Search Results (130)

Birnessite has a strong ability to fix rare-earth elements (REEs), but the transformation process of birnessite and its effects on the migration of these elements are not well understood. This study examines how pH and Mn(II) concentrations influence the transformation of cerium-adsorbed hexagonal birnessite (Ce/HB) and the behaviors of Ce and Mn. The results show that the effect of Mn(II) on Ce/HB transformation strongly depended on solution pH. At a pH of 5.0, HB initially underwent transformation into feitknechtite, followed by further disproportionation that resulted in the regeneration of HB and Mn(II). Concurrently, redox reactions occur between Mn(IV) in MnO₂ (a secondary phase of HB) and Ce(III)/Mn(II), creating a local redox gradient that facilitates partial HB transformation. At pH = 7.0, Mn(II) reduces the crystallinity of transformed products while enhancing the thermodynamic stability of feitknechtite, making it the dominant manganese oxide phase. At pH = 9.0, high-concentration Mn(II) causes lattice distortion in original HB; Ce(III) acts as a structural inducer, promoting mineral transition from hexagonal to orthorhombic symmetry, while excess soluble Mn(II) precipitates new feitknechtite. Additionally, surplus Mn(II) could engage in interfacial redox reactions with high-valent manganese oxides to generate secondary feitknechtite. Ce primarily exists as Ce(IV), forming CeO₂ on the mineral surface via oxidation reactions that significantly increase hydroxylation and surface reactivity. This study clarifies the transformation pathways of manganese oxides and the migration and transformation patterns of Ce and Mn in rare-earth-rich mining areas. Full article

Rare-earth elements (REEs) are integral in a wide range of advanced technologies. Increasing demand for REEs, geopolitical tensions that threaten supply chains, and environmental strain due to extraction operations necessitate the development of new separation and purification methods. Novel selective adsorbents offer a promising alternative to traditional precipitation and solvent extraction due to high selectivity, surface area, and reusability. This research provides insight into the loading and stripping behavior of the 2-D Metal–Organic Framework (MOF) ‘NCU-1’ over multiple pH conditions and time domains in chloride media. NCU-1 structures were synthesized using standard methods, then evaluated for kinetics and equilibria via batch testing. Pseudo-first-order kinetics was used to model the adsorption behavior of all REEs tested. The kinetic trends between elements support a mechanism in which sorption affinity and rate correlate with REE ionic radius and surface interaction strength. The preliminary evaluation presented here suggests that such units are highly useful for both solution purification and the separation of light rare-earth (LREE) from heavy rare-earth elements (HREE). Full article

The Nakexiuma area in the East Kunlun Orogen Belt hosts two spatially distinct mineralization systems: uranium-molybdenum (U-Mo) in schist and granitoid, and tungsten-molybdenum (W-Mo) in skarn and granitoid. To clarify their genetic relationship, we conducted U-Pb dating and trace element analyses on zircon, garnet, and uraninite. Zircon from granitoids yields a crystallization age of 250 ± 2.3 Ma, followed by W-Mo mineralization at 245 ± 2.1 Ma (garnet) and U-Mo mineralization at 235 ± 9 Ma (uraninite), indicating a prolonged magmatic-hydrothermal history spanning approximately 15 million years. Trace element data reveal a shift in fluid chemistry over time: Skarn garnets show high W contents, suggesting oxidizing, high-temperature fluids; uraninite displays REE depletion and negative Eu anomalies, precipitated from oxidizing fluids encountering a reducing environment. We propose that the W, U, and Mo mineralization in Nakexiuma is the result of this long-lived magmatic-hydrothermal system. The spatial separation of these mineralization systems is attributed to a multi-stage process involving host rock lithology and fluid redox evolution. Early oxidizing fluids from granitoids metasomatized carbonates to form W-Mo mineralization skarn. Later, meteoric water influx increased oxygen fugacity, generating U-rich, highly oxidizing fluids that precipitated uraninite and molybdenite upon interaction with the reducing meta-mafic rocks. These results highlight the roles of lithology and fluid chemistry in controlling spatially separated mineralization within the same system. Furthermore, they expand the Early Mesozoic metallogenic spectrum of the East Kunlun Belt, providing a refined model for polymetallic ore formation in a post-collisional extensional setting. Full article

The recovery of rare earth elements (REEs) from the spent NdFeB magnets has great strategic significance for ensuring the security of critical mineral resources. This process requires scientifically designed separation technologies to ensure high output and purity of the obtained rare earths. Hydrometallurgy has been widely applied to extract REEs from spent permanent magnets. This paper summarizes and reviews hydrometallurgical technologies, mechanisms, and applications for the separation and recovery of REEs and iron (Fe) from the spent permanent magnets. Key methods include: The hydrochloric acid total solution method, where the spent NdFeB is completely dissolved in hydrochloric acid, iron is precipitated and removed, and then REEs are extracted. The hydrochloric acid preferential dissolution method, where spent NdFeB magnets are first fully oxidized by oxidative roasting, converting Fe²⁺ to Fe³⁺, which hydrolyzes to Fe(OH)₃, and is precipitated and removed, allowing for the subsequent extraction of REEs to obtain rare earth oxides. Acid baking and water leaching, where spent NdFeB is calcined with acidification reagents, and the calcined products are dissolved in water to leach out REEs. At the same time, Fe is retained in the leaching residue. Electrolysis in aqueous solution, where Fe is electrolyzed at the anode or deposited at the cathode to separate it from REES. Organic acids leaching, where organic acids dissolve metals through acidolysis and complexation. Bioleaching, which utilizes microorganisms to recover metal through biological oxidation and complexation. Ionic liquid systems, where Fe or REEs are extracted using ionic liquid or leached by deep eutectic solvents. This paper provides an in-depth discussion on the challenges, advantages, and disadvantages of these strategies for recycling spent NdFeB magnets, as well as the leaching and extraction behavior of REEs. It focuses on environmental impact assessment, improving recovery efficiency, and decreasing reagent consumption. The future development direction for recycling spent NdFeB magnets is proposed, and a research idea of proposing a combined process to avoid the drawbacks of a single recycling method is introduced. Full article

Synthesis of published and new data from the Govorov and Kocebu guyots provide geochemical and chronostratigraphic constraints on hydrogenetic cobalt-rich Fe-Mn crusts from the Western Pacific Magellan Seamount Trail (MST). The history of the crusts began about 65–60 Ma, when the relict layer R was deposited in the Campanian—Maastrichtian and Late Paleocene along the shores of guyots. The growth of the old-generation crusts continued in the Late Paleocene—Early Eocene (Layer I-1) and in the Middle—Late Eocene (Layer I-2) in a shallow-water shelf environment. The younger layers formed in the Late Oligocene—Early Miocene (Layer I-2b), Miocene (Layer II), and Pliocene—Pleistocene (Layer III) at depths about the present sea level. The precipitation of Fe and Mn oxyhydroxides from seawater was interrupted by several times, with the longest gap from 38 to 26.5 Ma between the old (R, I-1, and I-2) and young (I-2b, II, and III) layers. Fe and Mn oxyhydroxides in the crusts were affected by two global events of phosphogenesis in the Pacific: Late Eocene—Early Oligocene, from 43 to 39 Ma (Layers R, I-1, I-2) and Late Oligocene—Early Miocene, from 27 to 21 Ma (Layer I-2b). The trace element patterns in different layers of the Co-rich Fe-Mn crusts are grouped using factor analysis of principal components (varimax raw) into four factors: (1) +(all REEs except Ce and La); (2) +(Ce, La, Ba, Mo, Sr, Pb); (3) +(Zr, Hf, Nb, Rb, As)/-Pb; (4) +(U, Th, Co, As, Sb, W)/-Y. The factor score diagrams highlight fields which are especially contrasting for Layers I-1, I-2, and II + III according to factors 2 and 4. Consistent REE and Y variations in Layers I-2b → II → III of the crust from Pallada Guyot correlate with gradual ocean deepening between the Late Oligocene—Early Miocene and Present when the MST guyots were submerging. Large variations in the trace element contents across coeval layers may be due to the hydrodynamics of currents on the guyot surfaces. Furthermore, the geochemistry of the crusts bears effects from repeated episodes of Cenozoic volcanism in the MST region of the Pacific Plate. Higher contents of Nb, Zr, As, Sb, and W in the younger layers II and III may result from large-scale volcanism, including Miocene eruptions of petit-spot volcanoes. Full article

Based on the physicochemical properties of waste phosphate-based rare earth phosphors containing glass, this paper proposes a novel recovery method for rare earth elements (REEs) that integrates pre-enrichment, alkali roasting, and enhanced leaching. Initially, preliminary enrichment of REEs was achieved through sieving to remove silicon (from glass components) and pickling to reduce calcium content (originating from calcium phosphate compounds). The enriched material was then subjected to alkaline roasting, followed by washing for impurity removal, hydrochloric acid leaching, and finally oxalic acid precipitation to extract the rare earth elements. Experimental results demonstrate that the overall recovery rate of rare earth oxides (REO) reached 96.6%, indicating highly efficient extraction and separation of REEs from the waste phosphors. Furthermore, the mechanism of the alkali roasting process was investigated via differential thermal analysis (TG-DSC). Microstructural and phase changes in the waste phosphors before and after roasting were systematically characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results indicate that green phosphor (REPO₄) was converted into rare earth oxides and water-soluble sodium phosphate under alkaline roasting conditions. The Na₃PO₄ could be effectively removed through washing, while the rare earth elements were retained in the form of oxides within the washed residue. This study provides an important theoretical foundation and technical approach for the efficient recovery of rare earth resources from waste phosphate-based phosphors. Full article

Coal ash represents an abundant secondary resource of rare earth elements (REEs), but their recovery is hindered by low concentrations in leachates and the presence of large amounts of competing matrix elements such as Fe, Al, Ca, and Mg. In this study, a stepwise pH-controlled precipitation approach was applied to real sulfuric acid coal ash leachates for selective recovery of Ce and La. The process combined impurity scrubbing, oxidative precipitation of Ce, and phosphate precipitation of La. Nearly complete recovery was achieved, with >95% of both Ce and La recovered and >99% phase purity. Selectivity analysis further demonstrated strong discrimination of REEs over matrix elements, with Ce showing >400 selectivity over Fe, Al, and Ca, and La showing ~170 over the same ions and ~17 over Ce. These results show the efficiency of the approach under realistic multi-element conditions. Full article

This study investigates the concentrations and geochemical behaviour of strategic elements—including Li, Co, Ni, Cu, Ga, Ge, rare earth elements (REEs), and yttrium (Y)—in bottom ash samples from the Afşin–Elbistan thermal power plant, Türkiye. Thirty bottom ash samples were analysed, revealing average ∑LREE and ∑HREE concentrations of 86.3 µg/g and 3.3 µg/g, respectively, resulting in an L/H ratio of 24.9, indicating pronounced enrichment in light REEs. The total ∑REE + Y concentration (111 µg/g) is comparable to the background value for coal but approximately 1.5 times lower than those reported for average Chinese coals and the upper continental crust (UCC). REE contents significantly exceed those of sedimentary (5.36 µg/g), mafic (16.77 µg/g), and felsic (3.60 µg/g) rocks. Elevated Li (30.5 µg/g) and Ni (114.4 µg/g) concentrations point to a mafic magmatic source, whereas Cu (28.7 µg/g) likely originates from basic volcanic rocks such as those of the Dağlıca Complex and the Kemaliye Formation. Chondrite-normalised REE patterns show Dy depletion relative to mafic rocks and Ho depletion compared to sedimentary rocks. Positive δEu anomalies (>1) support a mafic or UCC provenance, while slightly positive δCe values indicate hydrothermal leaching influences. The co-precipitation of Ce with Ca–Mg hydroxides and clay minerals in coal-bearing lacustrine sediments is suggested. Ga enrichment is attributed to aluminium-rich clay minerals and organic matter. Overall, these geochemical signatures reflect combined inputs from hydrothermal leaching and volcanic weathering within a coal-bearing lacustrine environment. Full article

The persistent occurrence of antibiotics like chloramphenicol (CAP) in aquatic systems poses serious environmental and public health risks. This study investigates the photocatalytic degradation of CAP using cerium oxide (CeO₂), lanthanum oxide (La₂O₃), and lanthanum-doped cerium oxide (Ce_xLa_yO_2−δ), synthesized via co-precipitation. The catalysts were tested under a solar simulator, UV-A, and UV-C radiation, both with and without hydrogen peroxide (H₂O₂). Structural characterization confirmed successful synthesis of nanometric catalysts, with La doping causing lattice expansion in CeO₂ and a reduction in crystallite size (from 27 nm in CeO₂ to ~20 nm in doped samples). Photolysis alone achieved limited CAP removal (~34–35%), while photocatalysis with La₂O₃ under UV-A and UV-C improved removal up to 58% and 55%, respectively. Complete degradation was obtained with La₂O₃ under UV-C in the presence of H₂O₂ within 15 min. Pareto analysis highlighted the dominant effect of the interaction between radiation and H₂O₂ (43%), while the catalyst type contributed minimally (0.23%). These findings confirm the potential of REE oxides, especially La₂O₃, in advanced oxidation processes and underscore the importance of light source and radical generation over catalyst selection alone. Full article

The Xiaobaihegou fluorite deposit is located in the southwest of the Altyn-Tagh Orogen, NW China. However, the provenance, thermodynamic properties, and enrichment mechanisms of the ore-forming fluids in this deposit remain unclear. Fluorite mineralization primarily occurs in the vicinity of the contact zone between the granite and the wall rocks. The zircon U-Pb age of the alkali-feldspar granite in the Xiaobaihegou fluorite deposit is 482.3 ± 4.1 Ma. The ore-hosting lithologies are mainly calcareous rock series of the Altyn Group. The ore bodies are controlled by NE-trending faults and consist primarily of veined, brecciated, massive, and banded ores. The ore mineral assemblage is primarily composed of calcite and fluorite. The rare earth element (REE) patterns of fluorite and calcite in the Xiaobaihegou deposit exhibit right-dipping LREE enrichment with distinct negative Eu anomalies, which closely resemble those of the alkali-feldspar granite. This similarity suggests that the REE distribution patterns of fluorite and calcite were likely inherited from the pluton. The ore-forming process can be divided into an early stage and a late stage. The massive ores formed in the early stage contain mainly gas-rich two-phase fluid inclusions and CO₂-bearing three-phase inclusions, with homogenization temperatures ranging from 235 °C to 426 °C and salinities from 28.59% to 42.40% NaCl equivalent. In the late stage, brecciated and stockwork ores were formed. They host liquid-rich two-phase and gas-rich two-phase fluid inclusions, with homogenization temperatures ranging from 129 °C to 350 °C and salinities from 0.88% to 21.61% NaCl equivalent. The results of hydrogen and oxygen isotope studies indicate that the ore-forming fluids were derived from a mixture of magmatic–hydrothermal and meteoric water. Fluorite precipitation in the early stage was mainly due to the mixing of magmatic–hydrothermal solution and meteoric water, as well as a water–rock reaction. In the late stage, fluid mixing further occurred, resulting in a decrease in temperature and the formation of brecciated and stockwork ores. The ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios of fluorite from the deposit range from 0.71033 to 0.71272 and 0.511946 to 0.512073, respectively, indicating that the ore-forming material originates from the crust. Based on the ore-forming characteristics, it is proposed that Ca may be primarily leached from the strata formation, while F may predominantly originate from magmatic–hydrothermal solutions. The formation of fluorite deposits is closely related to the transition of the Central Altyn-Tagh Block and Qaidam Block from a compressional orogenic environment to an extensional tectonic environment. Full article

Rare earth elements (REEs) have garnered significant global attention due to their essential role in advanced technologies. Sri Lanka is endowed with various REE-bearing minerals, including the apatite-rich deposit in the Eppawala area, commonly known as Eppawala rock phosphate (ERP). However, direct extraction of REEs from ERP is technically challenging and economically unfeasible. This study introduces a novel, integrated approach for recovering REEs from ERP as a by-product of nitrophosphate fertilizer production. The process involves nitric acid-based acidolysis of apatite, optimized at 10 M nitric acid for 2 h at 70 °C with a pulp density of 2.4 mL/g. During cooling crystallization, 42 wt% of calcium was removed as Ca(NO₃)₂.4H₂O while REEs remained in the solution. REEs were then selectively precipitated as REE phosphates via pH-controlled addition of ammonium hydroxide, minimizing the co-precipitation with calcium. Further separation was achieved through selective dissolution in a sulfuric–phosphoric acid mixture, followed by precipitation as sodium rare earth double sulfates. The process achieved over 90% total REE recovery with extraction efficiencies in the order of Pr > Nd > Ce > Gd > Sm > Y > Dy. Samples were characterized for their phase composition, elemental content, and morphology. The fertilizer results confirmed the successful production of a nutrient-rich nitrophosphate (NP) with 18.2% nitrogen and 13.9% phosphorus (as P₂O₅) with a low moisture content (0.6%) and minimal free acid (0.1%), indicating strong agronomic value and storage stability. This study represents one of the pioneering efforts to valorize Sri Lanka’s apatite through a novel, dual-purpose, and circular approach, recovering REEs while simultaneously producing high-quality fertilizer. Full article

In this article, we examine water chemistry and carbonate precipitation in the alkaline waterbody Lake Van in Turkey, analyzing the possible role of microbial communities in stromatolite formation. Lake Van represents a unique environment characterized by high salinity and pH and extensive microbial communities, as revealed by SEM observation. Microbial activity, including that of cyanobacteria, can influence carbonate precipitation processes, leading to the formation of authigenic carbonates through physicochemical or metabolic mechanisms such as photosynthesis or sulfate reduction. In these environments, which are often dominated by cyanobacteria, carbonate precipitation can be influenced by biologically induced processes. This study presents new data on the hydrochemistry of lake water, focusing on the behavior of rare-earth elements (REEs) in this water and the carbon and oxygen isotopic compositions of carbonate microbial mats. The oxygen isotope data suggest that inorganic carbonate precipitation is the dominant process, but a biological influence on inorganic precipitation cannot be ruled out. For a deeper understanding of the role of biological processes in Lake Van, further studies on microbialites are needed. Full article

The Mamuju region in West Sulawesi, Indonesia, is a High Background Natural Radiation Area (HBNRA) characterized by a significant enrichment of high field strength elements (HFSEs) and rare earth elements (REEs) within its lateritic deposits. This study investigates the geochemical behavior, mineralogical distribution, and enrichment processes of HFSEs and REEs in lateritic profiles of drill cores and surface samples derived from alkaline volcanic rocks. The mineralogy and geochemical content of HFSEs and REEs in the alkaline bedrocks indicate its potential to become a source of lateritic enrichment. An intense lateritic weathering process leads to the residual accumulation of HFSEs and REEs, particularly in B-horizon soils, where clay minerals and Fe–Al oxides are crucial in element precipitation. Moreover, groundwater redox conditions are a key factor for uranium precipitation in the lateritic profile. The findings provide insight into the potential of lateritic weathering as a natural mechanism for HFSE and REE concentration, contributing to the broader understanding of critical metal resources in Indonesia. These insights have implications for sustainable resource exploration and environmental management in areas with high natural radiation exposure. Full article

The Shuixie Cu–Co polymetallic orefield, located in western Yunnan Province (southeastern margin of the Qinghai–Tibet Plateau), is renowned for its Cu–Co mineralization. A recent resource reassessment identified Sb–Au and Cu–Co–Bi (Sb–Au) orebodies as genetically associated with primary Cu–Co mineralization. The mineralization characteristics and microscopic observations indicate that gold mineralization in the Sb–Au orebodies follow a pulsating fluid injection model. The model includes four pulses: (1) euhedral gold-poor pyrite (PyI₁) precipitation; (2) margin-parallel growth of gold-rich pyrite (PyI₂) on PyI₁; (3) continued growth of gold-rich pyrite (PyI₃) along PyI₂; and (4) outermost concentric gold-rich pyrite (PyI₄) formation. This study examined gold-bearing pyrite in orebodies and host rocks. In situ laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) analysis of pyrite and inductively coupled plasma mass spectrometry (ICP–MS) whole-rock trace element analysis were conducted to track the ore-forming fluid evolution. Compared with CI chondrite, pyrites from all pulses were enriched in LREEs over HREEs. The pyrite REE distribution curves exhibited right-skewed patterns, reflecting LREE enrichment. The Hf/Sm, Nb/La, and Th/La ratios were generally below 1, indicating high-field-strength element depletion. These results suggest a Cl-rich, F-poor ore-forming fluid. The pyrite trace elements showed enrichment in the chalcophile elements (e.g., Cu and Pb) and exceptionally high Bi levels compared with the continental crust. The chalcophile elements (e.g., Zn and Cd) were depleted, whereas iron-group elements (e.g., Co) were enriched and Ni was depleted. The pyrite δCe values (0.87–1.28, mean = 1.01) showed weak anomalies, indicating a reducing ore-forming environment. The δEu values of pyrite during pulses 1 to 4 ranged widely, from 0.2–3.01 (mean of 1.17), 0.27–1.39 (0.6), and 0.41–1.40 (0.96) to 0.4–1.36 (0.84), respectively, suggesting an initial temperature decline and subsequent increase in the ore-forming fluid. Significant variations were found in the Y/Ho, Zr/Hf, and Nb/Ta ratios across pulses, indicating the potential involvement of high-temperature hydrothermal fluids or late-stage alteration during ore formation. The Y/Ho ratio of pyrite overlapped most closely with that of the continental crust of China, indicating a close relationship between the ore-forming fluids and the crust. Full article

In the western Tarim Basin, Carboniferous granular dolostones deposited on a carbonate platform contain a small amount of terrigenous materials of sand-size fraction, agglomerated clay minerals, or similar phases. However, the role of terrigenous materials on dolomitization is still unclear. The aim of this study was to reveal the dolomitization mechanism. The granular dolomites have small crystal size, earthy yellow color, and fabric-retentive texture, with relatively good order. These features indicate dolomites precipitated during early diagenesis. The ratio of rare earth elements (RREs) abundance of the stable isotopes ⁸⁷Sr/⁸⁶Sr relative to Post-Archean Australian Shale (PAAS) normalized patterns was used to study the source of the dolomitizing fluids. The composition of REEs is characterized by heavy rare earth (HREE) enrichment (average Nd_SN/Yb_SN = 0.83). There is a positive (La/La*)_SN anomaly and slightly positive (Gd/Gd*)_SN and (Y/Y*)_SN anomaly; δ¹⁸O of seawater in fractionation equilibrium with granular dolostones was from −2.8‰ to 1.7‰ PDB, implying the dolomitizing fluid was contemporary, slightly evaporated seawater. The granular dolostones on the relatively thick shoals were subject to subaerial exposure before pervasive dolomitization, with evidence that the input of detrital kaolinite predated the formation of dolomites. Higher ⁸⁷Sr/⁸⁶Sr values and ∑REE in granular dolostones than the values in equivalent limestones indicate that dolomitization was related to terrigenous materials. Within the terrigenous materials, the negative-charged clay minerals may have catalyzed the dolomitization, resulting in dramatically decreased induction time for precipitation of proto-dolomites. A greater amount of terrigenous materials occurred on the shoals at the sea level fall, resulting from enhanced river entrenchment and downcutting. As a result, after subaerial exposure, the penesaline water flow through the limy allochems sediments lead to dolomitization, with the catalysis of illite on relatively thick shoals. Full article