0062. The internally consistent thermodynamic properties of these REE phosphates are incorporated into the computer program Supcrtbl, which is available online at Zhu’s research website. Full article

The Mount Weld rare earth element (REE) deposit, Western Australia, is one of the largest of its type on Earth. Current mining exploits the high-grade weathered goethite-bearing resource that lies above, and which represents the weathering product of a subjacent carbonatite. The mineralogy, petrography, deportment of lanthanides among the different components, and variation in mineral speciation, textures, and chemistry are examined. Microanalysis, involving scanning electron microscope (SEM) imaging, electron probe microanalysis (EPMA) and laser ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS), was conducted on sized fractions of three crushed and ground laterite ore samples from current and planned production, and a representative sample from the underlying carbonatite. High-magnification imaging of particles in laterite samples show that individual REE-bearing phases are fine-grained and extend in size well below the micron-scale. Nanoscale inclusions of REE-phosphates are observed in apatite, Fe-(Mn)-(hydr)oxides, and quartz, among others. These have the appearance, particularly in fluorapatite, of pervasive, ultrafine dusty domains. Apart from the discrete REE minerals and abundant nano- to micron-scale inclusions in gangue, all ore components analysed by LA-ICP-MS contain trace to minor levels of REEs within their structures. This includes apatite, where low levels of REE are confirmed in preserved igneous apatite, but also Fe- and Mn-(hydr)oxides in which concentrations of hundreds, even thousands of ppm are measured. This is significant given that Fe-(Mn)-(hydr)oxides are the most abundant component of the laterite and points to extensive mobility and redistribution of REEs, and especially HREE, during progressive lateritisation. Late-formed minerals, notably tiny grains of cerianite, reflect a shift to oxidising conditions. REE-fluorocarbonates are the main host for REEs in carbonatite and are systematically replaced by hydrated, Ca-bearing REE-phosphates (largely rhabdophane). The latter displays varied compositions but is characteristically enriched in HREE relative to monazite in the same sample. Fine-grained, compositionally heterogeneous rhabdophane is accompanied by minor amounts of other paragenetically late, hydrated phosphates with enhanced MREE/HREE relative to LREE (although still LREE-dominant). Minor, relict xenotime and zircon are significant HREE carriers. Ilmenite and pyrochlore group members contain REE but contribute only negligibly to the overall REE budget. Although the proportions of individual mineral species differ, the chemistry of key ore components are similar in different laterite samples from the current resource. Mineral signatures are, however, subtly different in the lower grade southeastern part of the deposit, including higher concentrations of HREE relative to LREE in monazite, rhabdophane, florencite and Fe-(Mn)-(hydr)oxides. Full article

This work explores the preparation of luminescent and biomimetic Tb³⁺-doped citrate-functionalized carbonated apatite nanoparticles. These nanoparticles were synthesized employing a citrate-based thermal decomplexing precipitation method, testing a nominal Tb³⁺ doping concentration between 0.001 M to 0.020 M, and a maturation time from 4 h to 7 days. This approach allowed to prepare apatite nanoparticles as a single hydroxyapatite phase when the used Tb³⁺ concentrations were (i) ≤ 0.005 M at all maturation times or (ii) = 0.010 M with 4 h of maturation. At higher Tb³⁺ concentrations, amorphous TbPO₄·nH₂O formed at short maturation times, while materials consisting of a mixture of carbonated apatite prisms, TbPO₄·H₂O (rhabdophane) nanocrystals, and an amorphous phase formed at longer times. The Tb³⁺ content of the samples reached a maximum of 21.71 wt%. The relative luminescence intensity revealed an almost linear dependence with Tb³⁺ up to a maximum of 850 units. Neither pH, nor ionic strength, nor temperature significantly affected the luminescence properties. All precipitates were cytocompatible against A375, MCF7, and HeLa carcinogenic cells, and also against healthy fibroblast cells. Moreover, the luminescence properties of these nanoparticles allowed to visualize their intracellular cytoplasmic uptake at 12 h of treatment through flow cytometry and fluorescence confocal microscopy (green fluorescence) when incubated with A375 cells. This demonstrates for the first time the potential of these materials as nanophosphors for living cell imaging compatible with flow cytometry and fluorescence confocal microscopy without the need to introduce an additional fluorescence dye. Overall, our results demonstrated that Tb³⁺-doped citrate-functionalized apatite nanoparticles are excellent candidates for bioimaging applications. Full article

KMeY(PO₄)₂:5% Eu³⁺ phosphates have been synthesized by a novel hydrothermal method. Spectroscopic, structural, and morphological properties of the obtained samples were investigated by X-ray, TEM, Raman, infrared, absorption, and luminescence studies. The microscopic analysis of the obtained samples showed that the mean diameter of synthesized crystals was about 15 nm. The KCaY(PO₄)₂ and KSrY(PO₄)₂ compounds were isostructural and they crystallized in a rhabdophane-type hexagonal structure with the unit-cell parameters a = b ≈ 6.90 Å, c ≈ 6.34 Å, and a = b ≈ 7.00 Å, c ≈ 6.42 Å for the Ca and Sr compound, respectively. Spectroscopic investigations showed intense ⁵D₀ → ⁷F₄ transitions connected with D₂ site symmetry of Eu³⁺ ions. Furthermore, for the sample annealed at 500 °C, europium ions were located in two optical sites, on the surface of grains and in the bulk. Thermal treatment of powders at high temperature provided better grain crystallinity and only one position of dopant in the crystalline structure. The most intense emission was possessed by the KSrY(PO₄)₂:5% Eu³⁺ sample calcinated at 500 °C. Full article

The accessory mineral assemblage (AMA) of igneous cumulate xenoliths in volcanoclastic deposits and lava flows in the Carpathian back-arc basin testifies to the composition of intrusive complexes sampled by Upper Miocene-Pliocene basalt volcanoes. The magmatic reservoir beneath Pinciná maar is composed of gabbro, moderately alkalic to alkali-calcic syenite, and calcic orthopyroxene granite (pincinite). The intrusive complex beneath the wider area around Fiľakovo and Hajnáčka maars contains mafic cumulates, alkalic syenite, carbonatite, and calc-alkalic granite. Both reservoirs originated during the basaltic magma underplating, differentiation, and interaction with the surrounding mantle and crust. The AMA of syenites is characterized by yttrialite-Y, britholite-Y, britholite-Ce, chevkinite-Ce, monazite-Ce, and rhabdophane(?). Baddeleyite and REE-zirconolite are typical of alkalic syenite associated with carbonatite. Pyrochlore, columbite-Mn, and Ca-niobates occur in calc-alkalic granites with strong peralkalic affinity. Nb-rutile, niobian ilmenite, and fergusonite-Y are crystallized from mildly alkalic syenite and calc-alkalic granite. Zircons with increased Hf/Zr and Th/U ratios occur in all felsic-to-intermediate rock-types. If rock fragments are absent in the volcanic ejecta, the composition of the sub-volcanic reservoir can be reconstructed from the specific AMA and zircon xenocrysts–xenolith relics disintegrated during the basaltic magma fragmentation and explosion. Full article

Luminescent lanthanide-containing biocompatible nanosystems represent promising candidates as nanoplatforms for bioimaging applications. Herein, citrate-functionalized calcium-doped terbium phosphate hydrate nanophosphors of the rhabdophane type were prepared at different synthesis times and different Ca²⁺/Tb³⁺ ratios by a bioinspired crystallization method consisting of thermal decomplexing of Ca²⁺/Tb³⁺/citrate/phosphate/carbonate solutions. Nanoparticles were characterized by XRD, TEM, SEM, HR-TEM, FTIR, Raman, Thermogravimetry, inductively coupled plasma spectroscopy, thermoanalysis, dynamic light scattering, electrophoretic mobility, and fluorescence spectroscopy. They displayed ill-defined isometric morphologies with sizes ≤50 nm, hydration number n ~ 0.9, tailored Ca²⁺ content (0.42–8.11 wt%), and long luminescent lifetimes (800–2600 µs). Their relative luminescence intensities in solid state are neither affected by Ca²⁺, citrate content, nor by maturation time for Ca²⁺ doping concentration in solution below 0.07 M Ca²⁺. Only at this doping concentration does the maturation time strongly affect this property, decreasing it. In aqueous suspensions, neither pH nor ionic strength nor temperature affect their luminescence properties. All the nanoparticles displayed high cytocompatibility on two human carcinoma cell lines and cell viability correlated positively with the amount of doping Ca²⁺. Thus, these nanocrystals represent promising new luminescent nanoprobes for potential biomedical applications and, if coupled with targeting and therapeutic moieties, they could be effective tools for theranostics. Full article

The paper consists of two main parts: a microscopic and spectroscopic investigation of the single crystal of 17-year-old ²³⁸Pu-doped Eu-monazite, and a theoretical calculation of the properties of several structural types of orthophosphates. It is shown that actinide-doped monazite is prone to the formation of mechanically weak, poorly crystalline crust, presumably consisting of rhabdophane. Its formation is likely promoted by the formation of peroxides and, potentially, acidic compounds, due to the radiolysis of atmospheric moisture. The calculations of mixing the enthalpies and Gibbs energies of binary solid solutions of Pu and rare earth element (REE) phosphates that were performed for the principal structural types—monazite, xenotime, rhabdophane—show that, in the case of light REEs, the plutonium admixture is preferentially redistributed into the rhabdophane. This process strongly affects the behavior of actinides, leached from a monazite-based waste form. The applications of these results for the development of actinide waste forms are discussed. The current data on the behavior of real actinide-doped monazite suggest that this type of ceramic waste form is not very resistant, even in relatively short time periods. Full article

Coal and coal by-products are considered as the potential raw materials for critical elements (e.g., rare earth elements, Li, Ga, Ge, etc.), which have attracted much attention in recent years. The purpose of this study is to investigate the mineralogical and geochemical characteristics, and controlling geological factors of lithium and rare earth elements in the Lopingian (Wujiaping Formation) coal from the Donggou Mine, southeastern Chongqing Coalfield, China. Results indicate that lithium and rare earth elements are significantly enriched in the Donggou coals, which could be new potential alternative sources for critical elements. Concentrations of lithium and rare earth elements in the Donggou coals gradually increase from top to bottom. Lithium is mainly associated with kaolinite, while rhabdophane, florencite, goyazite, and xenotime are the main hosts of rare earth elements. The controlling geological factor is the groundwater leaching of underlying tuff, and to a lesser extent, the terrigenous clastic materials input from the top layer of the Kangdian Upland. This study provides mineralization information for lithium and rare earth elements exploration in coal measures. Full article

The mineralogical and geochemical compositions of the Lopingian coals from an exploratory drill core (ZK4-1) in the Zhongliangshan Coalfield, southwestern China are reported in this paper. The Zhongliangshan coals are medium volatile bituminous in rank (random vitrinite reflectance, average 1.38%), characterized by a medium-ash yield (26.84%) and high sulfur content (3.38%). Minerals in the Zhongliangshan coals are mainly composed of clay assemblages (kaolinite, the illite/smectite mixed layer (I/S) and chamosite), pyrite, quartz, carbonate minerals (calcite, marcasite, ankerite, and dolomite), and anatase, followed by rutile, jarosite, natrojarosite, bassanite, gypsum and K-feldspar, with traces of apatite, rhabdophane and barite. Compared with the average concentrations of the world hard coals, some trace elements including Li, V, Co, Cu, Se, Y, Zr, Nb, rare earth elements (REE), Cd, Ta, Hf and Hg, are enriched in the Zhongliangshan coals. The modes of occurrence of chamosite, barite, rhabdophane, quartz and calcite in the Zhongliangshan coals indicate that the coals have probably been affected by the injection of low-temperature hydrothermal fluids. Based on the concentrations of Sc, V, Cr, Co, Ni, Cu and Zn, the ratios of Al₂O₃/TiO₂ and the upper continental crust-normalized rare earth element and yttrium (REY) distribution patterns of the Zhongliangshan coals, the dominant sediment source regions are the Leshan–Longnvsi Uplift, Hannan Upland, and Dabashan Uplift, with a small proportion of terrigenous materials from the Kangdian Upland. The K7 and the upper portion of K1 coals have the potential as raw materials for the recovery of REY. Full article

A novel and simple transcription strategy has been designed for the template-synthesis of CePO₄·xH₂O nanofibers having an improved nanofibrous morphology using a pH-sensitive nanofibrous hydrogel (glycine-alanine lipodipeptide) as structure-directing scaffold. The phosphorylated hydrogel was employed as a template to direct the mineralization of high aspect ratio nanofibrous cerium phosphate, which in-situ formed by diffusion of aqueous CeCl₃ and subsequent drying (60 °C) and annealing treatments (250, 600 and 900 °C). Dried xerogels and annealed CePO₄ powders were characterized by conventional thermal and thermogravimetric analysis (DTA/TG), and Wide-Angle X-ray powder diffraction (WAXD) and X-ray powder diffraction (XRD) techniques. A molecular packing model for the formation of the fibrous xerogel template was proposed, in accordance with results from Fourier-Transformed Infrarred (FTIR) and WAXD measurements. The morphology, crystalline structure and composition of CePO₄ nanofibers were characterized by electron microscopy techniques (Field-Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy/High-Resolution Transmission Electron Microscopy (TEM/HRTEM), and Scanning Transmission Electron Microscopy working in High Angle Annular Dark-Field (STEM-HAADF)) with associated X-ray energy-dispersive detector (EDS) and Scanning Transmission Electron Microscopy-Electron Energy Loss (STEM-EELS) spectroscopies. Noteworthy, this templating approach successfully led to the formation of CePO₄·H₂O nanofibrous bundles of rather co-aligned and elongated nanofibers (10–20 nm thick and up to ca. 1 μm long). The formed nanofibers consisted of hexagonal (P6₂22) CePO₄ nanocrystals (at 60 and 250 °C), with a better-grown and more homogeneous fibrous morphology with respect to a reference CePO₄ prepared under similar (non-templated) conditions, and transformed into nanofibrous monoclinic monazite (P21/n) around 600 °C. The nanofibrous morphology was highly preserved after annealing at 900 °C under N₂, although collapsed under air conditions. The nanofibrous CePO₄ (as-prepared hexagonal and 900 °C-annealed monoclinic) exhibited an enhanced UV photo-luminescent emission with respect to non-fibrous homologues. Full article

In order to understand the crystal chemical properties of hydrous rare-earth (RE) phosphates, REPO_4,hyd, that form at ambient temperature, we have synthesized REPO_4,hyd through the interaction of aqueous RE elements (REEs) with aqueous P at room temperature at pH < 6, where the precipitation of RE hydroxides does not occur, and performed rigorous solid characterization. The second experiment was designed identically except for using hydroxyapatite (HAP) crystals as the P source at pH constrained by the dissolved P. Hydrated RE phosphate that precipitated at pH 3 after 3 days was classified into three groups: LREPO_4,hyd (La → Gd) containing each REE from La-Gd, MREPO_4,hyd (Tb → Ho), and HREPO_4,hyd (Er → Lu). The latter two groups included increasing fractions of an amorphous component with increasing ionic radius, which was associated with non-coordinated water. RE_allPO_4,hyd that contains all lanthanides except Pm transformed to rhabdophane structure over 30 days of aging. In the experiments using HAP, light REEs were preferentially distributed into nano-crystals, which can potentially constrain initial RE distributions in aqueous phase. Consequently, the mineralogical properties of hydrous RE phosphates forming at ambient temperature depend on the aging, the pH of the solution, and the average ionic radii of REE, similarly to the well-crystalline RE phosphates. Full article