Important Rare Earth Research Articles

Recent Uses of Ionic Liquids in the Recovery and Utilization of Rare Earth Elements

The importance of rare earth elements as a basis for the development of new technologies or the improvement of existing ones makes their recovery from raw and waste materials necessary. In this recovery, hydrometallurgy and its derivative solvometallurgy play key roles due to their operational characteristics, which are emphasized with the use of ionic liquids. This manuscript reviews the most recent advances (2023 and 2024) in the use of ionic liquids in unit operations (leaching and separation technologies) aimed at the recovery of these valuable and strategic metals. Moreover, a comprehensive review is presented of the use of these chemicals in the development of advanced materials containing some of these rare earth elements.

Mineralization of Zr-REE-Y in the Ngaoumbol iron formations, central Cameroon: Insights from petrography, mineral chemistry and whole rock geochemistry

The increasing importance of rare earth elements (REE) and critical metals in contemporary society has led us to investigate the mineral potential of the Ngaoumbol area, located within Cameroon's Central African Fold Belt (CAFB). In this study, we have conducted a comprehensive analysis that includes petrography, whole rock geochemistry, and mineral chemistry, along with the application of an outlook coefficient known as Koult, with the aim to evaluate the prospectivity of the Ngaoumbol iron formations as a potential source of REE-Y resources. This coefficient is defined as the ratio of the relative abundance of critical Rare Earth Elements to the relative abundance of excess REE. The iron formations in the Ngaoumbol area are fine-to medium-grained foliated rocks with alternating magnetite and actinolite bands and quartz bands, suggesting a sedimentary parentage. These rocks have an average REE-Y content of 1438.43 ppm and a Koult of 0.77, indicating their potential as raw sources for REE. Furthermore, the investigated samples exhibit high average Zr content (7748 ppm), suggesting that the rocks may host potentially economic Zr ore. The Zr-REE-Y mineralization in the Ngaoumbol area is hosted in detrital zircon, monazite and xenotime, probably deriving from the weathering of alkaline/subalkaline rocks surrounding the deposits. Our findings suggest that the Ngaoumbol area has promising REE and Zr resources. However, further exploration and evaluation are necessary to determine the extent and economic viability of these resources.

Activated carbon from Camellia oleifera shells for adsorption of Y(iii): experimental and DFT studies.

Yttrium is an important rare earth element and is widely used in fields such as special glass preparation, metallurgy, and materials science. However, it is difficult to recover yttrium ion waste from dilute solutions with traditional processes, resulting in a significant waste of rare earth resources. The simple, effective, and easy-to-operate adsorption method is the most promising method for recovering yttrium, which is of great significance for sustainable development of the rare earth industry. In this study, activated carbon was prepared from Camellia oleifera fruit shells (COS) using phosphoric acid activation, and efficient recovery of Y(iii) from the Camellia oleifera fruit shell activated carbon was studied. Adsorption equilibrium data showed that this activated carbon had a Y(iii) adsorption capacity of 35.41 mg g-1, indicating significant potential for recovery of yttrium ions. The adsorption of Y(iii) by the activated carbon prepared from COS was consistent with the Langmuir model, and the adsorption data were consistent with the pseudo second-order kinetic model, indicating that the adsorption process was primarily chemical adsorption. After adsorption, the surface of the activated carbon contained large amounts of N, O, and Y, indicating that Y(iii) was stably adsorbed. The mechanisms for adsorption of Y(iii) on three types of activated carbon were studied through DFT calculations. The results showed that Y(iii) interacted with the carbon atoms on the surfaces to form new chemical bonds. The yttrium ion adsorption capacities for the three different activated carbons decreased in the order C I > C II > C.

Iron homeostasis as a cell detoxification mechanism in Mesorhizobium qingshengii J19 under yttrium exposure.

Yttrium (Y), an important rare earth element (REE), is increasingly prevalent in the environment due to industrial activities, raising concerns about its toxicity. Understanding the effects of Y on microorganisms is essential for bioremediation and biorecovery processes. This study investigates how Mesorhizobium qingshengii J19, a strain with notable resistance to Y, manages iron homeostasis as a detoxifying mechanism under Y stress. Using comparative genomic and transcriptomic analyses, we explored the gene expression profile of strain J19 to identify the mechanisms underlying its high Y resistance and effective Y removal from the medium. Genome-wide transcriptional profiling revealed 127 significantly differentially expressed genes out of 6,343 under Y stress, with 36.2 % up-regulated and 63.8 % down-regulated. Notably, Y exposure significantly affects cellular iron homeostasis and activates arsenic detoxifying mechanisms. A key finding was the 7.6-fold up-regulation of a TonB transporter gene, indicating its crucial role in Y detoxification. Real-time PCR (RT-PCR) analysis of the selected gene confirmed the accuracy of RNA sequencing results. Further validation showed that iron supplementation mitigates Y-induced growth inhibition, leading to reduced ROS production in strain J19. This study elucidates the molecular mechanisms by which strain M. qingshengii J19 adapts to Y stress, emphasizing the importance of iron in controlling ROS and protecting against Y toxicity. It also highlights critical pathways and adaptive responses involved in the strain's resilience to metal stress.

Removal of REE and Th from solution by co-precipitation with Pb-phosphates

The supply of technologically important rare earth elements (REE) is a concern in Europe, hence the recovery of REE from alternative sources has recently become widely investigated. One of the problems is the lack of cost-effective technologies for REE recovery from leaching solutions. The present work investigated the potential for recovering REE and Th from leaching solutions by co-precipitation with Pb phosphates. A set of four experiments were conducted using analytical reagent grade chemicals to analyze the effects of Pb and different pH on the efficiency of REE and Th removal from aqueous solutions. After selecting the best conditions, two additional experiments were performed using solutions obtained from leaching REE-rich apatite mine waste.The precipitates resulting from the experiments as well as the solutions before and after precipitation were analyzed. It was found that the formation of a crystalline mixture of REE- and Th- enriched pyromorphite, Pb5(PO4)3Cl, and Pb-phosphates, about which little has been known so far, was responsible for complete (>99%) removal of REE and Th from aqueous solutions at pH 4 and 6. At lower pH, the removal is incomplete except for Sc and Th, which probably form a distinct phases. Besides that, no fractionation of LREE and HREE was observed. The experiments included the study of solutions resulting from the leaching of REE-rich apatite waste, which may contribute to the development of new technologies for REE recovery from wastes.

Balancing economic growth and environmental protection: A sustainable approach to Malaysia's rare-earth industry

The rapid advancement of technology has highlighted the importance of rare earth elements (REE) for achieving sustainability. However, despite their potential, there are several challenges such as high demand, price fluctuations, supply risks, and unstable geopolitical landscapes that hinder their recovery efforts. Malaysia has been involved in the REE industry for decades, mainly by processing tin mining by-products into rare earth minerals (monazite). In 2012, Lynas, an Australian company, established a state-of-the-art manufacturing facility called Lynas Malaysia in the Gebeng Industrial Estate near the Port of Kuantan in Malaysia, where they separate and process Rare Earth materials from imported monazite (lanthanide concentrate) to produce Rare Earths Oxide (REO). However, the locals have raised concerns about the production of radioactive by-products, leading to an activist movement against Lynas. To counter this, Malaysia aims to establish a comprehensive REE business strategy that utilizes local rare earth minerals. Although the extraction of REE from local ion adsorption clays (IC) has been advantageous with minimal issues relating to radioactive waste production, this review explores alternative local secondary sources that could be a sustainable REE source for Malaysia. The review also addresses the causes of the public protests and political interferences that jeopardize the industry's long-term sustainability. A progressive framework is proposed to improve current mineral processing practices and provide Malaysia with a viable rare-earth industry from upstream to downstream.

Importance of Rare Earth Elements in Modern Society and their Potential Source in Coal Ashes

Introduction: Rare Earth Elements (REEs) are crucial for advanced technologies in modern society, ranging from electronics to renewable energy and defense. Their increasing demand in critical industries underscores the need for a consistent and sustainable supply. Historically extracted from REE-rich minerals such as bastnäsite and monazite, the search for alternative sources has gained prominence, among these, coal ashes stand out, produced by burning coal to generate energy, ashes contain REEs in relatively low concentrations but with significant potential due to their massive global volume. The importance of ensuring the resilience of the REE supply chain has driven research to extract these elements from coal ashes, diversifying sources and reducing reliance on specific minerals. As technologies advance and REE applications expand, the ability to recover them from unconventional sources like coal ashes could have a sustainable impact on our societies. Research into the extraction and utilization of REEs from ashes is in progress and may enhance supply security. This study highlights the global importance of finding alternative sources of REE, such as coal ash, emphasizing the need to ensure a consistent and sustainable supply of these essential elements.

Magnesium isotope fractionation in differentiation of mafic-alkaline-carbonatitic magma and Fe-P-REE-rich melt at Bayan Obo, China

The Bayan Obo area in the North China Craton (NCC) contains the largest rare earth element (REE) resources in the world. The key to this gigantic and efficient REE accumulation has been the focal point of century-long research efforts. Intense differentiation of mantle-derived alkaline magmas is envisaged as a highly viable process for REE enrichment based on the first discovery of mafic-alkaline-carbonatitic suite in the Bayan Obo region. Geochronological and Sr-Nd-Hf-O isotopic analyses revealed that these rocks derived from a common mantle source and evolved with magmatic differentiation at 1.31 Ga to 1.32 Ga. Elemental geochemistry and Mg isotopes in this magma series (alkaline diabase sill, syenite dyke and carbonatite) unambiguously support the differentiation model. The earliest ferrocarbonatite, with nearly undifferentiated REE concentrations, has mantle-like δ26Mg (−0.27 ± 0.03‰), and therefore can be considered as the original product of the mantle derived alkaline magma at Bayan Obo. The subsequent magnesiocarbonatites have a LREE enrichment feature, which is consistent with the alkaline diabase sills. The magnesiocarbonatites possess light Mg isotopic composition (from − 0.42‰ to − 0.50‰), whereas the alkaline diabase sills have heavy Mg isotopic composition (from − 0.03‰ to − 0.05‰). This rock assemblage should present two end members, which differentiated likely by immiscibility in the chamber from a common alkaline magma. The subsequent syenite dyke has no obvious Mg isotopic variation (from − 0.44‰ to − 0.39‰) during differentiation from the above alkaline magma. Notably, as the most important REE hosts, fine-grained ferrocarbonatites show large Mg isotopic variations (from − 0.85‰ to + 0.13‰) and present positive correlations with total MgO and CaO contents, but negative with total Fe2O3, P2O5 and REE contents. In fine-grained ferrocarbonatite, closely associated apatite, monazite, hematite and magnetite minerals occur as a special intergrowth texture. This unique paragenetic assemblage is likely the mineralization record of a Fe-P-REE-rich melt, which shows particular affinity of hydrothermal fluid and light Mg isotope in carbonatitic magma. By contrast, magnesian siderite phenocrysts as the early cumulates in carbonatitic magma are enriched in heavy Mg isotope (from − 0.07‰ to + 0.21‰). Immiscibility of Fe-P-REE-rich melt and fractional crystallization of carbonate minerals are responsible for large Mg isotope fractionation and giant REE enrichment in the Bayan Obo deposit.

Antibacterial activity of novel synthesized chitosan-graft-poly(N-tertiary butylacrylamide)/neodymium composites for biomedical application.

In this present study, composites of chitosan-graft-poly(N-tertiary butylacrylamide) (CH-graft-poly(N-tert-BAAm)) copolymer, with Neodymium (Nd), an important rare earth element, were prepared by precipitation technique. Nd was successfully incorporated into the polymer of different weight percentages (0.5%, 1%, and 2%) without any degradation. The effect of neodymium additives on the structural, morphological, and antibacterial activities against gram-positive bacteria and gram-negative bacteria of the polymer was analyzed using various instrument techniques. X-ray diffraction (XRD) results together with Fourier Transform Infrared (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) studies confirmed the morphology of Nd-doped CH-graft-poly(N-tert-BAAm) composites without any other impurities. The antibacterial effect of Nd was studied by adding it to the copolymer in a weight ratio of 0.5%-2%. The antibacterial effect of neodymium concentration on four different strains of bacteria was investigated: Escherichia coli (ATCC 25922) (E. coli), Pseudomonas aeruginosa (DSM 50071) (P. aeruginosa), Bacillus subtilis (DSM 1971) (B. subtilis), and Staphylococcus aureus subsp. aureus (ATCC 25923) (S. aureus). The antibacterial activities of the obtained composites were determined using the Agar Well Diffusion Assay Method. Experimental results show that Nd binds well to CH-graft-poly(N-tert-BAAm). Activity against E. coli, P. aeruginosa, B. subtilis, and S. aureus subsp. aureus creates a potential for pharmaceutical and biomedical applications.

The impact of objective and subjective valuations on behaviours: A case study of a rare earth processing plant

Despite the importance of rare earth elements in modern technologies, the establishment of rare earth plants often faces strong opposition from the community due to a fear of environmental impacts. This study examines information about actual and perceived pollution produced by a rare earth plant in Malaysia, Lynas Advanced Material Plant (LAMP), and the community's response to it. A survey of 570 respondents reveals that LAMP is perceived to have a high environmental impact in the long run, although its pollution levels are mostly below the limit set by the authorities. About 18% of respondents have undertaken averting behaviours (AB) such as protest, reduction in outdoor activities, and increased health expenditure. The estimated averting expenditure, excluding migration cost, is about 0.06% of household monthly income. Logit estimations show that perception is a significant determinant of AB, while Tobit estimations indicate that young, male, non-Malays and those exposed to poor surrounding air quality, low levels of trust and perceived high levels of environmental impact will incur additional cost. Rare earth companies and the authorities should therefore find ways to communicate with and gain trust from the locals to reduce their fear and to avoid unnecessary protective actions.

Detection and Relative Quantification of Neodymium in Sillai Patti Carbonatite Using Decision Tree Classification of the Hyperspectral Data.

A recent increase in the importance of Rare Earth Elements (REEs), proportional to advancements in modern technology, green energy, and defense, has urged researchers to look for more sophisticated and efficient exploration methods for their host rocks, such as carbonatites. Hyperspectral remote sensing has long been recognized as having great potential to identify the REEs based on their sharp and distinctive absorption features in the visible near-infrared (VNIR) and shortwave infrared (SWIR) electromagnetic spectral profiles. For instance, neodymium (Nd), one of the most abundant Light Rare Earth Elements (LREEs), has among the most distinctive absorption features of REEs in the VNIR part of the electromagnetic spectrum. Centered at ~580, ~745, ~810, and ~870 nm in the VNIR, the positions of these absorption features have been proved to be independent of the mineralogy that hosts Nd, and the features can be observed in samples as low in Nd as 1000 ppm. In this study, a neodymium index (NI) is proposed based on the 810 nm absorption feature and tested on the hyperspectral images of the Sillai Patai carbonatite samples to identify Nd pixels and to decipher the relative concentration of Nd in the samples based on the depth of the absorption feature. A preliminary spectral study of the carbonatite samples was carried out using a spectroradiometer to determine the presence of Nd in the samples. Only two of the absorption features of Nd, centered at ~745 and ~810 nm, are prominent in the Nd-rich samples. The other absorption features are either weak or suppressed by the featureless spectra of the associated minerals. Similar absorption features are found in the VNIR and SWIR images of the rock samples captured by the laboratory-based hyperspectral cameras that are processed through Minimum Noise Fraction (MNF) and Fast Fourier Transform (FFT) to filter the signal and noise from the reflectance data. An RGB false-color composite of continuum-removed VNIR reflectance bands covering wavelengths of 587.5, 747.91, and 810.25 nm efficiently displayed the spatial distribution of Nd-rich hotspots in the hyperspectral image. The depth of the 810 nm absorption feature, which corresponds to the concentration of Nd in a pixel, is comparatively greater in these zones and is quantified using the proposed NI such that the deeper the absorption feature, the higher the NI. To quantify the Nd-rich pixels in the continuum-removed VNIR images, different threshold values of NI are introduced into a decision tree classifier which generates the number of pixels in each class. The strength of the proposed NI coupled with the decision tree classifier is further supported by the accuracy assessment of the classified images generating the Kappa coefficient of 0.82. Comparing the results of the remote sensing data obtained in this study with some of the previously published studies suggests that the Sillai Patti carbonatite is rich in Nd and associated REEs, with some parts of the samples as high in Nd concentration as 1000 ppm.

Contrasting alteration textures and geochemistry of allanite from uranium-fertile and barren granites: Insights into granite-related U and ion-adsorption REE mineralization

AbstractAllanite is an important rare earth element (REE)-U-bearing mineral in granites, and it can act as a metal source for the formation of some hydrothermal uranium deposits and ion-adsorption REE deposits. To investigate the potential of allanite as a mineral probe of granite-related uranium mineralization processes and the formation of ion-adsorption REE deposits, we present textures, geochemistry, and in situ U-Pb isotope data for allanite from the fertile Changjiang granite associated with the Changjiang uranium ore field and barren Jiufeng granite in the Zhuguangshan batholith, South China. Alteration of allanite in the Changjiang granite is characterized by the altered domains with lower backscattered electron (BSE) intensities than the unaltered domains and replacement by other secondary minerals such as REE fluorocarbonates, calcite, fluorite, thorite, clay minerals, quartz, chlorite, and epidote. Crystals from the Jiufeng granite were partly replaced by the altered domains appearing darker in BSE images and minor REE fluorocarbonates. The darker domains of the Changjiang and Jiufeng allanite grains have higher Fe3+/(Fe3++Fe2+) ratios and U concentrations than those of the brighter domains, indicating that the alteration of allanite was probably related to more oxidized fluids. This study suggests that the Changjiang granite might have been subjected to the influx of F- and CO2-bearing fluids.The brighter domains of the Changjiang and Jiufeng allanite grains have weighted mean 207Pb-corrected 206Pb/238U ages of 156.7 ± 4.3 Ma and 161.6 ± 5.3 Ma, respectively, consistent with the corresponding zircon 206Pb/238U ages of 156.1 ± 1.4 Ma and 159.8 ± 1.8 Ma. The darker domains of the Changjiang allanite grains yield a weighted mean 206Pb/238U age of 141.4 ± 5.6 Ma, which overlaps within error the timing of a uranium mineralization event (~140 Ma) in the Changjiang uranium ore field and the age of a crustal extension event (140–135 Ma) in South China. The BSE images and elemental maps reveal that rare earth elements such as La and Ce have been released from the Changjiang allanites during alteration and were precipitated as REE-fluorocarbonates that are susceptible to chemical weathering, which sets the stage for the formation of an ion-adsorption REE deposit. Our study suggests that the regional crustal extension might have played an important role in the formation of both granite-related uranium and ion-adsorption REE deposits in South China, as it could have triggered alteration or breakdown of REE-U-bearing minerals in source rocks.

Characterization of nano-minerals and nanoparticles in supergene rare earth element mineralization related to chemical weathering of granites

AbstractIon adsorption-type rare earth element (REE) ore deposits in South China are a major source of heavy rare earth elements (HREE) around the world, which are of considerable economic and strategic significance. In these ores, REE is enriched in the clay minerals, specifically kaolinite and halloysite, which are derived from their parent granitoid by the weathering process. However, the mechanisms of supergene REE mineralization remain unclear. We investigated the nature and origin of supergene REE mineralization, based on a nanoscale study of a typical REE-mineralized granite regolith profile (ΣREEmax = 1201 ppm) in the Dazhou super-large, ion adsorption-type REE deposit, Guangxi Province, South China. Bulk mineralogical and geochemical analyses, coupled with novel nano-characterization techniques [i.e., hollow fiber flow field-flow fractionation inductively coupled plasma-mass spectrometry (HF5-ICP-MS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM)], were used to determine the nature of the nano-minerals and nanoparticles in the regolith samples. X-ray diffraction and SEM-EDS analyses revealed that ion-adsorption clay minerals are dominated by platy-shaped kaolinite and rod-like halloysite (10 and 7 Å) within the regolith. The average clay mineral contents decreased from 38 to 15% from the fully weathered horizon to the semi-weathered horizon, whereas the proportion of halloysite increased in the clay mineral fraction in the deep horizons. The REE-bearing nanoparticles consist predominantly of macromolecules of organic matter (2–5 nm) and clay minerals (5–40 and 40–80 nm) according to the HF5-ICP-MS analysis. There is a close association between REE and Al contents in particles with sizes of 5–40 nm in the semi-weathered horizons and 40–80 nm in the highly weathered horizons, which indicates that nanoscale clay minerals (halloysite and kaolinite, respectively) are important REE carriers. In addition, nanoscale secondary REE mineral phases, including oxide, silicate, and phosphate, were identified by the SEM and TEM observations. These phases are typically adsorbed onto the surfaces of clay minerals, specifically rod-like halloysite, but have different occurrences in the regolith profile. Cesium-oxide (cerianite) and Ce-silicate (cerite) occur mainly in the upper horizon of the regolith profile, whereas low-crystallinity REE phosphates [rhabdophane-(La)] occur mainly in the lower horizon of the profile. Our results indicate that nano-minerals and nanoparticles affect REE enrichment and fractionation during granite weathering. Migration and accumulation of REE-bearing nano-minerals were caused by leaching and neoformation of REE-bearing nano-minerals during secondary precipitation. These processes contribute to the formation of supergene REE mineralization in granite regolith.

Efficient Recovery of Rare Earth Elements and Zinc from Spent Ni-Metal Hydride Batteries: Statistical Studies.

Considering how important rare earth elements (REEs) are for many different industries, it is important to separate them from other elements. An extractant that binds to REEs inexpensively and selectively even in the presence of interfering ions can be used to develop a useful separation method. This work was designed to recover REEs from spent nickel–metal hydride batteries using ammonium sulfate. The chemical composition of the Ni–MH batteries was examined. The operating leaching conditions of REE extraction from black powder were experimentally optimized. The optimal conditions for the dissolution of approximately 99.98% of REEs and almost all zinc were attained through use of a 300 g/L (NH4)2SO4 concentration after 180 min of leaching time and a 1:3 solid/liquid phase ratio at 120 °C. The kinetic data fit the chemical control model. The separation of total REEs and zinc was conducted under traditional conditions to produce both metal values in marketable forms. The work then shifted to separate cerium as an individual REE through acid baking with HCl, thus leaving pure cerium behind.

NADİR TOPRAK ELEMENTLERİNİN UYGULAMA ALANLARI

Madenler insanlık tarihi boyunca hep vazgeçilmez bir öneme sahip olmuştur. Tarih boyunca toplumlarda madencilik faaliyetleri ile gelişmişlik düzeyi ve dolayısıyla refah seviyesi arasında doğrudan bir ilişki kurulabilir. Dünyada stratejik olarak bilinen hammadde kaynaklarından biri de nadir toprak mineralleridir. Zenginleştirme ve saflaştırma proseslerinde sonra nadir toprak elementleri (NTE’ler), nadir toprak metalleri (NTM’ler) ve nadir toprak oksitleri (NTO’lar) gibi çeşitli isimlerle tanımlanmaktadır. Nadir toprak elementlerinin (NTE) keşfi ve beraberinde getirdiği teknolojik gelişmeler de neredeyse hayatımızın her alanında etkisini göstermektedir. Nadir toprak malzemeleri eşsiz fiziksel ve kimyasal özelliklere sahiptir. Nadir toprak elementleri mıknatıs, katalizör, metal alaşımları, elektronik aygıtlar, lazerler, cam-seramikler, şarj edilebilir piller, medikal görüntüleme, telekominikasyon, aydınlatma ve yeni nesil yarıiletken aygıtlar içeren yüksek teknolojik uygulamalarda komponent olarak kullanılmaktadır. Ek olarak, samaryum (Sm), neodimium (Nd) disprosyum (Dy), praseodimium (Pr) ve erbiyum (Er) gibi bazı önemli NTE’ler savunma sanayi ve yenilenebilir enerji teknolojilerinde (rüzgar ve güneş enerjisi) kullanılmaktadır. Kritik teknolojilerde kullanılan bu hammaddelere olan talep gelecekte büyük oranda artacaktır. Bu makalede, nadir toprak elementlerinin önemli uygulamaları, kullanım alanları ve kritik önemleri kapsamlı bir şekilde tartışılmıştır.

U-Shaped Relationship of Rare Earth Element Lanthanum and Oral Cancer Risk: A Propensity Score-Based Study in the Southeast of China.

As an important rare earth element (REE) extensively applied to industry, agriculture, and medicine, lanthanum (La) has attracted a host of health concerns. This study aimed to explore the relationship between La exposure and the risk of developing oral cancer through a case-control study with a large sample size. Serum La levels of 430 oral cancer patients and 1,118 healthy controls were detected by inductively coupled plasma mass spectrometry (ICP-MS). The association of La level with the risk of oral cancer was assessed in two ways: (1) as a continuous scale based on restricted cubic splines (RCS); (2) as a priori defined centile categories using multivariate logistic regression model, based on propensity score matching (PSM) and inverse probability of treatment weighting (IPTW). The RCS revealed a non-linear U-shaped relationship between serum La and oral cancer risk. Serum La deficiency or excess was associated with an increased risk of oral cancer. When the La level was analyzed as a categorical variable, a similar U-shaped association was observed. Of note, compared to those with La concentrations of 0.243–0.341 μg/L (reference quantiles, 41st−60th), the risk was increased in those with the lower or higher quantiles (0.132–0.242 μg/L vs. 0.243–0.341 μg/L: OR = 1.80, 95%CI: 1.07–3.02; 0.342–0.497 μg/L vs. 0.243–0.341 μg/L: OR = 2.30, 95%CI: 1.38–3.84). The results were generally consistent with the PSM and IPTW analyses. This preliminary study provides strong evidence that there was a U-shaped relationship between serum La levels and oral cancer risk. Much additional work is warranted to confirm our findings.

Quantifying the controlling mineral phases of rare-earth elements in deep-sea pelagic sediments

Recent studies suggest that pelagic sediments can enrich rare-earth elements (REE) acting as a significant reservoir for the global REE budget as well as a potential resource for future exploitation. Although Ca-phosphate (e.g., bioapatite fossils) and Fe-Mn (oxyhydr)oxides (e.g., micronodule) have been considered important REE carriers in deep-sea sediments, the proportion of REE held by each mineral phase remains enigmatic. Here, we have investigated the sediments from two promising REE-rich prospective areas: the Tiki Basin in the Southeast Pacific (TKB) and the Central Indian Ocean Basin (CIOB). The mineral grains including bioapatite fossils and Fe-Mn micronodules have been inspected individually by in-situ microscale analytical methods. Correspondently, the REE bound to Ca-phosphate and Fe-Mn (oxyhydr)oxides have been sequentially extracted and quantified. The crucial role of Ca-phosphate is substantiated by sequential leaching which reveals its dominance in hosting ~69.3–89.4% of total REE. The Fe-Mn (oxyhydr)oxides carry ~8.2% to 22.0% of REE in bulk sediments, but they account for ~70.0–80.5% of Ce owing to their preferential adsorption of Ce over the other REE. Surface sediment on modern seafloor can accumulate high REE contents resulting from the REE scavenging by the host phases within the range of sediment-seawater interface. Differences between TKB and CIOB samples indicate that the REE enrichment in the deep-sea environment may be controlled by multiple factors including the productivity of overlying seawater (e.g., phosphorus flux), water depth relative to carbonate compensation depth (CCD), sedimentation rate, redox condition, and hydrothermal vent input (e.g., Fe-Mn precipitations).

Rare earth and trace elements enrichment and implications in black shales of Safaga-Qussier sector, Egypt

The electronic revolution in recent years points out the importance of rare earth elements (REEs) and trace elements (TEs) in these strategic industries. This study aimed to assess REEs and TEs in black shales from Duwi Formation of two mines, Um Al-Huwaitat and Hamadat, located in the Safaga-Qussier region. The chemical results indicated oxic marine along with warm and humid climate conditions of this sediment deposition. Um Al-Huwaitat Mine was highly enriched with total REEs (average 255.3–325.3 ppm) than Hamadat (average 157–207.4 ppm). Thus, it revealed that the total REEs decreased from Safaga to Qussier direction. The average content of REEs has nearly the same decreasing order of elements; they are arranged in decreasing order: Ce> Y> La> Nd> Sc> Sm and Ce> Y> La> Nd> Sc> Sm for Hamadat and Um El-Huwaitat Mines, respectively. The REEs and TEs concentrations are normalized to the UCC to investigate their distribution patterns. REEs and TEs concentration in the studied samples were higher than UCC, especially Y, Sc, Cs, Co, Zn, Zr, Mo, Cd, Hf, Ta, W, Bi, Se, Br, I, Th and U. The enrichment factor showed that Um Al-Huwaitat black shale is extremely enriched with Y, Cs, Sr, Mo, Cd, W, Bi, Se, I and U; and very high enriched with Ce, Nd, Sc, Co, and Br. La, Sm, Cr, Mn, Ni, Zn, and Th revealed significant enrichment. Clay minerals, especially montmorillonite, have been the major contributor to the enrichment of shale with REEs and TEs. Such findings point towards shale mineralisation with these elements. The current results shed light on the benefit optimization of ceased phosphate mines in the study area through using the associated black shale deposits as a source of REEs and TEs.

Sorption/desorption of Eu(III) on halloysite and kaolinite

Weathered crust elution-deposited rare earth (WED-RE) ores are important rare earth element (REE) resources around the world. In these ores, the REE are believed to mainly exist as exchangeable REE(III) ions on the surfaces of clay minerals, such as tubular halloysite and platy kaolinite. However, the mechanisms underlying the sorption and desorption of REE(III) ions on clay minerals in the environment of weathered crusts remain ambiguous. In this study, the sorption/desorption characteristics of Eu(III) ions onto halloysite and kaolinite were investigated. The results revealed that Eu(III) was adsorbed onto both clay minerals through inner-sphere complexation and outer-sphere complexation, where the former was the primary sorption mechanism. Halloysite displayed a higher sorption capacity for Eu(III) than kaolinite in a weakly acidic environment (pH 4–6). The desorption efficiency increased with the increasing concentration of NH4+ ions. When the NH4+ concentration was 0.002 mol/L, which is similar to the typical cation concentration of groundwater/rainwater, the amount and rate of Eu(III) desorption from halloysite were lower than those from kaolinite. The desorption of Eu(III) ions from the two clay minerals is proposed to be governed by the attraction between the outer-sphere complexes and clay minerals when the NH4+ concentration is 0.002 mol/L. Therefore, halloysite has a higher sorption capacity and stronger retention capacity for Eu(III) than kaolinite, which suggests that halloysite may play a greater role in REE(III) enrichment in WED-RE ores than kaolinite owing to the similar chemical properties of REE(III) ions. The fundamental results obtained in this study afford new insights into the migration of REE and the role of clay minerals in REE enrichment during ore formation.

Interfacial effects in the electro(co)deposition of Nd, Fe, and Nd-Fe from an ionic liquid with controlled amount of water

Neodymium is one of the most important rare earth elements due to its various applications, above all, in permanent magnets in consumer electronics and renewable power sources. Production of primary Nd is a rather complex and expensive process characterized by significant import dependency, which brings to the forefront Nd recovery from secondary sources. Electrowinning as one of the cheapest and processible solutions is not applicable for electropositive rare earths in aqueous systems but is a good option in the case of solutions based on ionic organic solvents. Nd electrodeposition and its induced codeposition with Fe are studied at room temperature in a fluorine-free dicyanamide ionic liquid (IL) using a complex set of electrochemical and physical (spectroscopic and microscopic) methods in dry solutions and in the presence of water. We show that the addition of water significantly promotes electrodeposition of individual metals in the respective single-component solutions but produces a hindering effect on the induced codeposition of Nd with Fe. We suggest an explanation for the acceleration of individual Nd and Fe in the presence of water based on the effects at the IL/electrode interface and for the inhibition of Nd-Fe deposition in the presence of water owing to the decelerating effect of formation of Nd oxide/hydroxide film. This is the first systematic study of the effect of water on the rare earth–transition metal codeposition in ILs providing information that can be essential for production of secondary rare earths and fabrication of novel lanthanide-based materials.