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Common collectors for rare earth mineral (REM) flotation, which include carboxylates and hydroxamates, face problems such as being non-selective and sensitive to impurity ions. A type of ionic liquid (IL), tetraethylammonium mono-(2-ethylhexyl)2-ethylhexyl phosphonate ([N2222][EHEHP]), has been investigated previously for rare earth elements (REE) solvent extraction, and was proven to be selective and effective. In this work, [N2222][EHEHP] was evaluated as a collector in bastnasite (a primary REM source for REE production) flotation for the first time. The results were compared with quartz and hematite, two common gangue minerals in REM deposits. Zeta potential measurements and Fourier-transform infrared spectroscopy (FT-IR) were completed to investigate the surface chemical properties involved in the flotation of these minerals using this collector. The findings were compared with microflotation results. FT-IR and zeta potential measurements suggest adsorption of the collector's phosphonate group onto bastnasite and hematite, likely through chemisorption; whereas for quartz, the minimum microflotation recovery is likely due to no adsorption of IL on its surface. Microflotation results show higher collectability of [N2222][EHEHP] for hematite than bastnasite, the latter only shows appreciable recovery at pH 5 with elevated dosage of IL (500 g/t). To achieve better separation, a two-stage flotation scheme was designed and evaluated by bench scale flotation on a synthetic mineral mixture. The concentrates and tails were analyzed by magnetic separation, and it is found that bastnasite recovery over 90% with maximum upgrade ratio 1.7 can be achieved with elevated collector dosage.

Isotopic dating studies have revealed that many carbonatite-related REE ore systems have protracted and complex temporal evolution histories. The mechanisms that cause these complex dating results remain poorly understood. Here, we present an in-situ Sm-Nd and Th-Pb isotopic investigation of monazite and bastnasite from a geologically-complicated deposit, the world-class Bayan Obo REE deposit of China, with the aim of defining the general mechanisms accounting for the protracted age spread observed in this and many other REE deposits. Monazite and bastnasite are two principle REE ore minerals in the Bayan Obo deposit. Most of the studied monazite and bastnasite grains have experienced fluid-aided modification. The modified grains have generally homogeneous Sm and Nd contents and Sm-Nd isotopic compositions, implying low mobility of Sm and Nd during the modification process. Thus, the Sm-Nd chronometer can be used to constrain the primary crystallization timing of the REE minerals at 1293 ± 48 Ma. However, altered REE minerals have apparent 208Pb-232Th ages (1248–261 Ma) that are variably younger than the primary crystallization age. In most samples, Th contents have no correlations with 208Pb-232Th ages, while Pb contents tend to decrease along with the younging trend of 208Pb-232Th ages. NanoSIMS mapping shows that 208Pb and 208Pb/232Th are heterogeneous, and irregularly distributed in the altered grains. Such results are indicative of variable Pb loss during the fluid-aided modification process. Thus, many Th-Pb ages represent partial isotopic resetting and, hence, are geologically meaningless. Completely reset ages cluster at 450–400 Ma or 280–260 Ma, representing two discrete episodes of post-ore hydrothermal activity. Small amounts of monazite and bastnasite that were newly crystallized during these two overprinting episodes have initial Nd isotopic signatures approaching the time-evolved isotopic compositions of primary ores, which suggests insignificant REE input to the primary ores during these events. This study provides critical evidence to resolve complex dating results and disparate ore genesis models for the giant Bayan Obo deposit. Moreover, our results indicate the resistance of Sm-Nd isotopes, but the susceptibility of Th-(U)-Pb isotopes, to fluid-aided modification. Therefore, younger Th-U-Pb dates in geologically-complicated deposits should be treated with caution as they may represent partial resetting results and/or may not represent events of increased metal tenor.

This study deals with the calcination of a rare earth bearing ore to produce rare earth oxides in a fluidized bed reactor, with the aim of demonstrating the advantage of calcining bigger particles to decompose stable minerals such as monazite by its mineral association within a particle. Rare earth oxides were produced by the decomposition of its bearing minerals, bastnasite and monazite along with the gangues. During the calcination, bastnasite decomposed at relatively low temperature while monazite reacted CaO at high temperature. The formation of cracks, revealed by BET and SEM analysis, allowed the particle’s degassing while the size remained constant, thus describing a crackling core behavior. The association of monazite to calcite for bigger particles (−60 mesh) allowed its decomposition to produce rare earth oxides with a monazite conversion of 50 %. Also, an extraction process comprised of calcination and mild acid leaching enriched the rare earth oxides in the ore by 3.34 and improved leaching efficiency of the gangues compared to smaller size (enrichment ration of 2.35). Using bigger particle sizes in the upstream process of a mining industry, i.e. comminution, can also reduce the energy consumption.

Rare earth element (REE) production is limited in part by inefficient strategies for beneficiation. Hydroxamic acid ligands are promising reagents for the selective flotation of bastnasite [(Ce,La)FCO3], a major REE ore mineral, but the mechanism and energetics of adsorption are not understood, interfering with the design of new, more efficient reagents. Here, the adsorption of octyl hydroxamic acid onto bastnasite was measured using a combination of experimental and computational methods. In-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy revealed changes in the hydroxamate functional group vibrational frequencies, corresponding to chelation with cerium cations at the bastnasite surface. The results indicate a monodentate chemisorption mechanism at low surface loading that changes to bidentate chemisorption at higher concentrations. This interpretation is supported by molecular vibrational frequency shifts calculated using density functional theory (DFT), and orientation of the hydrocarbon chain measured by sum frequency generation (SFG) vibrational spectroscopy. The binding enthalpies of octyl hydroxamic acid interacting with La and Ce-bastnasite surfaces were measured using isothermal titration calorimetry (ITC) revealing a stronger coordinating ability with bastnasite than with a common gangue mineral, calcite (CaCO3). Because octyl hydroxamate favors monodentate adsorption at low surface coverages, the relative chelating strength of metal ions could be a poor predictor for selectivity under monolayer adsorption conditions. At higher surface loadings, where the bidentate mode of adsorption is active, selectivity is likely to be limited by increased flotation of gangue ores.

Rare earths are critical to numerous materials and applications underpinning modern civilisation. The majority of the world's rare earth reserves are hosted in the three minerals bastnasite, monazite and xenotime. A key step in the processing of rare earth mineral concentrates is the chemical decomposition of the mineral structure to release the constituent elements. The sulfuric acid bake has historically been, and is also currently, one of the major processes used for this step. Current sulfuric acid bake processes for the Bayan Obo deposit in China and the Mt. Weld deposit in Australia together account for more than half of the world's rare earth production. In the sulfuric acid bake, the rare earth elements are converted to rare earth sulfates which are dissolved in a subsequent water leach. The conditions required to achieve mineral decomposition vary widely for different rare earth minerals. Adjustment of process conditions may often be used to achieve some degree of impurity rejection which is beneficial to downstream processing. This paper reviews the application of the sulfuric acid bake process to ores/concentrates containing mainly monazite, xenotime and bastnasite, and other less common rare earth minerals including euxenite, samarskite, fergusonite, loparite, allanite, eudialyte and pyrochlore. The reported effects of feed mineralogy and process variables such as reaction temperature, bake duration, acid to concentrate ratio and particle size are presented along with a brief review of current understanding of the bake chemistry and water leach results.

Dissolution in choline-chloride based deep eutectic solvents (DES) of rare earth elements (REE) from high-purity single carbonate salts of Y, La, Ce, Nd and Sm and from their multicomponent mixtures and also bastnasite mineral was assessed with a prospect to gain an understanding on the leaching behavior of bastnasite ores as REE source from DES suspensions. Urea, malonic acid and citric acid were used in different proportions with choline chloride in order to form deep eutectic solvents with desired viscosity and functionality. The results obtained prove promising for use insolvato-metallurgical processes in terms of selective dissolution of the higher-atomic-number (Z) rare earth elements at the expense of the lower-ZREEs and the gangue-originating metal impurities, thus initiating separation among the different REE members from the early hydrometallurgical steps.

Bastnasite is the main ore mineral in many carbonatite-related rare earth element (REE) deposits, which account for ∼51% of rare-earth oxide reserves worldwide. However, the occurrence, geochemistry, and genetic significance of bastnasite has not been methodically investigated. The Cenozoic Mianning–Dechang (MD) REE belt in Sichuan Province, SW China, contains the Maoniuping, Dalucao, Lizhuang, and Muluozhai deposits as well as numerous smaller REE occurrences. Individual deposits within the belt contain different types of bastnasite-bearing ore, which provides a unique opportunity to explore in detail the common mechanisms controlling the formation of bastnasite-rich REE deposits. Here, we present detailed results from field observations and petrographic, geochemical, and fluid inclusion studies of bastnasite from the main MD deposits. Calcite, fluorite, and barite form stable mineral assemblages that are commonly overprinted by bastnasite. Homogenization temperatures of fluid inclusions in bastnasite of ∼150–270 °C (Dalucao and Lizhuang deposits) and 155–210 °C (Maoniuping deposit) are systematically lower than those of fluid inclusions in gangue minerals. Therefore, the petrographic studies and homogenization temperatures both show that large-scale crystallization of bastnasite took place during the later stage of the hydrothermal system. The bastnasite, relatively geochemically homogeneous within all of the MD deposits, is enriched in Ba (293–8425 ppm), Th (16.4–2527 ppm), and U (4.19–92.7 ppm), and relatively depleted in high field strength elements such as Nb (0.15–17.4 ppm), Ta (0.06–6.48 ppm), Zr (0.71–31.1 ppm), Hf (0.62–5.65 ppm), and Ti ( carbonatite , and ore veins. In comparison, the samples from the study area show an increase in average REE contents from syenites to carbonatites to ore veins (i.e., bastnasite-bearing ores) and finally to bastnasite. Lanthanum and Ce were commonly substituted by Th, U, Sc, Ba, and Sr supplied by more evolved hydrothermal fluids. Combining the present results with existing data, we present a three-stage model for the formation of carbonatite-related REE deposits. First, partial melting of metasomatized sub-continental lithospheric mantle, fluxed by REE- and CO2-rich fluids, forms the parental carbonatite–syenite magma. Second, Sr, Ba, and REEs are strongly partitioned into carbonatite melts during liquid immiscibility in the carbonatite–syenite magmatic system. Third, hydrothermal fluids exsolved from the crystalizing syenite and carbonatite magmas form ore veins with early gangue minerals and later bastnasite overgrowths. Consequently, barite, calcite, and fluorite assemblages are a valuable guide in REE exploration.

The Taipingzhen deposit is a newly discovered REE deposit in the North Qinling Orogen (NQO), Central China. The REE ores are hosted in the altered fracture zones of Paleozoic strata and a granitic intrusion. The ore minerals mainly include bastnasite-(Ce)[(Ce(CO3)F], parisite-(Ce)[CaCe2(CO3)3F2], and synchysite-(Ce)[CaCe(CO3)2F], and this deposit also contains some uncommon minerals, such as tornebohmite-(Ce)[Ce2Al(SiO4)2(OH)], gatelite-(Ce) [CaCe3AlAl2Mg(Si2O7)(SiO4)3O(OH)2], fluocerite-(La)[LaF3] and F-rich cerite-(Ce)[(Ce,Ca)9 Mg(SiO4)3[SiO3(OH)]4F3], which are identified here for the first time in China. To determine the timing of REE mineralization and explore possible genetic relationships between mineralization and granitic magmatism, the U-Pb ages of bastnasite-(Ce) from ore and zircon from ore-hosting granite are obtained. The in situ LA-MC-ICP-MS U-Pb age of the bastnasite-(Ce) provides a reliable 238U/206Pb-207Pb/206Pb lower intersection point age of 409 ± 16 Ma, and ID-TIMS analyses yield an U-Pb age of 407.8 ± 3.3 Ma; the U-Pb dating of the magmatic zircon reveals that the wall rock was emplaced at 457.1 ± 4.9 Ma, and the hydrothermal zircon age of 399.4 ± 3.5 Ma records the time of hydrothermal alteration, thus indicating that the REE mineralization in the Taipingzhen deposit occurred at approximately 409–400 Ma. This age coincides well with the U-Pb ages of the bastnasite-(Ce) and zircon, revealing a genetic association between the hydrothermal fluid and the REE mineralization. The Hf isotopic compositions imply that the partial melting of Paleoproterozoic HP and UHP eclogite from the lower crust provided ore materials for the mineralization, and the deposit was generated in a retrograde metamorphic setting during the late Paleozoic postcollisional extension event in the NQO. Furthermore, combined with the geochronological data published for other U-REE metallic deposits in the NQO, our study indicates that the late Silurian-early Devonian granite-related U-REE metallic mineralization throughout the NQO mainly occurred during 421–395 Ma.

Carbonatite-related rare-earth element (REE) deposits are the most important source of the world’s REE resources. Hydrothermal fluids have been proposed to play a significant role in the transport and precipitation of REEs, but fluid inclusion data on the hydrothermal processes in carbonatitic settings are relatively sparse. The Dalucao deposit, located in the Mianning–Dechang (MD) REE belt, Sichuan, China, is a Cenozoic carbonatite-related REE deposit (c. 12 Ma) that offers an excellent opportunity to investigate the evolution of ore-forming fluids. Brecciated and weathered ores are common in this deposit. The former are characterized by mineral assemblages comprising fluorite + barite + celestite + calcite + quartz + bastnasite (No. 1 orebody) or fluorite + celestite + pyrite + muscovite + calcite + quartz + bastnasite (No. 3 orebody), whereas the latter contain REE minerals, clay minerals, and minor gangue minerals. We present a comprehensive study of fluid inclusions from the Dalucao deposit to constrain its hydrothermal evolution. Magmatic, pegmatitic, hydrothermal, and supergene stages have been recognized. During the pegmatitic stage, the main minerals that formed were coarse-grained fluorite, barite, celestite, calcite, and quartz, which host melt inclusions, melt–fluid inclusions, and minor high-salinity fluid inclusions. The presence of melt and melt–fluid inclusions suggests a magmatic origin for the ore-forming fluids. Hydrothermal processes included at least two stages, characterized by hydrothermal veins that are developed in fractures within the carbonatite–syenite complex: (1) Fluid inclusions during the formation of the fluorite–quartz–barite veins in the pre-REE stage were trapped under immiscible conditions, as evidenced by the presence of CO2-bearing inclusions coexisting with aqueous ones. These immiscible CO2-bearing inclusions recorded a range of pressures from 1050 to 1600 bar. All of fluid inclusions in this stage exhibited homogenization temperatures varying from 278 to 442 °C, with salinities ranging from 3.2 to 45.1 wt% NaCl equivalent (equiv.). (2) The REE-stage fluids were represented by abundant aqueous inclusions, characterized by homogenization temperatures ranging from 147 to 323 °C and salinities between 1.1 and 9.5 wt% NaCl equiv. These data suggest that the ore-forming fluids forming the Dalucao deposit evolved from high-temperature, high-pressure, high-salinity, CO2-rich to low-temperature, low-pressure, low-salinity, CO2-poor. Gas- and ion-chromatographic analyses combined with mineralogical features indicate that the initial fluids were rich in REEs, (SO4)2−, Cl−, F−, Na+, K+, Ca2+, and volatile components (e.g., H2O, CO2, N2, CH4, Ar, and C2H6). H–O isotope analyses of quartz suggest that the hydrothermal fluids had a dominantly magmatic signature and were gradually diluted by meteoric waters. Hydrothermal REE transport was probably controlled by F−, (SO4)2−, and Cl− as complexing ligands. We propose that fluid cooling and mixing rather than immiscibility led to the precipitation of bastnasite during the waning stage of hydrothermal activity. Taken together, the inclusion data and observations of alteration, paragenesis and mineralization have provided insights into the development of REE mineralization and the further exploration of carbonatite-related REE resources.

Bastnasite is an important mineral resource in the production of rare earth materials and is usually beneficiated by flotation. The flotation of bastnasite is problematic due to the competitive adsorption of hydroxamate collector on bastnasite and its associated calcium-bearing gangue minerals such as fluorite. One strategy to solve this problem is to use effective depressants to depress the gangue minerals. However, the current depressants all have some drawbacks. In this study, the effect of ethylenediamine tetraacetic acid (EDTA) as a depressant was tested in the flotation of single mineral of bastnasite and fluorite and their mixture. The mechanism underpinning the role of EDTA was investigated through theoretical thermodynamic calculation, zeta potential and X-ray photoelectron spectroscopy (XPS) measurements. The results show that fluorite was significantly depressed, while the flotation of bastnasite was almost unaffected when EDTA was present. The separation index between bastnasite and fluorite increased from 1.18 to 12.66 with the increase of EDTA concentration from 0 to 7.79 kg/t. It was found that EDTA could dissolve the chemically adsorbed octyl hydroxamic acid (OHA) on fluorite through the formation of soluble Ca-EDTA complexes, whereas the chemically adsorbed OHA on bastnasite was more stable and could not be transformed into Ce-EDTA spontaneously. Therefore, the flotation of fluorite was selectively depressed by EDTA. The results show that EDTA was a promising depressant for fluorite gangue mineral in bastnasite flotation.

A number of gravity separation techniques for rare earth elements (REE) minerals have been investigated and reported in the literature. These include the use of dense/heavy media, Falcon concentrators, Knelson concentrators, spiral concentrators, laboratory scale jigs, and shaking tables. Most of these methods have provided considerable REE minerals recovery and upgrade; but remain at the laboratory testing stage. There are vast quantities of iron-oxide-silicate rich tailings (IST) containing low grade REE in Australia. This work is part of research and development studies currently underway at the University of South Australia to develop economically viable methods to exploit selected IST for their REE contents. In this investigation, the feasibility of exploiting the differences in specific gravity to concentrate REE minerals from a typical IST sample was studied using two gravity separation units, a Knelson concentrator (KC) and Wilfley shaking table. The feed sample and gravity separation products were characterised using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN) to study and compare the performance of the KC and shaking table as gravity preconcentration methods. The results indicated that the performance of both the KC and shaking table are significantly dependent on the mineralogical and particle size characteristics of the feed, however, the tabling was found to be the preferred choice over the KC, due to its greater selectivity. Tabling of >38 μm feed samples produced the desired split between the iron oxides and silicate minerals. The results suggest that desliming of the feed to remove fine/ultrafine particles (

Common rare earth (RE) minerals, such as bastnasite and monazite, may be formed in deposits associated with carbonate gangue, such as calcite and dolomite. Sodium oleate is a widely used collector for the flotation of both RE and gangue minerals, which might, therefore, be an inefficient process due to the lack of selectivity of this collector. Since these minerals are also sparingly soluble in solution, they could release their constituent ions into the solution, which could affect the floatability of other minerals. In this study, the interactions of sodium oleate with bastnasite and monazite in the presence of dissolved dolomite species have been investigated. Microflotation tests were carried out to explore the effects of these dissolved species on the floatability of the RE minerals. Zeta potential measurements and XPS characterization were carried out to understand how the species affect the collector adsorption. To complement these characterizations, density functional theory (DFT) simulations were conducted to investigate the collector-mineral and collector-adsorbed species (on the mineral surface) interactions. The results show that collector-dolomite interaction energy is greater than that of collector-adsorbed species, but lower than collector-monazite interaction energy, explaining the decrease in the minerals' recovery upon exposure to the dissolved mineral species. It is also shown that oleate ions (Ol–) have the strongest interaction with the minerals compared to other oleate species such as acid soap (HOl2–) and oleate dimer (Ol22−). The behavior (strength and selectivity) of sodium oleate towards RE minerals and dolomite, as compared to other RE mineral collectors (such as aromatic hydroxamate), is attributed mainly to the collector's and the minerals' structure. The long hydrocarbon chain of sodium oleate which imparts hydrophobic characteristic to the minerals, makes it stronger collector than benzohydroxamate. Moreover, sodium oleate (with linear structure), unlike the aromatic hydroxamate, can approach the mineral easier due to lesser steric hindrance effect and higher reactivity of O involved in the interaction, making it less selective. In addition, it can interact easily with dolomite due to the presence of more exposed active sites than RE minerals.

The carbonatite dike swarm and vein stockwork at the center of the Paleogene Bear Lodge alkaline complex (BLAC), Wyoming, USA, is host to diverse REE mineral assemblages that are largely a result of subsolidus modification and REE redistribution. Pseudomorphic replacement of primary burbankite by an assemblage of ancylite, strontianite, and barite is the result of interaction with late-stage hydrothermal fluids that added Sr, Ba, S, F, and REE, analogous to the replacement processes described for some carbonatite complexes of Russia's Kola Peninsula. Carbon and oxygen stable isotope ratios indicate that the primary carbonatite mineralogy experienced degassing/pneumatolysis and alteration by fluids of variable temperature, CO2/H2O ratios, and/or meteoric water content. Isotopic differences of matrix calcite between Group 1 carbonatites (avg. δ13C = −7.3‰; δ18O = 9.1‰) and Group 2 carbonatites (avg. δ13C = −9.9‰; δ18O = 10.2‰) are consistent with loss of CO2 during degassing. The open-system alteration of burbankite caused a pronounced positive δ18O-shift in bulk ancylite pseudomorphs (δ18O: 14.3–25.7‰) relative to matrix calcite (δ18O: 8.7–11.2‰). Oxygen isotope compositions of biotite (δ18O: 4.5–5.9‰) and K-feldspar (δ18O: 7.3–7.9‰) in unoxidized carbonatite are typical of primary magmatic silicates and suggest that fluids responsible for the burbankite-to-ancylite conversion remained predominantly magmatic (carbohydrothermal). Concomitant increases toward the surface in 13C and 18O, oxidation, matrix carbonate dissolution, and the replacement of REE carbonates (ancylite, carbocernaite, and burbankite) by Ca-REE fluorocarbonates (bastnasite, parisite, synchysite) suggest interaction with late-stage, low temperature (

Apatite is one of the important host minerals of the rare earth elements (REEs). Separation of REEs from apatite has not been studied extensively compared with other main minerals such as monazite, bastnasite and xenotime. Therefore, it is essential to develop an effective method for recovery of REEs from apatite-based ores. This paper presents the results of laboratory studies for the recovery of rare earth elements from an apatite ore sample by using sulphuric acid leaching, solvent extraction, and precipitation processes. Results showed that the most effective dissolutions of light REEs (>85%) and heavy REEs (>89%) from the apatite ore sample were achieved with a dilute sulphuric acid solution (1 M H2SO4) at a temperature of 20 °C in an hour. The heavy REEs present in the pregnant leach solution were almost entirely extracted using 1.2 M di-(2-ethylhexyl) phosphoric acid (D2EHPA) as a cation exchanger, while the most light REEs remained in the raffinate. The heavy REEs loaded into the organic phase were stripped completely by 3 M H2SO4 solution. REEs remained in raffinate and stripped into the aqueous solution were precipitated as RE oxalates by the addition of 0.08 M oxalic acid.

Carboxylates, hydroxamates and organic phosphoric acids are typical collectors used for rare earth mineral flotation. Carboxylates are not selective, while hydroxamates, though selective, require high concentrations to recover a significant amount of rare earth minerals. Other collectors such as organic phosphoric acids, which showed promising rare earth minerals collecting potential, have recently been explored. However, the mechanism of organic phosphoric acid adsorption on the surface of rare earth minerals has not been very well investigated. In this study, zeta potential measurements were conducted to study the surface property of dolomite, monazite and bastnasite in the presence of benzohydroxamate (hydroxamate), sodium oleate (carboxylate) and Flotinor 1682 (phosphoric acid ester). These measurements, complemented with ATR-FTIR spectroscopy, evaluated the adsorption of the collectors at the surface of the minerals. The adsorption of the collectors was found to be highly influenced by the mineral cations present at the mineral/solution interface and in the solution. Possible adsorption mechanisms are proposed and discussed; some of which agree with those presented in the literature, while others provided different perspective. Although benzohydroxamate was the most selective, potential flotation processes to recover rare earth minerals using sodium oleate and Flotinor 1682 were also suggested.

The silico-carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartzbearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnasite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnasite and parisite where replaced by synchysite-(Ce) and rontgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution re carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphateminerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE.Mass balance considerations indicate hydrothermal HREE to themineralisation. The evolution of the in may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferentialHREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexationmay have been important for preferential HREE transport. AlongsideHREE-enrichedmagmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.flects the evolution from magmaticfluids must have contributedfluorcarbonate mineral assemblage requires an increaseaCa2+ and aCO3 2− in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite−) may account

Rare metal-bearing, alkaline granites have attracted extensive interests because of their economic significance. The Early Permian (∼290 Ma) Boziguo’er alkaline granitic pluton, exposed in the middle segment of the South Tianshan Terrane, Xinjiang, NW China, contain Nb-Ta-, Zr-, Th-U- and REE-bearing accessory minerals, and host a large-scale rare metal deposit. The unalterated alkaline granites are mainly composed of alkali feldspars (∼40 vol% orthoclase/microcline and ∼30 vol% albite), quartz (∼20 vol%), arfvedsonite (∼5 vol%) and biotite (∼5 vol%), with accessory minerals at least including zircon, monazite, pyrochlore, Fe-Ti oxides, xenotime, bastnasite and astrophyllite. The existence of two types of alkaline feldspars, which respectively show nearly pure Ab and Or end member compositions, suggest that the Boziguo’er pluton can be classified as “subsolvus granites”. Rare metal elements in the pluton are mainly contained by pyrochlore (Nb-Ta), zircon (Zr-Hf, Th-U and HREE) and monazite (LREEs) grains. Mineral chemistry suggests that the pyrochlore and monazite are of primary igneous mineral. Based on morphology, internal texture and mineral chemistry, four types of zircons have been identified. Type-I zircon may have crystallized from volatile-undersaturated early-stage magmas, while type-IIA zircon crystallized from volatile (fluorine)-saturated magmas. The type-IIB and type-III zircons could have grown in an LREE-depleted silicate melt after the crystallization of the LREE-rich minerals (e.g., monazite) or an early aqueous fluid during the transition from a magmatic to hydrothermal system. The type-IV zircons can be regarded as low-temperature hydrothermal ones. A semiquantitative calculation, based on mineral compositions of biotites, yields 0.51–2.14 wt% for F contents in granitic melts. The high contents of fluorine in the hydrous minerals suggest a fluorine-enriched characteristic for melt, which would not only prolong the duration of the magmatic differentiation but can also enhance the solubility of ore-forming elements in magma. The magmatic differentiation was mainly dominated by fractional crystallization of alkali feldspar and amphibole. Extensive rare metal mineralization in the pluton likely occurred within a limited temperature interval and was related to the crystallization of a highly evolved intergranular melt at the latest magmatic stage.

Flotation is the most commonly used beneficiation method for rare earth (RE) ores. Due to the dissolution characteristics of the RE minerals and the gangue minerals, they may behave similarly in a flotation system. Previous work has shown that dissolved mineral species from gangue could precipitate/adsorb at the mineral surface affecting the minerals’ flotation behavior. In this work, the effect of dolomite supernatant on the surface of bastnasite, monazite and dolomite are presented. Zeta potential measurements, complemented with flotation tests, were conducted with and without the presence of the supernatant using benzohydroxamate as the collector. XPS results confirmed the surface speciation, and DFT simulations detail the possible mineral - collector, mineral - precipitated species and precipitated species - collector interactions. The results show that carbonate precipitates and Ca2+ from the supernatant could adsorb onto the mineral surface through covalent bonding, both affecting the zeta potential and reducing collector adsorption. Another important finding of this study is the potential loss of the collector in the solution due to complexation with ions from the supernatant. These findings confirm that an effective rare earth mineral separation through flotation does not rely solely on the strength of collector-mineral interaction, but rather is highly dependent on the chemistry of the flotation solution. Taking advantage of, or controlling, the surface reactions should be the main target to developing a more efficient and cost-effective flotation process. Different measures have been proposed to reverse/reduce the detrimental effects of the dolomite supernatant to RE mineral flotation.

The potential of ionic liquid-ionic liquid mineral separation process as a novel ionic liquid-based system to beneficiate rare earth element (REE) bearing minerals was investigated. This multiphase beneficiation system was prepared using two mutually immiscible ionic liquids (IL) as dispersed and continuous phases. A phosphonium/ammonium based ionic liquid as droplet phase and three different ionic liquids as continuous phase were applied to evaluate this approach of beneficiation of REE complex ore. Ionic liquid-ionic liquid mineral separation tests were performed on an actual rare earth complex ore with its main composing minerals consisting of monazite, bastnasite, ankerite, calcite and dolomite. Fourier Transform Infrared (FTIR) spectroscopy, Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) analyses were performed to unveil the nature of interactions between IL droplet phase and each of the minerals composing the ore. Bastnasite and monazite have been found to exhibit stronger chemisorption interactions with phosphonium/ammonium based ionic liquid in comparison with calcite, ankerite and dolomite. Density Functional Theory (DFT) simulations were also conducted to reveal the configuration of ionic liquid moieties on the surface of the minerals through ionic liquid adsorption. It was found that the IL anionic moiety directly interacts with the metal cations on the mineral surfaces through covalent bonds, at the expense of the cationic moiety which is only involved in weaker solvophobic interactions. DFT simulation also indicated that the adsorption geometry of IL is based on cis-conformation where the cationic and anionic moieties adsorb next to each other on the mineral surfaces.

In this study, the ionic liquid betainium bis(trifluoromethylsulfonyl)imide (HBetTf2N), has been applied directly as a leaching agent on a low-grade rare earth element (REE) ore called Rodberg, from the Fen carbonatite complex ore deposit located in Norway. REE in Rodberg are mainly present in the form of fluoro-carbonates of bastnasite group minerals. Factors studied during leaching were water ratio into ionic liquid, leaching temperature, pulp density (%w/v) and retention time. Leaching of Rodberg ore with HbetTf2N resulted to 65–100% recovery of light REE and 40–60% recovery of heavy REE. Additionally > 80–90% of Ca and Mg content dissolves, whereas the HbetTf2N is selective against iron and silicon resulting in a Fe/Si rich residue. The metals dissolved into HbetTf2N after leaching are stripped with an aqueous acidic solution, regenerating the ionic liquid for reuse. Through acid stripping, REE concentration is doubled in the aqueous acidic solution, for further purification. The carboxylic acid functional group attached to the cation side of HbetTf2N is capable of dissolving bastnasite thus enabling the development of new alternative methods for treating low-grade REE primary resources.

Rare earth elements (REEs) are a focus of current research due to their importance in a wide range of industries and technologies. Bayan Obo in China is the largest REE deposit in the world. Although some studies have investigated the banded REE ores in the Bayan Obo deposit, the origin and formation processes of the ores are unclear. In this study, we used X-ray powder diffraction, electron microprobe, laser ablation–inductively coupled plasma–mass spectrometry, and mass spectrometry methods to investigate the mineral assemblages and geochemical characteristics of minerals in banded ores in the Bayan Obo REE deposit. Based on petrographic observations, the early minerals that precipitated were alkali- and Fe-rich silicates, such as aegirine–augite and arfvedsonite, followed by bastnasite, fluorite, barite, calcite, and monazite in the late stage. The REE minerals in the banded REE ores are mainly monazite, bastnasite, and parisite (1–10 vol%) that overprinted gangue minerals, suggesting that REE mineralization occurred during the late hydrothermal stage. The sequence of mineral formation and their evolution caused progressive enrichment in REEs, F, Sr, and Ba. For example, fluorite in the banded REE ores has high concentrations of Sr (252–1910 ppm), Ba (1040–8230 ppm), and light REEs (1001–16,079 ppm), but is depleted in Nb and Ta. The bastnasite is enriched in Sr (885–4046 ppm), Ba (1073–80,809 ppm), and ΣREEs (99,631–158,227 ppm). The fluorite, arfvedsonite, and bastnasite in the banded REE ores have ɛNd(t) values of −3.68–1.78, −5.54, and 0.05, and initial (87Sr/86Sr)i (ISr) ratios of 0.70352–0.70478, 0.70620, and 0.70346, respectively. Based on these data, and the regional geological setting and Pb isotope data, it is proposed that fluorite and bastnasite crystallized from ferrocarbonatite and fine-grained dolomite, and the REE source was a mixture of HIMU mantle and global marine sediments. We also suggest that the carbonatite- or dolomite-hosting ores in Bayan Obo formed by melting of the subcontinental lithospheric mantle, which might have been previously metasomatized by REE- and CO2-rich fluids derived from subducted marine sediments.

Rare-earth-element (REE) bearing minerals have been recognized for the first time within rare-element granitic pegmatite pockets from Lagoa Real Uranium Province (LRUP), Bahia state, NE Brazil. The Province is one of the chief U deposits in the world and the largest in South America. Notwithstanding its economic and strategic importance, there are gaps in the geological knowledge about other mineral resources which could occur in the area. One of them, is the lack of petrographic and chemical data sets on its REE content, especially in pegmatite pockets which occur in the contact between Juazeirinho (1755 ± 6 Ma) and Sao Timoteo (1741 ± 4 Ma) granites. In this paper, it is reported a petrographic description and geochemical characterization of allanite, bastnasite, monazite, xenotime, cheralite, and parisite recognized in three spongy mineral assemblages within unzoned granitic pegmatite pockets from Lagoa Real Uranium Province. The REE-bearing minerals present moderate-to-high REE content with significant amounts of Ce, La, Y, and critical REE such as Nd, Er, and Yb, totalling to up to 49 wt%. Petrographical and geochemical evidence arguably indicate that the REE-enrichment in granitic pegmatite pockets of Lagoa Real Uranium Province is a result of late-magmatic and hydrothermal events involving F−, OH−, CO32− and PO43− REE-bearing fluids. The report and characterization of these recently recognized minerals indicate that the Lagoa Real Uranium Province, might hold important REE mineralization as U by-product.

Carbonatite-related rare earth element (REE) deposits are the most significant source of REEs worldwide. The processes of REE precipitation, enrichment, and mineralization remain controversial. The Cenozoic Mianning–Dechang (MD) REE belt, located in Sichuan Province, southwestern China, comprises one giant (Maoniuping), one large (Dalucao), and two small–medium (Muluozhai and Lizhuang) deposits. These deposits provide a continuous record of fluid evolution, and thus are ideal for investigating the processes of REE mineralization in carbonatite-related REE deposits. Given that sulfate (i.e., barite and celestite) and sulfide (i.e., pyrite and galena) minerals crystallized and precipitated in the pegmatitic to hydrothermal stages, respectively, the REE minerals formed later than the sulfate minerals. However, the formation sequence of the sulfide minerals and bastnasite is unclear, although both pyrite and bastnasite formed in the late hydrothermal stage. We used S isotope data for sulfate and sulfide minerals and Fe isotope data for pyrite to investigate the composition and evolution of ore-forming fluids during the magmatic–hydrothermal stages. The sulfate minerals have positive δ34SCDT values (+3.2‰ to +8.3‰), and the sulfide minerals have negative δ34SCDT values (−13.5‰ to − 5.6‰) in the four REE deposits. In the Maoniuping deposit, δ34SCDT values for barite from the pegmatitic stage (+4.7‰ to +5.7‰) are higher than for barite from the hydrothermal stage (+4.1‰ to +4.5‰), which indicate that hydrothermal activity led to relative enrichment in isotopically light S. The δ34SCDT values for barite (+3.2‰ to +5.5‰) are lower than for celestite (+6.2‰ to +7.2‰) from the pegmatitic stage in the Dalucao deposit. The δ34SCDT values for galena (−13.5‰) are also lower than for pyrite (−13.5‰ to −7.2‰) from the hydrothermal stage in the Guangtoushan section. In general, δ34SCDT values change from positive to negative values (+8.3‰ to −16.4‰) as the fluids evolved from the pegmatitic to hydrothermal stages, which can be attributed to a decrease in oxygen fugacity (fO2) and addition of sediment containing isotopically light S. Iron isotopic compositions of pyrite from the hydrothermal stage show significant variations (δ56FeIRMM-014 = −0.03‰ to +0.65‰ for the Maoniuping deposit; −0.14‰ to 0.00‰ for the Dalucao deposit; +0.05‰ to +0.35‰ for the Lizhuang deposit), and are higher than those for the carbonatites (δ56Fe IRMM-014 = −0.47‰ to −0.17‰). These data indicate there are two sources of Fe in the MD REE belt, which are the carbonatite–nordmarkite magma and 56Fe-rich sediment. Paleozoic–Mesozoic volcanic–sedimentary and Mesozoic clastic and carbonate rocks are exposed in the MD REE belt. In general, the S–Fe isotope data, along with geological and petrographic observations, indicate that the REE minerals formed later than the sulfate minerals, and the S–Fe were derived from both carbonatite magma and sediment containing isotopically light S and heavy Fe.

Hydrothermal rare earth element (REE) precipitation in carbonatite is generally attributed to increase in pH or decrease in temperature when REE-bearing acidic fluids interact with carbonates. Here, we document microtextures comprising intergrowth of bastnasite, hydroxyl-parisite, rontgenite, synchysite, and pyrochlore, with calcite that pseudomorphically replaces patches of hematite with cellular boxwork-type structure, in calciocarbonatites from the Kamthai alkaline complex in western India. The nature of the REE mineralization grades from proximal bastnasite-dominated to distal hydroxyl-parisite dominated in the boxworks. The microtextural relations and trace element chemistry of hematite, magnetite and calcite, and C-O isotope composition of carbonate are suggestive of extensive low-temperature hydrothermal alteration of the carbonatites. The hematite boxwork structure and the REE mineral-calcite intergrowths often have squarish outlines and are interpreted to have pseudomorphed primary magnetite during fluid-rock interaction. We propose a new mechanism of REE precipitation in magnetite-rich carbonatites involving influx of acidic hydrothermal fluids, which scavenged the REE and other trace elements from magmatic carbonates and apatite. These acidic fluids were responsible for the protonation of magnetite and leaching out of Fe2+, converting them to hematite through a non-redox transformation. The reaction results in 32% volume reduction for every mole of magnetite consumed, generating significant rock porosity, which further aided and abetted fluid-rock reaction and hydrothermal alteration. More importantly, it consumed proton, which increased the fluid pH triggering precipitation of bastnӓsite-group minerals (including bastnӓsite, parasite, rontgenite, synchysite). Close to the magnetite-hematite reaction front, fluor-dominated bastnӓsite-group minerals (mainly bastnӓsite) appear, while away from such fronts, mineralization was enriched in hydroxyl-bastnӓsite group minerals (mainly parisite) as a consequence of decreasing activity of F‐ and/or increasing activity of OH‐ with the progress of magnetite-to-hematite transformation.

Rare earth elements (REEs) are one of the most important elements used for transformation of the fossil era into a decarbonized future. REEs are essential for wind, electric and hybrid vehicles, and low-energy lighting. However, there is a general understanding that REEs come along with multiple environmental problems during their extraction and processing. Life cycle assessment (LCA) is a well-established method for a holistic evaluation of environmental effects of a product system considering the entire life cycle. This paper reviews LCA studies for determining the environmental impacts of rare earth oxide (REO) production from Bayan Obo and ion adsorption clays (IAC) in China, and shows why some studies lead to over- and underestimated results. We found out that current LCA studies of REE production provide a good overall understanding of the underlying process chains, which are mainly located in China. However, life cycle inventories (LCI) appear often not complete. Several lack accuracy, consistency, or transparency. Hence, resulting environmental impacts are subject to great uncertainty. This applies in particular to radioactivity and the handling of wastewater and slurry in tailing ponds, which have often been neglected. This article reviews 35 studies to identify suitable LCAs for comparison. The assessment covers the world's largest REO production facility, located in Bayan Obo, as well as in-situ leaching of IACs in the Southern Provinces of China. A total of 12 studies are selected, 8 for Bayan Obo and IACs each. The LCIs of these studies are reviewed in detail. The effects of over- and underestimated LCIs on the life cycle impact assessment (LCIA) are investigated. The partly controversial results of existing LCAs are analyzed thoroughly and discussed. Our results show that an increased consistency in LCA studies on REO production is needed.

Growing demand for the rare earth elements, particularly the heavy REE (HREE), has fuelled a boom in mineral exploration and scientific research on carbonatite-hosted deposits, especially those with unusual HREE enrichment. The Ashram REE deposit is such a HREE-enriched carbonatite-hosted REE deposit. Magmatic processes were important in the genesis of the deposit, but hydrothermal mobilization was the main process responsible for the concentration of the REE to potentially economic levels and the fractionation of the HREE. The REE minerals in the Ashram deposit were precipitated from hydrothermal fluids. They comprise monazite-(Ce) and bastnasite-(Ce), with lesser monazite-(Nd) and trace xenotime-(Y) and aeschynite-(Nd). This mineralization occurs as disseminations in breccia matrices, in veins, and as vug fillings. Monazite-(Ce) was the earliest mineral to form, followed by xenotime-(Y) and bastnasite-(Ce). The composition of monazite-(Ce) varies with location in the deposit and is preferentially enriched in the light REE (LREE) with increasing distance from a large, irregular breccia body, underlying the zone of HREE enrichment. This body is interpreted to have been the main conduit for the mineralizing fluids which, on exiting, deposited monazite as a result of the cooling and pH buffering that accompanied their interaction with the adjacent carbonatites. Bastnasite-(Ce) replaced monazite-(Ce) through ligand exchange (F−, CO32− for PO43−), preserving the original REE distribution. Interaction of a compositionally evolving fluid with host rocks of variable bulk composition and buffering capacity resulted in a deposit-scale fractionation and zonation of the REE.

Carbonatites and associated alkaline rocks are the primary sources for REE mineralization. The Ambadongar Carbonatite Complex (ADCC) from NW Deccan Volcanic Province (DVP) constitutes the largest Carbonatite Associated REE Deposits (CARD) in India. ADCC belongs to the final stages of the Late Cretaceous alkaline-carbonatite magmatism associated with main Deccan basalt volcanic activity. The ADCC is an envisioned diatreme structure in which four carbonatitic phases are recognized, mainly calcio-carbonatites and ferro-carbonatites. Each successive carbonatite phase shows higher REE enrichment. The primary REE mineralization with bastnasite as the dominant REE phase is hosted by pervasive hydrothermally altered ferro-carbonatite plugs. The secondary mineralogy formed with barites in the main orebody during late- to post-magmatic hydrothermal fluid alteration is fluorite, quartz, ankerite, and other REE-bearing minerals like bastnasite, parisite, synchysite, strontianite, florencite, monazite and columbite. Carbonatite samples contain 18.61% to 52.42% of CaO, and the LOI varies from 5.28% to 38.79%. Most can be classified as calcio-carbonatites. Since all the samples also contain an appreciable amount of Fe2O3 (4.13% to 20.20%) and MnO (0.07% to 5.46%), some may be classified as ferro-carbonatites. Total REE content varies from 0.6 to 4%, with a high Ce concentration and LREE/HREE ratio. The highest values for La, Ce, Pr, and Nd are 1.95%, 1.56%, 0.16%, and 0.45%, respectively. Metasomatism of SCLM from asthenospheric melts followed by the low degree partial melting of the SCLM region is responsible for fertile carbonatite generation in ADCC. The multiphase liquid immiscibility of carbonatite melts from carbonate-silicate magma followed by immiscibility of REE rich carbonatite melt and REE deficient fluoride-rich aqueous fluids explain the higher level of REE enrichment in each successive phases of carbonatites in ADCC. The mineralizing fluids were probably the result of residual magmatic volatiles that brought mainly REE and later SiO2 into the overprinted rocks. Ambadongar carbonatites' stable isotopic compositions agree with a magmatic origin (δ13C = −4.1 ± 1.9‰ [PDB] and δl8O = 10.3 ± 1.7‰ [SMOW]). The C–O stable isotopic modeling indicates re-equilibration under hydrothermal conditions between 180 °C and 70 °C. Significant amounts of REE fluorocarbonate minerals, relatively Sr- and Th-rich, were deposited during re-equilibration. The REE fluorocarbonate bastnasite-(Ce) occurs as late individual crystals, overgrown on the synchysite and parisite polycrystals. Textural and chemical reactions between the REE fluorocarbonates provide insights into rare-earth elements' mobility during fluid-rock interaction. Early crystallization of synchysite/parisite indicates the high activity of Ca2+, OH−, (SO4)2−, Al and Si in the fluid. Later, the fluid was characterized by increased activity of F−, (SO4)2−, REE and Si, and decreased activity of Ca2+ as reflected in the association of barite, fluorite, quartz, and bastnasite typical of strongly overprinted ferro-carbonatites. Re-equilibration and recrystallization of the primary minerals in the presence of OH−, (SO4)2−, F−, REE, Al, and Si carried in solution by the hydrothermal fluid is the leading cause behind the refixing of REE in the form of REE fluorocarbonate in REE rich ferro-carbonatites.

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnasite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ18O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO43−/CO32− and F−/CO32− ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.

Rare earth elements are a critical component in many clean energy technologies. Extraction of individual rare earth elements from natural ores or recycled material is challenging due to the very similar chemical properties across the lanthanide series. Supercritical carbon dioxide has emerged in recent years as a possible extraction medium for rare earth elements, due to its tunability and selectivity as a solvent. In this study, rare earth elements were recovered from bastnasite concentrate using supercritical carbon dioxide extraction with nitric acid/tributyl phosphate adducts. Two bastnasite pretreatment methods were used to render the rare earth elements amenable to recovery: 1) dry roasting of the source material at 730 °C for 3 h, and 2) decomposition with 50% sodium hydroxide solution at 150 °C for 4 h. These pretreated powder samples were extracted in supercritical carbon dioxide at 34 MPa and 65 °C, with kinetic samples obtained at 15–30 min intervals. A range of tributyl phosphate/nitric acid adduct compositions (from 2 mol/L H+ to 6 mol/L H+) were used in order to determine the effect of adduct composition on recovery rate. The results showed the fastest extraction with an adduct containing approximately 4 mol/L H+. Adducts with higher acidity showed reduced extraction of cerium, praseodymium, and neodymium. This could be due to the formation of aqueous droplets which dissolve rare earth elements and create an equilibrium limitation, or due to competition between the rare earth nitrates and nitric acid for coordination with tributyl phosphate. Extraction with various adduct concentrations in supercritical CO2 showed the expected increase in reaction rate with increased adduct concentration. For the 4 mol/L H+ adduct at 5.0 mol% adduct concentration, roasted bastnasite recoveries were 72% for La, 96% for Ce, 88% for Pr, and 90% for Nd after 120 min. For 4 mol/L H+ adduct at 5.1 mol% adduct concentration, NaOH digested bastnasite recoveries were 93% for La, 100% for Ce, 99% for Pr, and 101% for Nd after 90 min. Though further research is needed, these results are a key step in demonstrating applicability of supercritical extraction to rare earth element ores.

The potential of liquid-liquid mineral separation mediated by ionic liquids (ILs) to beneficiate rare earth (RE) bearing minerals was investigated for the first time. Liquid-liquid separation tests were performed on actual RE-bearing ores whereas the role of ionic liquids was exposed using model monazite, bastnasite, calcite and dolomite single minerals. The multiphase beneficiation system consisted of aqueous pulps in which IL/kerosene and IL/ n -hexane non-polar phases were emulsified using three types of phosphonium/ammonium ionic liquids to evaluate their chelation potential. The aqueous pulp pH played a crucial role in terms of mineral recoveries with the highest RE mineral recoveries achieved at pH 4–7. Also, the newly proposed beneficiation method was found to outperform micro-flotation of the same minerals in terms of selectivity. Zeta potential measurements, Fourier transform infrared spectroscopy, and density functional theory simulations were used to interpret the mechanisms governing this new mineral separation route. The ionic liquid anionic moiety was demonstrably found to directly interact through formation of covalent bonds with the metal cation active centers, contrary to the cationic moiety which at most was involved in weaker “non-surface” Coulombic/van de Waals interactions as ion-pair co-ion. Hence with regard to the potential of ionic liquids in minerals beneficiation, liquid-liquid mineral separation could be envisaged as a new alternative for RE mineral separation instead of flotation.

Data are presented on detailed sampling of the surface and pore waters of soda Lake Doroninskoye (Eastern Transbaikalia, Russia). Particular attention has been paid to the possible REE precipitation species from both water types. Thermodynamic modeling at 25 °C and 1 bar total pressure was performed with the “HCh” code using a free-energy minimization algorithm. We modeled the heterophase 43-component system; both individual minerals and ideal solid solutions of the REE and numerous dissolved species were incorporated into the model. According to the calculations, redox conditions in the lake waters are established by the sulfur species. The main result is that the surface water is slightly supersaturated with respect to CaCO 3 -REE (65%) and F-apatite-REE (35%) solid solutions, as well as bastnasite Ce 0,5 La 0,25 Nd 0,2 Pr 0,05 CO 3 F. A trend of the HREE predominance in the solution during the process of early diagenesis has been confirmed. Nevertheless, the thermodynamic model does not entirely explain the REE fractionation in pore waters (pore solutions are enriched in the LREEs in situ but are drastically depleted according to the thermodynamic model). The results of this study suggest that further considerations about solid solutions should be taken into account to model and understand exact REE fractionation during water-rock interaction in salt lakes.

In the present work, a novel α-aminophosphonate extractant (Cextrant 230) was synthesized for the extraction and recovery of cerium and thorium from sulphate medium. The introduction of amine group into the phosphate molecule would enhance the extraction of Ce(IV) and Th(IV). The effects of extractant concentration, H2SO4 concentration and temperature on the metal extraction were investigated in detail. It was found that the extraction of Ce(IV), Th(IV) and REs (La, Gd, Yb) in sulphate medium decreased in the following order: Ce(IV)>Th(IV)>REs(III). A solvent extraction process to extract and recover cerium and thorium from bastnasite leaching was proposed, in which the purities of cerium and thorium products reached 99.9% and 99% with yield of 92% and 98%, respectively.

Ion-adsorbed rare earth element (REE) deposits supply the majority of world heavy REE production and substantial light REE production, but relatively little is known of their occurrence outside Southeast Asia. We examined the distribution and forms of REEs on a North American pluton located in the highly weathered and slowly eroding South Carolina Piedmont. The Hercynian Liberty Hill pluton experiences a modern climate that includes ~ 1500 mm annual rainfall and a mean annual temperature of 17 °C. The pluton is medium- to coarse-grained biotite-amphibole granite with minor biotite granite facies. REE-bearing phases are diverse and include monazite, zircon, titanite, allanite, apatite and bastnasite. Weathered profiles were sampled up to 7 m-deep across the ~ 400 km 2 pluton. In one profile, ion-adsorbed REEs plus yttrium (REE + Y) ranged up to 581 mg/kg and accounted for up to 77% of total REE + Y in saprolite. In other profiles, ion-adsorbed REE + Y ranged 12–194 mg/kg and only accounted for 3–37% of totals. The profile most enriched in ion-adsorbed REEs was located along the mapped boundary of two granite facies and contained trioctahedral smectite in the saprolite, evidence suggestive of hydrothermal alteration of biotite at that location. Post-emplacement deuteric alteration can generate easily weathered REE phases, particularly fluorocarbonates. In the case of Liberty Hill, hydrothermal alteration may have converted less soluble to more soluble REE minerals. Additionally, regolith P content was inversely correlated with the fraction ion-adsorbed REEs, and weathering related secondary REE-phosphates were found in some regolith profiles. Both patterns illustrate how low P content aids in the accumulation of ion-adsorbed REEs. The localized occurrence at Liberty Hill sheds light on conditions and processes that generate ion-adsorbed REEs.

Fenitization is an alkali metasomatism that widely occurs in and around the alkaline-carbonatite complex, and is closely associated with rare earth elements (REE) mineralization. However, the origin and nature of the fenitizing fluids and its role in REE mineralization are poor understood. The Lizhuang REE deposit in the Panxi region, SW China, is hosted in a syenite-carbonatite complex with low- and high-grade fenitization. In this study, we conducted detailed petrographic, compositional and isotopic studies on the fresh/unaltered syenite and low- and high-grade fenites to reveal the origin and nature of the fenitizing fluids and their effects on REE mineralization. Our results show that the whole-rock Na/K ratios gradually increase from the fresh syenite, low-grade fenites to high-grade fenites, as well as mineral replacements, such as K-feldspar is replaced by albite and Ca-rich clinopyroxene is replaced by Na-rich clinopyroxene, indicating that sodic fenitization occurred in the Lizhuang syenite system. In situ U-Pb dating of the unaltered and altered apatite shows that the hydrothermal alteration processes are nearly simultaneous with the emplacement of syenite and carbonatite during 27.4–25.3 Ma, maybe lasting for ~2 Ma. In addition, the altered regions of feldspar, clinopyroxene and apatite have in situ 87Sr/86Sr ratios ranging from 0.70580 to 0.70674, which is consistent in error with those of the unaltered regions and host rock syenite-carbonatite complex (0.70566–0.70666). It is suggested that the fenitizing fluids were exsolved from the syenite-carbonatite complex in a relatively closed system. As the increase of alteration degree, the proportion of hydrothermal minerals (e.g., barite, calcite, fluorite and bastnasite) in fenite increased gradually, indicating that the fenitizing fluids are enriched in SO42−, CO32− and F−. This is also supported by the elevated F and SO3 contents from the unaltered to altered apatite. The increasing REE concentrations, from the fresh syenite, low-grade fenite to high-grade fenite, indicate that REE minerals such as bastnasite were precipitated from the fenitizing fluids during fenitization processes. In-situ analyses on the altered clinopyroxene and apatite show variable REE losses compared to the unaltered precursors, which indicates the successive remobilization and transferring of REE by fenitization fluids. Therefore, two discrete stages of fenitization have been identified in the Lizhuang REE deposit, resulted from fluids exsolved from the syenite and carbonatite, respectively. Meanwhile, such fenitization fluids are effective extracting agents of REE in post-magmatic stage, which is crucial to REE remobilization and precipitation to form economic deposit.

We investigated the calcination of a rare earth carbonatite ore from Niobec in Quebec, Canada, containing bastnasite and monazite. The bastnasite decomposed at a relatively low temperature of approximately 400 °C while the monazite decomposed through solid-state reactions with associated minerals at temperatures exceeding 700 °C. A global kinetic model was developed that represented the calcination kinetics of the whole ore based on the individual calcination kinetics of the minerals nested in the ore. The decomposition of bastnasite and the interaction of monazite with calcium oxide in the ore was used to estimate rare earth oxide production during calcination. Initially, the model was developed for small particles and was thus adapted to larger particle sizes by including a coefficient based on physical particle size cut parameters such as surface area, density, and particle diameter.

To separate and enrich rare-earth elements (REE) minerals from their ores through flotation process has become an attracting topic for REE’s strategic position. In the present investigation, the floatability of bastnasite [(Ce,La)CO3F] was explored by using 1-hydroxydodecylidene-1,1-diphosphonic acid (HDDPA) as a collector. The micro-flotation results showed that bastnasite displayed an eminent floatability under pH 7.0–10.0, and HDDPA realized an efficient separation of bastnasite from calcite at pH around 8.0. Zeta potential and solution chemistry inferred that at pH 7.5–9.3, HDDPA3− anions were glad to replace the CO32- ions of Ce(Ⅲ) carbonates in/on bastnasite interface, resulting in a high flotation recovery of bastnasite. With increasing OH- concentration, the competition ability of OH- against HDDPA anion intensified, gradually the surface Ce(III) hydroxide species increased, and the floatability of bastnasite reduced. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) recommended that the surface Ce(III) of bastnasite interacted with the O atoms of HDDPA’s O P(O)O group to generate a four membered ring configuration, which hydrophobized bastnasite particles.

Rare earth minerals (REM) may be beneficiated using a variety of separation techniques with froth flotation being the most commonly applied in operating REM separation plants. Many different collectors have been tested with traditional REM such as bastnasite. The most successful are the hydroxamic acids. The Nechalacho deposit contains many REM for which there is minimal processing information in literature. Thus, experimental investigation into their flotation behaviour is required. This work focuses on understanding the effect of a benzohydroxamic acid collector on the flotation of a REM enriched pre-concentrate from the Nechalacho deposit (after lab-scale gravity and magnetic separation steps). The lab-scale flotation response of the REM is quantified using mass recoveries, water recoveries, QEMSCAN and chemical assay data and TOF-SIMS in order to study the recovery, entrainment and kinetics of different REM. Three different flotation schemes are investigated to determine the effect of a secondary addition of collector as well as the addition of lead ions, a known activator in hydroxamic acid flotation. It is important to note that the goal of this work is to determine fundamental flotation properties of the different REM in the Nechalacho deposit. As such, the process investigated here is not indicative in any way of the current process design for this deposit.

Application of tetrabutylammonium bis(2-ethylhexyl)-phosphate ([N 4444 ][DEHP]), a room temperature ionic liquid (IL), as an aqueous collector for flotation of model monazite and bastnasite minerals was investigated through micro-flotation tests, zeta potential measurements, Fourier Transform Infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The ionic liquid was shown to have superior performance to float both model rare-earth (RE) minerals as compared with calcite, dolomite and quartz minerals as typical gangue minerals. Parallel to this, micro-flotation tests of a rare-earth ore containing bastnasite and monazite minerals were found in line with [N 4444 ][DEHP] stronger collecting power towards RE model minerals even outperforming hydroxamic acid-containing collectors. With regard to the mineral surface chemistry, zeta potential measurements, FTIR characterization and XPS analysis, it was established that [N 4444 ][DEHP] uptake on bastnasite and monazite surfaces was via chemisorption involving specifically the P O and P O groups of the IL anionic moiety. IL anionic and cationic interactions during RE mineral flotation were rationalized in terms of an inner synergistic pathway: IL anionic moiety chemisorbing on bastnasite and monazite surfaces prompting uptake of cationic moiety via electrostatic attraction and/or via hydrophobic chain interactions of the cation alkyl chains with the chemisorbed IL anionic layer. Finally, for calcite as the most responsive among gangue minerals, the characterization techniques divulged the weaker IL-surface interactions. Hence, this investigation opens up new prospects for more selective ionic-liquid collectors to be used in the flotation of RE minerals.

Rare earth metals are essential ingredients for the development of modern industry as well as designing and developing high technology products used in our daily lives. Consequently, the worldwide demand of rare earth metals is rising quickly and predicted to surpass the supply by 40,000 tons annually. However, their availability is declining, mainly due to the export quotas imposed by the Chinese government and actions taken against illegal mining operations. This has laid emphasis to exploit and expand technologies to meet the future necessities of rare earth metals. Bastnasite, monazite, and xenotime are their chief mercantile sources, which are generally beneficiated by flotation, gravity or magnetic separation processes to get concentrates that are processed using pyro/hydrometallurgical routes. To develop feasible and eco-friendly processes, R&D studies are being conducted for the extraction of rare earth metals from leached solutions (chloride, nitrate, sulfate, thiocyanate, etc.) using different cationic, anionic and solvating solvents or ions depending on material and media. Commercial extraction of rare earth metals has been carried out using different extractants viz. D2EHPA, Cyanex 272, PC 88A, Versatic 10, TBP, Aliquat 336, etc. The present paper reviews the methods used for the recovery of rare earth metals from primary as well as secondary resources, with special attention to the hydrometallurgical techniques, consisting of leaching with acids and alkalis followed by solvent extraction, ion exchange or precipitation. The piece of comparative and summarized review will be useful for the researchers to develop processes for rare earth recovery under various conditions.

Rare earth elements (REEs) have found applications in the aerospace, automotive, consumer electronics and lighting industries, among others. A special class of REEs known as heavy rare earths (HREEs) is of particular importance to energy applications. With the growing clean energy technologies incorporating HREEs, it is valuable to examine their environmental emissions and energy requirements. Currently, extraction of HREEs is mainly carried out in China, where they are extracted mainly via open pit mining of bastnasite and/or monazite and leaching of ion-adsorption clays. Leach mining varies significantly from open pit mining technique in that the ores have much lower REE content but REEs stay as cations thus there is no need for physical and chemical beneficiation. To date limited life cycle assessment (LCA) studies have been done on REEs production and all of them are for the bastnasite/monazite route. This paper presents the first LCA of in-situ leach mining of REEs from ion adsorption clays in southern China. The function unit was defined as production of 1 kg of mixed rare earth oxides (REOs) of purity 92%. Ecoinvent 3.0 database was adopted for inventory analysis with material and energy flow information gathered from Chinese literature. To facilitate the use of results in U.S. and EU, TRACI and ILCD in SimaPro 8 were used for environmental impact assessment and cumulative energy demand was also considered as one additional category. The results showed that the environmental impacts for REOs derived from ion adsorption clays are similar in categories such as global warming and cumulative energy demand, but differs significantly in categories of eutrophication and acidification. Since the content of high value HREEs is much higher in ion adsorption clays, when economic value based allocation is used individual REO from in situ leaching has lower environmental impacts across all categories considered. With estimates of HREEs derived from ion-adsorption clays accounting for approximately 35% of the Chinese output, this LCA is a step towards getting a full understanding of the true environmental impact of technologies incorporating HREEs.

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnasite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnasite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnasite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnasite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce3 +, released from bastnasite rapidly, entered the rhabdophane lattice before being oxidized to Ce4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce3 + was oxidized into Ce4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnasite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.

The Bayan Obo deposit is a world-class Fe-REE-Nb deposit, and its reserves of rare earth element (REE) resources rank the first over the world. In the face of the current situation of insufficient utilization rate of rare earth resources and scarcity of middle-heavy rare earth elements (M−HREE) resources, the Bayan Obo deposit with such a huge amount of M−HREE cannot be underestimated. In this paper, the occurrence characteristics of M−HREE in different types of iron ore in the Bayan Obo main ore body are studied by using field emission scanning electron microscope (FESEM), energy dispersive spectrometer (EDS) and advanced mineral identification and characterisation system (AMICS), and the enrichment mechanism is also discussed. The results show that both Sm and Y are the most abundant M−HREE in each type of iron ore in the main ore body, and the content of M−HREE accounts for 1.41%–5.57% of total REE, among which the content of M−HREE in aegirine type Nb-REE-Fe ore (824.47 ppm) and fluorite type Nb-REE-Fe ore (794.82 ppm) are higher, and the content of M−HREE in massive type Nb-REE-Fe ore is lower (318.49 ppm). The main minerals containing M−HREE are bastnasite, parisite, Huanghoite, monazite, aeschynite and fergusonite, among which the content of M−HREE in fergusonite and aeschynite are the highest. According to the characteristics of mineral paragenetic association of REE in this ore district, it is believed that the REE migrates mainly in many different forms of complexes. Heavy rare earth elements (HREE) mainly experienced carbonatite magmatism stage, sodium-fluorine metasomatism stage and late vein mineralization stage, and finally got enrichment.

Summary Separating rare-earth-element-rich minerals from unwanted gangue in mined ores relies on selective binding of collector molecules at the interface to facilitate froth flotation. Salicylhydroxamic acid (SHA) exhibits enhanced selectivity for bastnäsite over calcite in microflotation experiments. Through a multifaceted approach, leveraging density functional theory calculations, and advanced spectroscopic methods, we provide molecular-level mechanistic insight to this selectivity. The hydroxamic acid moiety introduces strong interactions at metal-atom surface sites and hinders subsurface-cation stabilization at vacancy-defect sites, in calcite especially. Resulting from hydrogen-bond-induced interactions, SHA lies flat on the bastnäsite surface and shows a tendency for multilayer formation at high coverages. In this conformation, SHA complexation with bastnäsite metal ions is stabilized, leading to advanced flotation performance. In contrast, SHA lies perpendicular to the calcite surface due to a difference in cationic spacing. We anticipate that these insights will motivate rational design and selection of future collector molecules for enhanced ore beneficiation., Graphical Abstract, Highlights • Salicylhydroxamic acid (SHA) is an effective collector for flotation of bastnäsite • DFT calculations show that the phenol group anchors SHA flat to bastnäsite surface • Spectroscopic results suggest SHA multilayers on bastnäsite at high coverage • This peculiar adsorption explains efficacy of SHA in bastnäsite flotation from ores, Chemical Engineering; Spectroscopy; Physical Inorganic Chemistry; Surface Chemistry

The rare earth element (REE) mineralization of Gakara (Burundi) has first been discovered in 1936 and has periodically been the subject of geological studies, at times when the exploitation of bastnasite-(Ce) and monazite-(Ce) was economically interesting. This study focuses on the establishment of a mineral paragenesis for Gakara, with special attention to the REE-bearing phases, to understand the formation history of the deposit. The paragenesis can be subdivided into 3 stages: primary ore deposition, brecciation stage and supergene alteration. Evidence for fenitization processes (i.e. pinkish-red cathodoluminescence of K-feldpar, brecciation stage) and the strong enrichment of light REEs in bastnasite and monazite substantiate the hypothesis of a structurally controlled hydrothermal mineralization with a strong carbonatitic affinity. This likely confirms the association of the Gakara REE deposit with the Neoproterozoic alignment of alkaline complexes and carbonatites along the present-day Western Rift. It suggests a direct link with a – currently unidentified – carbonatitic body at depth, possibly derived from a predominantly metasomatized lithospheric mantle.

Rare-earth elements play a crucial role in modern technologies and are necessary for a transition to a green economy. Potentially economic deposits of these elements are typically hosted in minerals such as monazite, bastnasite, and eudialyte (a complex Na-Ca-Fe-Zr silicate mineral with Cl), making these prime targets for geological research. Globally, rare-earth mineral deposits commonly show evidence of polyphase development and mineralisation processes, which need to be better understood to improve exploration strategies. The Norra Karr alkaline complex (Sweden) contains a globally significant deposit of rare-earth elements, hosted in the mineral eudialyte. In this study, we focussed on eudialyte crystals in undeformed, cross-cutting pegmatoid veins from Norra Karr. In order to determine their age, we refined an established micromilling method to enable sampling of minerals rich in rare-earth elements for precise analysis of major and trace elements, Nd isotope ratios, and Sm-Nd geochronology down to a scale of

In this work, decanedioic hydroxamic acid (DDHA) was introduced as a novel collector for the flotation separation of bastnӓsite and calcite, and the results were compared with those obtained for the conventional hydroxamic acid collectors benzohydroxamic acid (BHA) and octyl hydroxamic acid (OHA). The microflotation results showed that DDHA had better selectivity than BHA and OHA for the flotation of bastnӓsite from calcite. The flotation of artificially mixed minerals confirmed that the effective separation of bastnӓsite from calcite could be realized in the presence of DDHA. The zeta potentials of mineral surfaces with or without these collectors were measured, and the results indicated that DDHA strongly interacted with the bastnӓsite surface but was not adsorbed on the calcite surface.

Elevated uranium concentrations have been reported in many IOCG deposits, but detailed information about the occurrences of uranium minerals and their relationships with other minerals remains scarce, which hinders understanding of the mineralization mechanisms and the nature of the association of these metals. This paper reports a new case of uranium enrichment in an IOCG system, the Lala Cu-Fe deposit in the Kangdian region, SW China. Whole-rock analyses of ores and barren rocks yielded highly variable U concentrations ranging from 0.76 to 266 ppm. Uranium shows a strong positive correlation with Mo, broadly positive correlations with Cu and ΣREE, and a vague, negative correlation with Th. Four uranium minerals, uraninite [UO2], uranothorite [(Th,U)SiO4], polycrase [(Y,Ca,Ce,U,Th)(Ti,Nb,Ta)2O6], and coffinite [U(SiO4)1-x(OH)4x], were identified. The uraninite is divided into two phases: phase 1 (Ur1) characterized by corroded or irregular crystal shapes, and phase 2 (Ur2) showing well-developed, subhedral to euhedral crystal shapes. Ur1 is interpreted to be formed in the primary Cu – Fe – Mo – REE – U mineralization, together with the bulk of Cu and other metal sulfides, as well as other U and REE minerals, including uranothorite, polycrase, bastnasite and xenotime, and accompanied by K-alteration (K-feldspar and biotite). Ur2 is interpreted to be formed in a secondary hydrothermal event characterized by introduction of fluorite and carbonates, in which U and Mo, and to lesser extent Cu and REE, were remobilized, while Th remained relatively stable. The primary mineralization is inferred to have taken place in a period from ca. 1086 to 1053 Ma based on previous Re-Os geochronology, and the secondary mineralization (remobilization) likely took place from ca. 888 to 828 Ma, as suggested by uraninite chemical ages obtained in this study and other published geochronological data. These ages correspond to tectonomagmatic events taking place in generally extensional environments, in the western margin of the Yangtze Block during the Meso- to Neoproterozoic time. The Lala Cu-Fe deposit represents a new case of IOCG deposits with U (and REE) enrichment, the economic potential of which warrants further examination.

As a key source of strategic commodities for advanced technologies, carbonatite-related (carbonatite–nordmarkite complex) rare earth element (REE) deposits are globally important resources. Such deposits have different ore types, scales, ore-formation structures, and evolutionary processes. However, the causes of these variations have not been well studied, which prevents us from understanding the formation of such deposits. The factors that lead to the formation of large carbonatite-related REE deposits have also not been carefully documented. Fortunately, the Cenozoic Mianning–Dechang (MD) REE belt in eastern Tibet contains several medium- and large-scale carbonatite-related REE deposits, including brecciated, weathered, and disseminated ores, providing an ideal opportunity to investigate these factors. Current and this studies show that the deposits in the MD belt have similar formation stages, crystallization sequences, sources, and REE mineralization conditions. Previous studies have shown that the REE mineralization occurred alongside the formation of large-scale overprinted gangue minerals, such as barite, fluorite, and calcite during the lowest-temperature hydrothermal stage ( 4 2−, and CO2 are important for transporting and precipitating REE. Detailed geological mapping suggests that the variation in ore type was caused by local ore-controlling structures, rather than being due to different depths of formation. Bastnasite has similar initial 87Sr/86Sr (0.7059–0.7080), 143Nd/144Nd (0.5123–0.5124), 207Pb/204Pb (15.594–15.648), and 208Pb/204Pb (38.422–71.488) ratios along the whole belt, implying that all the deposits have the same source and the REE were sourced directly from a mixture of crustal and mantle material. The C–O isotopic compositions of the carbonatites (δ18OV-SMOW = 6.4‰ to 10.5‰, δ13CV-PDB = − 3.9‰ to − 8.5‰) and bastnasite (δ18OV-SMOW = 9.5‰–16.3‰, δ13CV-PDB = − 4.7‰ to − 9.3‰) suggest that low-temperature alteration occurred along with REE mineralization. Development of pegmatitic stage and aegirine–augite and arfvedsonite fenitization alteration may promote the formation of large-scale REE deposits. The giant Maoniuping and Dalucao deposits both had pegmatitic stages that involved the formation of coarse-grained barite, fluorite, and calcite with REE contents of up to 6305 ppm, suggesting the pegmatitic stage suggest another REE enrichment event after the magmatic stage, and large-scale REE mineralization. The intense alkali alteration that forms arfvedsonite and aegirine–augite in carbonatite–nordmarkite complexes was only found in the Maoniuping deposit, whereas biotitation was found in the Dalucao and Lizhuang deposits. This suggests that the Maoniuping deposit experienced more intense alteration, which may have led to more effective REE migration from the wallrock into the ore-forming fluids. The mantle source, the evolution of the magma, the presence of a pegmatitic stage, the composition of the fluids, and the high degree of alkaline alteration could have affected the scale of the deposits, in addition to the large volume of carbonatite–nordmarkite complexes and multiple phases of tectonism.

The Morro dos Seis Lagos niobium rare earth element, Ti-bearing lateritic deposit (Amazonas, Brazil) is derived from a primary siderite carbonatite. The complex is the only example of a Nb deposit in which Nb-rich rutile is the main Nb ore mineral. Apart from the laterites, at the current level of exposure the complex consists only of siderite carbonatite; silicate rocks are absent. Three types of siderite carbonatite are recognized: (1) a brecciated and oxidized core siderite carbonatite consisting of up to 95 vol% siderite together with: hematite; pyrochlore; Nb-brookite; Ti-maghemite; and thorobastnasite; (2) a REE- and P-rich variety of the core siderite carbonatite consisting of siderite (up to 95 vol%), hematite, minor pyrochlore, monazite and bastnasite; (3) a border hydrothermal siderite carbonatite with ~70 vol% siderite, barite (~15 vol%), gorceixite (~7 vol%) and minor rhabdophane and pyrochlore. The country rock gneiss in which the carbonatite was emplaced was affected by potassic fenitization, with the formation of phlogopite and orthoclase together with monazite, fluorapatite and bastnasite. The siderite carbonatites exhibit a wide variation of δ13C (−5.39‰ to −1.40‰), accompanied by a significant variation in δ18O (17.13‰ to 31.33‰), especially in the REE-rich core siderite carbonatite, and are explained as due to the presence of both H2O and CO2 in the magma. The core siderite carbonatite is the richest in Fe (48.64–70.85 wt% Fe2O3) and the poorest in Ca (up 0.82 wt% CaO) example of a siderite carbonatite yet recognized The ferrocarbonatite has significant contents of Mn, Ba, Th, Pb and LREE, and a very high Nb (up to 7667 ppm) content due to the presence of Nb-brookite. The substitution 3Ti4+ = Fe2+ + 2Nb5+ recognized in Nb-rich brookite explains enrichment of Nb in the core siderite carbonatite and indicates formation in a reducing environment. The high Nb/Ta ratio (1408–11,459) of the carbonatite is compatible with residual liquids derived by fractional crystallization. The 87Sr/86Sr (0.70411–0.70573) and 144Nd/143Nd (0.512663–0.512715) isotopic data suggest the carbonatite is mantle-derived with essentially no crustal contamination and is younger than the maximum age of 1328 ± 58 Ma (U Pb in zircon). We suggest that the Morro dos Seis Lagos carbonatite complex represents the upper-most parts of a differentiated carbonatite magmatic system, and that the siderite carbonatite is related to late-magmatic-to-carbo-hydrothermal processes.