Heavy Rare Earth Research Articles

Effect of Fractionation Columns on the Elution of Rare Earth Elements Recovered from Acid Mine Drainage

Rare earth elements (REE) can be found in expressive contents in different secondary sources, such as acid mine drainage (AMD). This work evaluated separation of light and heavy rare earth elements (REE) from an acid mine drainage (AMD) generated in a former uranium mine in Brazil by using ion exchange. This AMD presents pH 3.50, total REE content of 97 mg L−1 and 1.3 g L−1 of sulfate and was used in the REE loading experiments. Loading experiments were carried out in columns using a commercial strong acid cation (SAC) exchange resin. Elution was performed with 0.01 mol L−1 NH4EDTA in systems with one, two and three columns. Regarding the loading step, the resin presented a total loading capacity of 0.58 mmol g−1. The resin proved to be more selective for light REE with adsorption efficiency of 78% and 48% for heavy REE. Regarding elution, high efficiencies between 90 and 100% were achieved for REE. The final REE solution is approximately 10 times more concentrated in the liquor related to the acid mine water. Better fractionation results were achieved for the system with three columns. Although the complete separation of the REE into pure elements was not possible, two distinct fractions of heavy and light REE could be obtained, and La was completely separated from the other REE. In order to improve fractionation and separate the REE into individual ones, the concentrated fractions can proceed to subsequent ion exchange systems.

Neoarchean high-Mg basalt and rhyolite bimodal complex in the Yinshan Block, North China Craton: Petrogenesis and tectonic implications

Plate tectonics plays an important role in Earth’s evolution, but it is a difficult and controversial issue to trace the operation of plate tectonics in the Archean. Calc-alkaline magmas are a diagnostic feature of modern subduction-related magmatism and thus identification of Archean subduction-related calc-alkaline magmas is crucial for understanding when Archean plate tectonics operated. Here we present zircon U-Pb, whole-rock geochemical and Sr-Nd isotopic data for a metamorphosed Neoarchean calc-alkaline bimodal volcanic complex from the Yinshan Block, the North China Craton. Zircon U-Pb dating results indicate that these meta-volcanic rocks were erupted in the late Neoarchean (∼2570 Ma). Its mafic unit is characterized by high contents of K2O (0.68–4.20 wt%), MgO (Mg# = 62.0-73.4), Cr (332-904 ppm), Ni (105-269 ppm), and is enriched in light rare earth elements (REEs), but depleted in heavy REEs and Nb, Ta and Ti. These geochemical features are similar to those of high-Mg basalts in the Phanerozoic arc setting. They have positive εNd(t) values (+1.3 to + 2.4), indicating that they were derived from the depleted mantle wedge. The felsic unit has variable K2O content (1.42–4.95 wt%) and K2O/Na2O ratios of 0.23–1.36 with positive εNd(t) values (+0.7 to + 3.1). They show characteristics of modern adakites with high Sr/Y and LaN/YbN ratios, suggesting that they were generated by partial melting of the thickened juvenile mafic lower crust. We conclude that the studied Neeoarchean bimodal meta-volcanic complex was formed during subduction-zone retreating and root delamination in a Neoarchean arc. Our results further indicate that plate tectonics had already operated in the Neoarchean in the Yinshan Block.

Rare Earth Elements in Shells of Black Sea Molluscs: Anomalies and Biogeochemical Implications

Rare earth elements (REE) are a class of increasingly used high-tech product components and new emerging environmental pollutants, which are accumulated, in particular, in marine biota. In this study, REE contents were estimated in shells of several molluscs common in the Black Sea. The summed REE contents in mollusc shells decreased in the following order of species: Magallana gigas = Anadara kagoshimensis > Flexopecten glaber ponticus ≥ Rapana venosa > Mytilus galloprovincialis, ranging from 0.46 to 1.9 mg·kg−1. Canonical analysis of principal coordinates allowed for the correct identification of species based on the REE composition in no fewer than 67% of the samples. The mollusc shells were anomalously enriched in Sc, Y, La, Eu and Tb, most likely due to anthropogenic contamination. The Y/Ho ratios in all samples were represented by two fit values: 23.2 (chondritic) and 67.6 (superchondritic, mainly associated with A. kagoshimensis). A new universal relationship linking the contents of three light and heavy REE in Black Sea mollusc shells was proposed: Ce0.3 Er0.7/Yb = 2.00 ± 0.46 (mean ± standard deviation).

Organic Ligand-Mediated Dissolution and Fractionation of Rare-Earth Elements (REEs) from Carbonate and Phosphate Minerals.

Global efforts to build a net-zero economy and the irreplaceable roles of rare-earth elements (REEs) in low-carbon technologies urge the understanding of REE occurrence in natural deposits, discovery of alternative REE resources, and development of green extraction technologies. Advancement in these directions requires comprehensive knowledge on geochemical behaviors of REEs in the presence of naturally prevalent organic ligands, yet much remains unknown about organic ligand-mediated REE mobilization/fractionation and related mechanisms. Herein, we investigated REE mobilization from representative host minerals induced by three representative organic ligands: oxalate, citrate, and the siderophore desferrioxamine B (DFOB). Reaction pH conditions were selected to isolate the ligand-complexation effect versus proton dissolution. The presence of these organic ligands displayed varied impacts, with REE dissolution remarkably enhanced by citrate, mildly promoted by DFOB, and showing divergent effects in the presence of oxalate, depending on the mineral type and reaction pH. Thermodynamic modeling indicates the dominant presence of REE-ligand complexes under studied conditions and suggests ligand-promoted REE dissolution to be the dominant mechanism, consistent with experimental data. In addition, REE dissolution mediated by these ligands exhibited a distinct fractionation toward heavy REE (HREE) enrichment in the solution phase, which can be mainly attributed to the formation of thermodynamically predicted more stable HREE-ligand complexes. The combined thermodynamic modeling and experimental approach provides a framework for the systematic investigation of REE mobilization, distribution, and fractionation in the presence of organic ligands in natural systems and for the design of green extraction technologies.

A cost-effective dual-layer grain boundary diffusion strategy to significantly enhance coercivity of sintered Nd-Ce-Fe-B magnets

In an attempt to obtain cost-effective sintered Nd-Ce-Fe-B magnet and overcome the coercivity-remanence trade-off challenge caused by heavy rare earth (HRE) diffusion, a novel dual-layer coating method has been proposed for the grain boundary diffusion process (GBDP). A high coercivity increment of 8.56 kOe is achieved by dual-layer coated DyHx/Pr80Al20 (DH/PA) diffusion with 0.8 wt% DyHx and a slight remanence reduction from 12.85 to 12.71 kG. Although the DyHx diffused magnet has a coercivity increment of 9.24 kOe, it consumes twice as much DyHx as the DH/PA diffused magnet at the great sacrifice of remanence. This can be attributed to the formation of continuous grain boundary phase and thin Dy-rich shell via microstructural observations. Further TEM characterization indicates that the amorphous triple junction grain boundary phase (TJP) gradually transforms into the crystalline Nd2O3 structure after GBDP. The coexistence of cubic-Nd2O3 phase and hexagonal-Nd2O3 phase found in the dual-layer coated Pr80Al20/DyHx (PA/DH) diffused magnet creates a more intricate grain boundary phase structure, hindering the diffusion of Dy. Comparably, the formation of single cubic-Nd2O3 (Ia3̅ structure) grain boundary phase in the DH/PA and DyHx diffused magnets is an important reason for the significant increase in coercivity. Based on the evaluation of magnetic performance and cost, the DH/PA diffused magnet achieves a higher price-performance ratio (PPR). This cost-effective bilayer grain boundary diffusion strategy provides a valuable reference for high PPR Nd-Ce-Fe-B magnet fabrication.

A hydrous sub-arc mantle domain within the northeastern Neo-Tethyan ophiolites: Insights from cumulate hornblendites

Being a part of the large-scale Indus-Tsangpo suture zone ophiolites of the Alpine-Himalayan orogenic system, the Neo-Tethyan ophiolites of eastern Arunachal Himalaya, northeast India, are important in understanding the formation and evolution of the Neo-Tethyan lithosphere. This study focuses on the hornblendite dykes occurring within serpentinized peridotites of the Mayodia ophiolites in eastern Arunachal Himalaya, to ascertain the origin and evolution of such hydrous mineral cumulates within the ophiolite complex. Texturally and chemically, the hornblendites contain three types of amphiboles, Amp1 (pargasite), Amp2 (Mg-hornblende), and Amp3 (actinolite). The pargasites occur as large cm-sized phenocrysts and show cumulate textures while Mg-hornblende appears as both intercumulus grains between cumulus pargasites and surrounding partially resorbed clinopyroxene grains. Actinolite occurs along the breakdown zone of pargasite and is associated with other secondary minerals. The hornblendites are characterized by high MgO (~12–20 wt%) and low SiO2 (~42–44 wt%) with depleted light rare earth elements (REE) [(La/Sm)N = 0.29–0.52] and almost flat heavy REE [(Gd/Yb)N) = 0.89–1.11]. Moreover, the samples are characteristically depleted in high field strength elements (Nb, Ta, Ti, Hf) while being enriched in Pb. Geothermobarometric calculations yield high magmatic temperatures of ~950 and ~840 °C for pargasite and Mg-hornblende, respectively, and variable pressures with pargasite having the highest pressures (1.6–1.7 GPa) followed by Mg-hornblende (1.1–1.2 GPa) and finally actinolite (~0.55 GPa). Furthermore, fO2 calculations for the cumulus pargasites revealed highly oxidizing conditions (ΔNNO+2) and water content of parental melts (H2Omelt% = ~14.25 %). Parental melt calculations using whole-rock REE concentrations suggest formation from a hydrous sub-alkaline basaltic melt. Whole-rock initial SrNd isotopic ratios of the hornblendites reveal a primary signature for them, falling in the mantle array in proximity to the high-μ (HIMU) mantle reservoir. All these signatures point towards a magmatic arc affinity for these hornblendites. The host peridotite unit shows highly enriched REE concentrations (ƩREE = 18.13 ppm) with flat REE patterns compared to the other peridotites of the locality, which show depleted signatures. Olivine chemistry of the host peridotite unit depicts primary compositions falling in the mantle array. The olivine-liquid thermometer yields temperatures ~1000 °C, which are much lower than those of peridotites occurring in spreading centers (MOR or back-arc). These evidence suggest that the hornblendites and their host peridotite unit represent an island arc root complex, which further imply the hydrous nature of the Neo-Tethyan sub-arc mantle.

Enhancement of the magnetic property of Nd-Fe-B sintered magnets through novel powder rounding modification

Two types of sintered Nd-Fe-B magnets were fabricated by the process of powder metallurgy technology through two different powder preparation processes i.e., conventional powder preparation process and novel powder rounding modification. The microstructure, composition and properties of the two type powders have been studied including the particle size distributions and flowabilities. Furthermore, magnetic properties, microstructure and alignment degree of the magnets prepared by the corresponding powder also have been investigated. The novel powder rounding modification rounds the sharp edges and corners of the particles compared to the conventional powder preparation process, thereby reducing friction between the particles and improving flowability of the powder. As a result, the alignment degree of the sintered magnet is enhanced, which contribute to the improvement of the remanence and the energy product density. The powder that experienced rounding process changed the distribution of RE (rare earth)-rich particles, causing tiny RE-rich particles to adhere around the main phase particles, facilitating the compact of bulk during liquid-phase sintering process and achieving uniform distribution of RE-rich phases around the Nd2Fe14B main phase, resulting in increasing the magnet density and coercivity. As a consequence, we have produced the magnet with Br = 1.43 T, Hcj = 1049 kA/m and (BH)max = 393.2 kJ/m3, which is fully superior to conventional magnet with Br = 1.41 T, Hcj = 969 kA/m and (BH)max = 383.7 kJ/m3 by adopting powder rounding process. This indicates that the novel powder rounding modification is an efficient approach for synchronous improvement of magnetic performance of sintered Nd-Fe-B without any heavy rare earth elements.

RARE-EARTH elements in the topsoils of a Russian industrial city: Sources and human health risk assessment

Research on rare-earth elements (REEs) in urban soils of Russian industrial cities is extremely limited. This study investigates the potential sources and human health risks of REEs contained in the topsoils of the industrial Russian city of Chelyabinsk. The study also takes into account natural sources of REE as the city is located on the border of granites (Urals) and sedimentary rocks (Western Siberia). We analyzed the concentration and distribution of REEs in the soils of four types of locations: residential courtyards, city parks, roadsides, and industrial locations. The total REE concentrations ranged from 44 to 255 mg/kg, with average concentrations of 140, 124, 113 and 89 mg/kg in the courtyards, roadsides, industrial location and city parks, respectively. The REE content in courtyard soils could be influenced by poor cleaning of fallen leaves. The ratios of light REE (LREE) to heavy REE (HREE) ranged from 9.5 to 10.1, revealing an obvious fractionation between them. The fractionation of LREE and HREE, and the REE/ES (European Shale) pattern showed that REE accumulation in Chelyabinsk soils has been disturbed by human activities. It was shown that the dust from industrial emissions was the main anthropogenic source of REE accumulation in urban soil. The largest amounts of REEs are emitted from an electrometallurgical plant and zinc production plant. Fortunately, the estimated daily intakes of REE from soils for children and adults were well below the safety thresholds. At the same time, in order to prevent social tension and reduce the anthropogenic load on the urban area, it is recommended to use phytoremediation technologies, smart landscaping of industrial and residential areas, more thorough cleaning of fallen leaves and road dust. It is also recommended to move the most dangerous production processes outside the urban area.

Garnet geochronology, major and trace element geochemistry of the Huanggangliang Fe-Sn polymetallic deposit, NE China

Cu-Fe (Au), W-Sn (Mo), Pb-Zn (Ag) and other element assemblages are common in many skarn deposits, but examples of Fe and Sn coexistence in nature are relatively rare. The Huanggangliang deposit in the southern Great Xing'an Range is the largest Fe-Sn polymetallic deposit in northern China, and there are five main mining areas (SK Ⅰ–SK Ⅴ) distributed along a SW–NE trend. SK Ⅰ and SK Ⅲ are the two larger mining areas in the Huanggangliang deposit, and their mineral assemblages and wall-rocks are significantly different: cassiterite and metal sulfides are duncommon in SK Ⅰ (andesite), while they are widely distributed in SK Ⅲ (marble). Garnet is widely distributed in SK Ⅰ and SK Ⅲ mining areas, and provides a good opportunity to explore the mechanism of Fe-Sn assemblage differentiation. Three types of garnet are distinguishable (Grt 1, Grt 2 and Grt 3) based on their mineral associations, textures and locations, and they mainly belong to the andradite-grossular solid solution series. The LA–ICP–MS U-Pb ages of the garnets from SK Ⅰ and SK Ⅲ are 136.0 ± 1.2 Ma (n = 25, MSWD = 1.9) and 136.2 ± 2.6 Ma (n = 37, MSWD = 1.8), respectively, suggesting that magmatic-hydrothermal activity in these two mining areas began at the same time. Grt 1 (located deep in SK Ⅰ and SK Ⅲ) and Grt 2 (located shallowly in SK Ⅰ) are mainly andradite, while Grt 3 (located shallowly in SK Ⅲ) is mainly grossular. They are all enriched in high field strength elements (HFSEs) and depleted in large ion lithophile elements (LILEs), and their REE patterns are enriched in light rare earth elements (LREEs) and depleted in heavy rare earth elements (HREEs). However, Grt Ⅰ-1a and 1b (deep garnets in SK Ⅰ) exhibit obvious positive Eu anomalies, while the other garnet types exhibit negative or no obvious Eu anomalies. Additionally, Grt 3 has high contents of V, Sn, U, Th, Zn and Y, and low contents of W and Mo. This pattern implies that the garnets in deep SK Ⅰ may have formed under oxidizing conditions with high temperatures, high oxygen fugacity (fO2) and weak acidity, while the garnets in shallow SK Ⅲ formed under reducing conditions with moderate temperatures, moderate fO2 and near-neutral pH. The garnets in shallow SK Ⅰ and deep SK Ⅲ may have formed under weak oxidation–reduction conditions at moderate to high temperatures, moderate fO2 and weakly acidic to neutral pH conditions. Our newly reported field geological, mineralogical, and geochemical data from garnet suggest that the ore-forming fluids of the Huanggangliang were magmatic-hydrothermal fluids mixed with slightly acidic external fluids, chloride complexes may have been the main transport ligands of REEs. The metallogenic environment may be an important factor leading to the difference of mineral assemblages in the Huanggangliang deposit.

Geochemical characteristics, hazards impact assessment and radiogenic heat production of the alkaline rocks.

This study primarily investigates the natural radioactivity level in alkaline rocks collected from the Wadi El-Dib ring complex (WDRC) in North Eastern Desert of Egypt, and assesses potential health risks associated with their use as decorative building materials. The work was accomplished using a high-purity germanium detector as well as ICP-MS and ICP-AES techniques. The WDRC composed essentially of trachyte, quartz syenite, granite and syenite. Geochemically, these rocks contain high SiO2 and alkalis with metaluminous to slightly peraluminous features. All rocks contain high concentrations of rare earth elements (∑REEs = 109-1075ppm), with clear enrichment in light REEs compared to heavy REEs [(La/Yb)N = 8.3-25.3. Radiometrically, the concentrations of the natural radioisotopes (238U, 232Th, and 40K) in the studied rock types surpassed the worldwide average values assigned for building materials by UNSCEAR. This elevation of the radioisotope concentration values is due to the presence of supplement minerals such as monazite, zircon, allanite, and rutile. Granites exhibit the highest mean concentrations of 238U (av. 164.24 ± 14.76Bq/kg) and 232Th (av. 214.37 ± 23.33Bq/kg), while trachytes demonstrate the highest 40K (av. 1352.56 ± 65.56Bq/kg) concentrations. In contrast, syenites exhibite the lowest mean concentrations for 238U (av. 54.51 ± 6.81Bq/kg) and 232Th (av. 56.76 ± 6.25Bq/kg), while quartz syenites display the lowest mean concentration of 40K (av. 1144.78 ± 96.19Bq/kg). The radiogenic heat production (RHP) associated with U, Th, and K range between 1.41 to 9.33μW/m3, exceeding the typical crustal mean value of 0.8 to 1.2μW/m3. The radiological parameters and indices evaluating risks of the outdoor and indoor radiation doses due to the investigated rocks were assessed. The results indicated that these rocks meet globally accepted values and safety standards (approved by UNSCEAR, ICRP, and EC) for surface building materials, as well as they underscore the importance of adhering to safety protocols to safeguard workers from radiation exposure within the WDRC area. Ultimately, the data herein provide a valuable database for assessing the compatibility of geochemical data and natural radioactivity level in WDRC rocks. Additionally, it reveals that from the radiological perspective, the investigated rocks are considered safe for use as decorative construction materials.

Localization of High-Titanium Dolerites in Kimberlite Fields: Possible Causes and a New Criterion for Kimberlite Search

Abstract ––The generalized chemical composition data on the studied dolerites from the Vilyui–Markha dike swarm (Vilyui paleorift) allowed detecting geochemically anomalous areas among them. It has been found that percentage of TiO2 and a number of heavy rare-earth elements (Th, Ta, Hf, Y, Nd) in the dolerites of dikes located within the kimberlite fields show almost twofold increase compared to the normal content for these elements in the Vilyui–Markha dolerites. Similar behavior of these elements is also observed in the dolerite dikes near the Kuoika kimberlite field (the Molodo dike swarm, Olenek paleorift). It is inferred that there is a connection between the increase in abundances of titanium and rare-earth elements in the dolerites and that the latter occur within the lithosphere blocks hosting kimberlite fields. The areas of lithospheric mantle roots linked with the formation of proto-kimberlites may have had bearing on the composition of tholeiite melt both in the processes of its generation and during its ascent to the Earth’s surface, which led to its local enrichment in titanium and a number of other elements. While the processes of the alignment of the geochemical composition between the high-titanium basites and the rest of the melt beyond the contours of the lithospheric blocks with kimberlite fields were weakly pronounced, they were responsible for appearance of zones enriched in titanium. Kimberlite fields that formed before or after basite magmas intrusion overlap with placements of high-titanium dolerite dikes. Thus, high-titanium dolerites in dike swarms (belts) can be used as one of the criteria for kimberlite searches. In view of the above, two new potential zones (Tenkelyakh and Kyulenke areas) for kimberlite exploration have been identified within the Vilyui–Markha dike swarm.

Re-melting of the Neoproterozoic juvenile mafic lower crust: The origin of adakitic and non-adakitic felsic suites in the southwest margin of Yangtze Craton

Eocene-Oligocene adakitic and non-adakitic shoshonitic felsic intrusions from the southwest margin of the Yangtze Craton provide a crucial geological record for studying crust-mantle interactions at the craton boundary. Despite their significance, the petrogenesis and source properties of these intrusions remain debated. This study suggests that the adakitic and non-adakitic features of these intrusions result from the re-melting of Neoproterozoic juvenile lower crust, as evidenced by zircon U-Pb dating, geochemical analyses, and petrogenetic investigations. The Ninglang-Yongsheng shoshonitic felsic intrusions, characterized by high Mg#, MgO, Ni, and Cr contents, exhibit isotopic characteristics akin to mantle-derived magma and juvenile mafic lower crust. Their U-Pb ages span 32–36 Ma, and they show similar patterns in major and trace elements, rare earth elements (REEs), and isotopes, with enrichment in large ion lithophile elements (LILEs) and depletion in high field strength elements (HFSEs) like Nb, Ta, and Ti. These intrusions also demonstrate significant fractionation between light and heavy REEs, with a modest negative Eu anomaly. Their (87Sr/86Sr)i and εNd(t) values range from 0.7060 to 0.7069 and − 4.4 to −1.5, respectively, while Pb isotopic compositions vary slightly.This paper, along with prior research, has developed a genetic model for the Ninglang-Yongsheng shoshonitic felsic intrusions. The adakitic quartz monzonite porphyries likely originated from high-degree partial melting of the juvenile lower crust, whereas the non-adakitic shoshonitic syenite porphyries resulted from lower-degree melting. The composition of the juvenile lower crust may be garnet amphibolite-pyroxenite. This suggests distinct compositional variations within the Ninglang-Yongsheng juvenile lower crust. Moreover, the region's shoshonitic felsic intrusions have assimilated mantle-derived magma. In conclusion, the juvenile lower crust on the Yangtze Craton's southwest margin displays zonal characteristics, with the Liuhe-Beiya area's lower crust showing higher potassium content and more enriched isotopic signatures compared to the Ninglang-Yongsheng region.

Pressure-temperature-time evolution of the Milin pelitic schists: Implications for the tectonic evolution of the eastern Indus-Yarlung suture zone, eastern Himalaya

We report an integrated comprehensive dataset composed of petrography, pressure-temperature (P-T) calculations, monazite U-Th-Pb ages, and trace-element data from pelitic schists in the eastern Indus-Yarlung suture zone in the Milin area of the eastern Himalaya. These rocks represent the exposure of subduction-related rocks within the eastern Indus-Yarlung suture zone accretionary complex. The dominant mineral assemblages of the pelitic schists are garnet + kyanite + staurolite + biotite + quartz and garnet + kyanite + staurolite + biotite + paragonite + sillimanite with quartz, plagioclase, and ilmenite assemblages. Phase equilibrium modeling of sillimanite-bearing pelitic schists yielded peak P-T conditions of ∼670−680 °C at ∼8.6 kbar, similar to that of kyanite-bearing schists (∼670 °C, ∼8.8 kbar). Monazite grains with complex internal structures retained variable ages ranging from 28 Ma to 15 Ma, which correlate systematically with changes in the concentrations of Y, Th, U, and heavy rare earth elements and ratios of Th/U. Combined with petrologic analysis, we conclude that the pelitic schists experienced a long-lived prograde metamorphism from ca. 28 Ma to ca. 22 Ma. Peak metamorphism occurred in the period 22−21 Ma, followed by quasi-isothermal decompression until 15 Ma. The discrepancies among metamorphic P-T-t paths in the eastern Indus-Yarlung suture zone indicate the presence of not only collision-related regional metamorphism at medium P-T conditions, but also subduction-related high-pressure−low-temperature terranes in the Milin region. These two domains experienced different P-T evolution and tectonic histories and were juxtaposed in the early Neogene during the India-Asia continental collision.

Triple Inverse Sandwich versus End-On Diazenido: Bonding Motifs across a Series of Rhenium-Lanthanide and -Actinide Complexes.

While synthesizing a series of rhenium-lanthanide triple inverse sandwich complexes, we unexpectedly uncovered evidence for rare examples of end-on lanthanide dinitrogen coordination for certain heavy lanthanide elements as well as for uranium. We begin our report with the synthesis and characterization of a series of trirhenium triple inverse sandwich complexes with the early lanthanides, Ln[(μ-η5:η5-Cp)Re(BDI)]3(THF) (1-Ln, Ln = La, Ce, Pr, Nd, Sm; Cp = cyclopentadienide, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). However, as we moved across the lanthanide series, we ran into an unexpected result for gadolinium in which we structurally characterized two products for gadolinium, namely, 1-Gd (analogous to 1-Ln) and a diazenido dirhenium double inverse sandwich complex Gd[(μ-η1:η1-N2)Re(η5-Cp)(BDI)][(μ-η5:η5-Cp)Re(BDI)]2(THF)2 (2-Gd). Evidence for analogues of 2-Gd was spectroscopically observed for other heavy lanthanides (2-Ln, Ln = Tb, Dy, Er), and, in the case of 2-Er, structurally authenticated. These complexes represent the first observed examples of heterobimetallic end-on lanthanide dinitrogen coordination. Density functional theory (DFT) calculations were utilized to probe relevant bonding interactions and reveal energetic differences between both the experimental and putative 1-Ln and 2-Ln complexes. We also present additional examples of novel end-on heterobimetallic lanthanide and actinide diazenido moieties in the erbium-rhenium complex (η8-COT)Er[(μ-η1:η1-N2)Re(η5-Cp)(BDI)](THF)(Et2O) (3-Er) and uranium-rhenium complex [Na(2.2.2-cryptand)][(η5-C5H4SiMe3)3U(μ-η1:η1-N2)Re(η5-Cp)(BDI)] (4-U). Finally, we expand the scope of rhenium inverse sandwich coordination by synthesizing divalent double inverse sandwich complex Yb[(μ-η5:η5-Cp)Re(BDI)]2(THF)2 (5-Yb), as well as base-free, homoleptic rhenium-rare earth triple inverse sandwich complex Y[(μ-η5:η5-Cp)Re(BDI)]3 (6-Y).

Petrogenesis of the Early Cretaceous Tietonggou Diorite and Its Geological Implications

The Tietonggou pluton is mainly composed of gabbroic diorite and diorite. The petrology, zircon U-Pb age, and geochemistry of the Tietonggou diorite have been studied to determine its petrogenesis and metallogenic significance. The diorite samples have 56–58 wt% SiO2 and 11–14 wt% Al2O3 and are peraluminous and sodic (Na2O/K2O = 1.29–2.07). All the samples are enriched in light rare earth elements (LREEs) and large-ion lithophile elements (LILEs; e.g., Rb, Ba, and Sr) but depleted in heavy rare earth elements (HREEs) and high field strength elements (HFSEs; e.g., Zr, Nb, and Ta), suggesting subduction-related affinities. The rocks have narrow ranges of (206Pb/204Pb)t (18.5–19.0), (207Pb/204Pb)t (15.71–15.75), and (208Pb/204Pb)t (38.4–39.0) ratios, respectively. Zircons from the Tietonggou diorite yielded a weighted average U-Pb age of 132.86 ± 0.92 Ma (MSWD = 0.48), whilst those from the nearby Laowa diorite yielded 129.72 ± 0.61 Ma (MSWD = 1.05). This suggests that the rocks represent Early Cretaceous plutons, coeval with the peak lithospheric thinning in eastern North China Craton (NCC). The magma likely originated from partial melting of the enriched lithospheric mantle and was contaminated by ancient lower NCC crustal materials. Our study clarifies the tectonic background of the Tietonggou pluton and provides support for the study of the genesis of Fe–skarn deposits in western Shandong.

Discovery of Late Permian Adakite in Eastern Central Asian Orogenic Belt: Implications for Tectonic Evolution of Paleo-Asian Ocean

The Permian to Triassic period represents a pivotal phase in the evolution of the Paleo-Asian Ocean, marked by significant tectonic transitions from subduction, collision, and post-orogenic extension. The timing of closure of the Paleo-Asian Ocean in northeastern China has always been controversial. In this contribution, the petrology, zircon U-Pb geochronology and geochemistry are conducted on granite found in well HFD1, Songliao Basin, eastern part of Central Asian orogenic belt. Zircon U-Pb dating indicates that granite crystallized at 258.9 ± 2.2 Ma, as the product of magmatism occurred in the early Late Permian. The rocks have high SiO2, Al2O3, Na2O content, negative Eu anomaly, light enrichment of rare-earth elements, depletion of heavy rare-earth elements, high Sr (448.29–533.11 ppm, average 499.68 ppm), low Yb (0.49–0.59 ppm, average 0.54 ppm), Y (4.23–5.19 ppm, average 4.49 ppm), and high Sr/Y ratios (98–125, average 112) and can be classified as O-type adakite. This is the first discovery of late Paleozoic adakite in the Songliao Basin and the neighboring areas. The geochemistry of adakite indicates derivation by partial melting of MORB-type subducted oceanic crust, indicating that the subduction of the Paleo-Asian Oceanic lithosphere lasted until at least 258.9 Ma.

Organic-mineral colloids regulate the migration and fractionation of rare earth elements in groundwater systems impacted by ion-adsorption deposits mining in South China

Ion-adsorption rare earth element (REE) deposits distributed in the subtropics provide a rich global source of REEs, but in situ injection of REEs extractant into the mine can result in leachate being leaked into the surrounding groundwater systems. Due to the lack of understanding of REE speciation distribution, particularly colloidal characteristics in a mining area, the risks of REEs migration caused by in situ leaching of ion-adsorption REE deposits has not been concerned. Here, ultrafiltration and asymmetric flow field-flow fractionation coupled with inductively coupled plasma mass spectrometry (AF4-ICP-MS) were integrated to characterize the size and composition of REEs in leachate and groundwater from mining catchments in South China. Results show that REEs were associated with four fractions: 1) the <1 kDa fraction including dissolved REEs; 2) the 1 – 100 kDa nano-colloidal fraction containing organic compounds; 3) the 100 kDa – 220 nm fine colloids including organic-mineral (Fe, Mn and Al (oxy)hydroxides and clay minerals); 4) the >220 nm coarse colloids and acid soluble particles (ASPs) comprising minerals. Influenced by the ion exchange effect of in situ leaching, REEs in leachate were mostly dissolved (79 %). The pH of the groundwater far from the mine site was increased (5.8 – 7.3), the fine organic-mineral colloids (46 % – 80 %) were the main vectors of transport for REEs. Further analysis by AF4 revealed that the fine colloids can be divided into mineral-rich (F1, 100 kDa – 120 nm) and organic matter-rich (F2, 120 – 220 nm) populations. The main colloids associated with REEs shifted from F1 (64 % ∼ 76 %) to F2 (50 % ∼ 52 %) away from the mining area. For F1 and F2, the metal/C molar ratio decreased away from the mining area and middle to heavy REE enrichment was presented. According to the REE fractionation, organic matter was the predominant component capable of binding REEs in fine colloids. Overall, our results indicate that REEs in the groundwater system shifted from the dissolved to the colloidal phase in a catchment affected by in situ leaching, and organic-mineral colloids play an important role in facilitating the migration of REEs.

Enrichment and fractionation of rare earth elements (REEs) in ion-adsorption-type REE deposits: Constraints of an iron (hydr)oxide–clay mineral composite

Abstract Ion-adsorption-type rare earth element (REE) deposits are the source of more than 90% of global heavy REEs (HREEs). Thus, understanding the ore genesis of REEs, particularly the distribution characteristics and enrichment mechanisms of HREEs, is vital for efficient exploration and mining of ion-adsorption-type REE deposits worldwide. The characteristics and petrogenesis of bedrock, and the aqueous mobility of REEs, are known to be important factors controlling REE accumulation and fractionation in the weathering crust of REE deposits. However, the effect of REE adsorption on secondary minerals, which is a crucial step in deposit formation, remains poorly understood. This problem was addressed by the study described herein, which involved a systematic analysis of the complete weathering profile (78 m) of the Renju ion-adsorption-type REE deposit in South China and a simulated adsorption experiment. Clay minerals and iron (Fe) (hydr)oxides are the dominant REE adsorbents in the weathering crust and most are micro-to-nanosized particles. Thus, the fine particle fraction (&amp;lt; 2 μm) was separated from field samples, to better disclose their effects on the concentration and redistribution of REEs. Phase compositions and morphologies were characterized by X-ray diffraction, Mössbauer spectrometry, and scanning/transmission electron microscopy (SEM/TEM), which revealed that various clay minerals and Fe (hydr)oxides form composites along the profile of the deposit. Composites of ferrihydrite–kaolinite, goethite–kaolinite/halloysite, and hematite–kaolinite/halloysite were found to be distributed in the semi-weathered, completely weathered, and topsoil layers, respectively, with different sizes and shapes. The concentrations and partition patterns of REEs in different occurrence states were distinguished after sequential extraction. Ion-exchangeable-REEs were the major state and enriched in the upper completely weathered layer. These species were found to be adsorbed onto kaolinite and halloysite via electrostatic attraction, without obvious fractionation. Fe (hydr)oxides were determined to comprise ca. 20% of REEs at most depths and over 50% of REEs in the topsoil and semi-weathered layer. It was found that Fe (hydr)oxides scavenge REEs through complexation and oxidation, resulting in HREE enrichment and a positive cerium (Ce) anomaly, respectively. In addition, compared with crystalline Fe (hydr)oxides, amorphous Fe (hydr)oxides immobilize more REEs but exhibit weaker preferential adsorption of HREEs. The above-described findings are consistent with the results of simulated experiments for REE adsorption onto a clay mineral–Fe (hydr)oxide composite (Bt-60), which was obtained from hydrothermal processing of biotite. Furthermore, the distributions and stabilities of LREEs and HREEs were distinguished by TEM–energy–dispersive spectroscopy (EDS) of Bt-60 before and after REE extraction by ammonium sulfate. The phase transformation pathways of clay minerals and Fe (hydr)oxides, and their different enrichment and fractionation characteristics in REEs, were also discussed in terms of the structure and surface properties of minerals, adsorption mechanisms, and variations in chemical properties across the REE group. The results shed new light on how clay minerals and Fe (hydr)oxides affect the enrichment and fractionation of REEs in ion-adsorption-type deposits.

The Petrography and geochemistry of iron-bearing units from Mingo’o area (Ntem complex, southern Cameroon)

The banded iron formation (BIF) of the Mingo’o region is located on the northern edge of the Congo Craton. They constitute a significant component of the southern Cameroonian Archean to Paleoproterozoic. Petrographic description indicates that the most characteristic facies of the Mingo'o BIFs are quartz-magnetite BIFs (QMB), which are mostly composed of magnetite and quartz. Geochemistry analyses show that the major elements of this BIF are very simple, with SiO2 and Fe2O3 representing 95.25 wt. % of the bulk rock on average. The low concentrations of Al2O3, TiO2, and HFSE reveal that these chemical sediments are detritus-free. According to Paerson's major element correlation matrix, there is a slight contribution of detrital material to chemical sediment, as confirmed by the strong positive correlation (r = 0.72) of Al and Ti, also by the binary diagrams Al vs. Σ(Y + Nb + Zr) with a weak positive correlation (r2 = 0.31) and Al vs. ΣREE with a zero correlation (r2 = 0.08), indicating that the detrital input was insignificant. The transition metals Zn, Cr, Sr, and V are among the trace elements with low enrichments. This suggests the direction of the volcanogenic hydrothermal input in chemical precipitates. The mean ∑REE concentration of the studied BIF is 26.74 ppm, with a range of 8.82 to 36.74 ppm. Pure chemical sediments are comparable to that. The shale-normalized patterns display minor positive europium anomalies, a sharp decrease in heavy REE, and enrichment in light REE. These geochemical characteristics suggest that the hydrothermal activity in the deep ocean, coupled with seawater, was the source of the Fe and Si. Low-temperature hydrothermal solutions play a key role in the studied BIF, as shown by the absence of a notable positive Eu anomaly. Ce anomalies are seen in the chrondrite-normalized REE patterns, which are characterized by LREE-enriched (mean LaCN/YbCN = 5.28) and HREE depletion (mean TbCN/YbCN = 1.04) patterns. This may indicate that the BIF within the Mingo’o region was formed in place of the basin towards redoxcline, alternating at different times and under various influences from the influx of seawater that has been oxidized.

Template-free efficacious morphology of electrosynthesized polyaniline/β-cyclodextrin host-guest complex on Au/rGO modified electrode for removal and recovery of rare-earth and heavy elements from seawater

Global water pollution and scarcity of water resources are turning increasingly into serious threats to the survival of all living organisms on Earth. This study offers an influent strategy for the electrosynthesis of reduced graphene oxide/polyaniline/β-cyclodextrin (rGO/PAni/βCD) nanocomposite and its application to the removal/recovery of heavy elements (HEs) and rare-earth elements (REEs). Besides physicochemical and electrochemical studies, the surface morphological and statistical properties of fabricated nanocomposite electrode were examined. The textural and morphological characteristics of nanocomposite electrode were investigated via AFM data based on statistical, stereometric, and fractal theory. The cohesive, porous, and well-developed morphology of fabricated nanocomposite electrode has enabled the electrodeposition technique to achieve significant simultaneous removal/recovery efficiency of HE and REE ions such as Pb(II), Cu(II), Cd(II), Hg(II), Ce(IV), and Nb(V). Therefore, using rGO/PAni/βCD, considerable removal of HEs and REEs was achieved under optimized pH, 0.1 M KNO3, and 35 mg L−1 metal ion initial concentration during 20 min. Removal capacity of the nanocomposite electrode is preserved subsequent to 10 cycles of electrodeposition/desorption, according to the desorption investigation through eluted adsorbent at time intervals in deionized water and adjusted acidic pH values. Then, using rGO/PAni/CD nanocomposite, simulated seawater remediation was accomplished successfully. This interdisciplinary approach reveals that the removal/recovery efficiency enhance linearly along with the improvement of well-developed morphology for electrosynthesized composites. Thus, these results suggest how the morphological features of the polymer composites could improve remediation of water resources.