Heavy Rare Earth Research Articles

Decoding Apatite in Volcanic Carbonatitic breccia from Mongra, Northwest of Amba Dongar Carbonatite Complex, Gujarat, India: Insights to Genesis & Rare Earth Element Budgets

Chemical variations in apatite in context to carbonatites and trace element partitioning between apatites and carbonatite-rich liquids are important in assessing the petrogenesis and evolution of the carbonatites as well as the associated carbonatitic breccia due to apatite's sensitivity to surrounding magma composition. Volcanic carbonatitic breccia is one of the constituent rock types found outside the ring structure of the Amba Dongar Carbonatite Complex (ADC) situated in western India. In the present work, we report the mineral chemistry of apatites from the carbonatitic breccias of the Mongra region (ADC outer core) and compare them to apatites from ADC carbonatites. Apatite chemistry from Mongra displays a larger concentration of rare earth elements, manganese, and chlorine when compared to those of ADC carbonatites. Morphology and distinct zoning of these apatites represent late-stage magmatic processes with high heavy rare earth element concentrations (high Lutetium), followed by interaction of fluids from the surrounding alkaline rocks. Variation in sulphur concentration in the apatites of this study indicates crystallisation under mildly reducing conditions. Integrated field observations, petrography, and apatite mineral chemistry from the Mongra region allow for an understanding of the genesis of apatites in the ADC outer core, with possible implications for late-stage mineral-melt interactions.

Selective Recovery of Rare Earth Elements from Waste Magnets by Molten Salt Electrochemical Process

Neodymium magnets are the strongest permanent magnets with Nd2Fe14B as the main phase. In applications where high temperature operation is expected, such as motors for electric vehicles (EVs) and hybrid electric vehicles (HEVs), Dy is added to prevent degradation of magnetic properties. Currently, the demand for EVs and HEVs is growing rapidly, and Dy-doped NdFeB magnets are used in these vehicles. Thus, a large amount of waste magnets will be generated in the future. Moreover, for heavy rare earths such as Dy, high-quality resources are extremely unevenly distributed in the world, and there are already concerns about their stable supply. Given the above background, there is a need to develop an efficient recycling process that can replace the conventional wet recycling process, which has a large environmental impact and energy consumption.Our research group has proposed a process for the separation and recovery of rare earth elements (REEs) from the waste of neodymium magnet using molten salt electrolysis and alloy diaphragms [1,2]. The principle of this process is shown in Fig. 1. First, the Nd and Dy ions in the waste magnet used as the anode are dissolved into the molten salt by anodic dissolution. Next, the dissolved Nd or Dy ions are reduced on the surface of the diaphragm, which functions as a bipolar electrode, and only one of the ions is reduced to form an alloy. Furthermore, Nd or Dy diffuses through the alloy diaphragm and is dissolved into the molten salt by anodic dissolution on the cathode chamber side surface of the diaphragm. Finally, Nd and Dy are separated and recovered on the cathode.So far, we have reported that selective permeation of Dy [2] and Nd [3] is possible using LiCl-KCl as the molten salt and a solid Ni-RE alloy as the diaphragm. In the present study, we selected LiF-CaF2 as a more practical fluoride-based molten salt and Hastelloy as a more durable diaphragm, and investigated the electrochemical permeation of RE. We also considered that liquid Fe-RE alloy is expected to be a more desirable diaphragm with higher durability and faster permeation. As a fundamental study, the formation behavior of liquid Fe-Nd and Fe-Dy alloys was investigated, and the results will also be reported.[1] T. Oishi, H. Konishi, T. Nohira, M. Tanaka, and T. Usui, Kagaku Kogaku Ronbunshu, 36, 299 (2010). [in Japanese][2] T. Oishi, M. Yaguchi, Y. Katasho, H. Konishi, and T. Nohira, J. Electrochem. Soc., 167, 163505 (2020).[3] T. Oishi, M. Yaguchi, Y. Katasho, and T. Nohira, J. Electrochem. Soc., 168, 103504 (2021). Figure 1

Lower Gondwana palaeobotany and geochemistry of phosphorite occurrence in the north‐western part of Ib‐River Coalfield, Odisha, India, and their implications

The present investigation breaks new ground by examining the Raniganj sediments in the Kendudihi section of the Ib‐River Coalfield, Odisha, India. The study identifies a megaflora consisting of 25 species of Glossopteris, Vertebraria indica, stem casts and equisetaceous stems. The microflora is predominantly composed of Striatopodocarpites spp., with a secondary presence of Densipollenites spp. The lithological signatures, including off‐white fine‐grained sandstone with thin bands of silty shale and grey shale, indicate that these sediments belong to the Late Permian succession of the Lower Gondwana sequence, specifically the Raniganj Formation. The macrofloral assemblage found in the lowermost grey shale can be attributed to the Wordian–Capitanian age, while the microfloral assemblage in the upper silty shale resembles that of the Wuchiapingian‐Changhsingian age. Well‐preserved palynomorphs and megafossils, along with the abundant occurrence of lath‐shaped translucent phytoclasts in the grey and silty shale of the Raniganj sediments exposed in the Kendudihi section, explicitly suggest that the sediments were deposited in proximal, low‐energy swampy settings. Additionally, the moderate occurrence of charcoal (20%), along with the existence of degraded organic matter (DOM: 7.6%) and amorphous organic matter (AOM: 16.4%), indicates that the sediments might have been deposited in oxic–dysoxic conditions. The palynological and megafloral studies reveal a warm‐temperate climate with low humidity and intermittent spells of hot and cold seasons, associated with abundant rainfall. The occurrence of phosphorite in the form of nodules and thin lenses, as well as biogenic structures at the juncture of the Raniganj and Barren Measures formations, suggests a marine incursion in the area during the deposition of the late Barren Measures and early Raniganj sediments. X‐ray diffraction (XRD) analysis identified fluorapatite (Ca5(PO4)3F) as the predominant phosphatic mineral phase in the phosphatic nodule, siltstone and claystone. The Post‐Archean Australian Shale composition, normalized rare earth element (REE) patterns of samples from this area, reveals slight positive La (average La anomaly: 1.02) and Gd (average Gd anomaly: 1.05) anomalies and heavy REE enrichment compared to light REE, explicitly indicating a marine environment.

Virus-Based Separation of Rare Earth Elements.

The utilization of biomaterials for the separation of rare earth elements (REEs) has attracted considerable interest due to their inherent advantages, including diverse molecular structures for selective binding and the use of eco-friendly materials for sustainable systems. We present a pioneering methodology for developing a safe virus to selectively bind REEs and facilitate their release through pH modulation. We engineered the major coat protein of M13 bacteriophage (phage) to incorporate a lanthanide-binding peptide. The engineered lanthanide-binding phage (LBPh), presenting ∼3300 copies of the peptide, serves as an effective biological template for REE separation. Our findings demonstrate the LBPh's preferential binding for heavy REEs over light REEs. Moreover, the LBPh exhibits remarkable robustness with excellent recyclability and stability across multiple cycles of separations. This study underscores the potential of genetically integrating virus templates with selective binding motifs for REE separation, offering a promising avenue for environmentally friendly and energy-efficient separation processes.

Tailoring the physicochemical and electrical properties of ZnO thin films by doping with light and heavy rare-earth element via wet chemical approach

Tailoring the physicochemical and electrical properties of ZnO thin films by doping with light and heavy rare-earth element via wet chemical approach

In Situ High-Pressure Correlated Transportation of Heavy Rare-Earth Perovskite Nickelates as Batch Synthesized within Eutectic Molten Salts at MPa-pO2.

The multiple magneto-/electrical quantum transitions discovered with d-band correlated metastable perovskite oxides, such as rare-earth nickelate (ReNiO3), enable applications in artificial intelligence and multifunctional sensors. Nevertheless, to date such investigation merely focuses on ReNiO3 with light or middle rare-earth composition, while the analogous explorations toward heavy rare-earth (ReHNiO3, ReH after Gd) are impeded by their ineffective material synthesis relying on GPa pressure. Herein, for the first time we synthesized the powder of ReHNiO3 in grams/batch with ∼1000 times lower pressure and ∼300 °C lower temperature in comparison to the previous ∼101 milligram/batch results, assisted by their eutectic precipitation and heterogeneous growth within alkali-metal halide molten salt at MPa oxygen pressures. Further in situ characterizations under high pressures within a diamond anvil cell reveal a distinguishing pressure predominated bad metal transport within the nonequilibrium state of ReHNiO3 showing high-pressure sensitivity up to 10 GPa, and the temperature dependences in electrical transportations are effectively frozen.

Spatial distribution of soil rare earth elements in Sicily (Italy)

Rare earth elements (REEs) are becoming increasingly interesting as indicators of soil processes, and modelling their spatial distribution has become a fundamental requirement for this purpose. This study aims to model and quantify the spatial distribution of soil REEs taking into account their compositional nature in their mapping, and to assess the associated spatial uncertainty. In particular, the cerium anomaly (Ce⁎) and the ratio of the sum (Σ) of light to heavy REEs (ΣLREEs/ΣHREEs) were calculated and analysed. The study was carried out in Sicily (Italy), one of the largest (25,832 km2) and most populous island in the Mediterranean Sea. Soil REE data were obtained from the soil database of Sicily region. Soil REEs were transformed into a vector of isometric log-ratio (ilr) coordinates and analysed using a geostatistical approach for predicting their values at unsampled locations and generating 100 REEs realizations using turning bands simulation. Each REE element and Ce⁎ were mapped as well as the ΣLREEs/ΣHREEs ratio. The joint variability of the investigated REEs and the ΣLREEs/ΣHREEs ratio provided insights into their abundance and distribution patterns. From the simulated realizations, standard deviation maps were calculated for the Ce⁎ and the ΣLREEs/ΣHREEs ratio, providing a measure of their spatial uncertainty. Although with some limitations, the study established a first baseline of the Ce⁎ and the ΣLREEs/ΣHREEs ratio. The maps of spatial uncertainty may be a useful tool for planning future soil sampling and optimise the choice of new sampling locations.

Role of (Pr20Nd80)60Tb15Cu15Ga10 intergranular addition on the magnetic properties of Nd-Fe-B sintered magnet

Intergranular addition using heavy rare earth (HRE) Dy/Tb containing alloys has been an effective way to modulate the microstructure and chemical distribution towards fabricating high-coercivity Nd-Fe-B sintered magnets. In this work, (Pr20Nd80)60Tb15Cu15Ga10 (at%) intergranular alloy powders were designed and introduced with dual purposes of forming Tb-rich matrix shell and antiferromagnetic RE6Fe13Ga grain boundary phase (GBP). With 3 wt% (Pr20Nd80)60Tb15Cu15Ga10 addition, the coercivity Hcj is significantly increased from 11.1 kOe to 17.9 kOe, accompanied with a high utilization efficiency of Tb (11.8 kOe/%) and a superior temperature coefficient of coercivity β(−0.531%/K). Microstructural analysis suggests that the improved wettability of grain boundary by (Pr20Nd80)60Tb15Cu15Ga10 addition is beneficial to form the Tb-rich matrix shell and antiferromagnetic RE6Fe13Ga GBP throughout the bulk magnets. Micromagnetic simulation is implemented to study the effect of formed ferromagnetic/antiferromagnetic GBP and Tb-rich matrix shell on the magnetization reversal process. Results show that the synergy of Tb-rich shell surrounding Nd/Pr-rich core and antiferromagnetic Nd/Pr-rich RE6Fe13Ga GBP is an effective way to promote the coercivity with high utilization efficiency of HRE Tb.

Plagioclase Megacrysts in Mesoproterozoic Amphibolites from the New Jersey Highlands, USA: Indicators of Mixed-Source Magma and Fractionation Interruption in Anorthosite-Dominated Terrains

Rare amphibolite in the New Jersey Highlands containing plagioclase megacrysts ≤13 cm long forms bodies 0.5 to 2 m thick that preserve a penetrative metamorphic fabric and have sharp, conformable contacts against Mesoproterozoic country rocks. The megacrystic amphibolites were emplaced as thin dikes along extensional faults between 1160 and 1130 Ma. Amphibolites contain weakly zoned, subhedral andesine megacrysts (An29–44) in a matrix of plagioclase (An18–38), magnesio-hastingsite, biotite, diopside, Fe-Ti oxides, and apatite. The whole-rock major oxide composition of the megacrystic amphibolite matrix has high TiO2 (2.07 wt.% ± 2.0%), Al2O3 (17.03 wt.% ± 0.87%), and Fe2O3t (12.84 wt.% ± 3.2%) that represents an Al-Fe-rich mafic magma type that is characteristic of anorthosite associations globally. The whole-rock, rare earth element (REE) composition of the megacrystic amphibolite matrix is characterized by enrichments in light rare earth elements (LREEs) (La/YbN = 1.73–10.69) relative to middle (MREEs) and heavy (HREEs) rare earth elements (Gd/YbN = 1.30–1.85), and most samples have small positive Eu anomalies (Eu/Eu* = 0.95–1.25). The megacrystic amphibolite matrix is also enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs) (e.g., Ba/Nb = 24–22). Megacrystic amphibolites formed through partial melting of subduction-modified lithospheric mantle that fractionated olivine and plagioclase, producing a high-Al-Fe mafic magma. Plagioclase megacrysts formed through extraction of a plagioclase-rich crystal-liquid mush from anorthosite that mixed with mafic magma and collected in the upper part of the mid-crustal magma (depth of ~20 km based on Al-in-hornblende geobarometry) chamber through flotation. Periodic tapping of this mixed source by extensional fractures led to emplacement of the amphibolites as dikes and may have interrupted the extensive fractionation and plagioclase separation necessary to form voluminous anorthosite intrusions.

Slab break-off of the Kalamaili oceanic slab revealed by the latest Carboniferous mafic–ultramafic rocks in eastern North Tianshan (NW China)

Identifying the tectonic transition from oceanic subduction to collision is crucial for tracking the final stage evolution of ancient orogenic belts. In this study, we present new geochronological and geochemical data for the Mozbaysay mafic–ultramafic complex in the Balikun area, eastern North Tianshan of the southern Central Asian Orogenic Belt. This complex had intruded into the late Carboniferous volcano-sedimentary rocks and is comprised mainly of hornblende gabbro and lherzolite. Zircon U-Pb ages of the hornblende-gabbros reveal that this complex was emplaced at ca. 305 Ma. Geochemical analyses suggest these mafic–ultramafic rocks are characterized by slight enrichment of light rare earth elements (LREEs) and relatively depleted heavy rare earth elements (HREEs), resembling enriched mid-ocean ridge basalt (E-MORB). They also exhibit restricted (87Sr/86Sr)i ratios (0.702396–0.704295) and εNd(t) values (+7.0 to +9.1), indicative of a depleted mantle source with minimal crustal contamination. Incompatible element ratios (i.e., Nb/Ta, Zr/Hf, Rb/Nb, and Ba/Nb) suggest the involvement of subducted slab-derived aqueous fluids in their mantle source. These collectively indicate that the parental magmas of the Mozbaysay mafic–ultramafic rocks may have been generated by a mixed mantle source consisting of the E-MORB-like asthenospheric mantle, subcontinental lithospheric mantle (SCLM), and hydrous fluids from subducted slab. Furthermore, a slab break-off model is proposed to explain the generation of these latest Carboniferous mafic–ultramafic rocks. Integrating these findings with regional geological data, we propose that the tectonic transition from subduction (slab roll-back) to collision (slab break-off) along the Kalamaili suture zone occurred at ca. 305–300 Ma.

Design and Computational Validation of γ-Ray Shielding Effectiveness in Heavy Metal/Rare Earth Oxide-Natural Rubber Composites.

This study involved the preparation of natural rubber-based composites incorporating varying proportions of heavy metals and rare earth oxides (Sm2O3, Ta2O5, and Bi2O3). The investigation analyzed several parameters of the samples, including mass attenuation coefficients (general, photoelectric absorption, and scattering), linear attenuation coefficients (μ), half-value layers (HVLs), tenth-value layers (TVLs), mean free paths (MFPs), and radiation protection efficiencies (RPEs), utilizing the Monte Carlo simulation software Geant4 and the WinXCom database across a gamma-ray energy spectrum of 40-150 keV. The study also compared the computational discrepancies among these measurements. Compared to rubber composites doped with single-component fillers, multi-component mixed shielding materials significantly mitigate the shielding deficiencies observed with single-component materials, thereby broadening the γ-ray energy spectrum for which the composites provide effective shielding. Subsequently, the simulation outcomes were juxtaposed with experimental data derived from a 133Ba (80 keV) γ-source. The findings reveal that the simulated results align closely with the experimental observations. When compared to the WinXCom database, the Geant4 software demonstrates superior accuracy in deriving radiation shielding parameters and notably enhances experimental efficiency.

Anthropogenic impact of rare earth elements on groundwater and surface water in the watershed of the largest freshwater lake in China

Limited knowledge exists regarding the potential risks associated with anthropogenic release of rare earth elements (REEs) in the environment. This study aimed to investigate REE signatures in the watershed Poyang Lake, the largest freshwater lake in China. Samples of surface water, wastewater, and groundwater were collected from five rivers discharging into the lake. Results revealed wastewater from wastewater treatment plants contained total REE concentrations from 231 to 904 μg/L, exceeding those found in surface water (0.4 to 1.3 μg/L) and groundwater (0.5 to 416 μg/L). Samples with elevated REE were found in Ca-Mg-Cl/SO4 type waters and exhibited an 18OD deviation from local meteoric water line. Wastewater exhibited a higher positive Gd anomaly compared to surface water and groundwater, attributed to anthropogenic input of Gd (Gdanth). The determined Gdanth concentration ranged from 0.04 to 0.21 μg/L, and from 0.06 to 0.37 μg/L, accounting for 4 % to 21 % and 49 % to 84 % of total Gd concentrations in groundwater and surface water, respectively. Gdanth concentration in wastewater (0.19 to 0.43 μg/L) remained constant in effluent after wastewater treatment. Surface water displayed relatively complex normalized REE patterns influenced by anthropogenic activities and natural processes (weathering and complexation), while groundwater exhibited heavy REEs enrichment, due to carbonate solution complexation. Additionally, Gdanth concentration showed a positive correlation with ΣREE, Pb, Ni, and Co concentrations in groundwater, indicating a good pollution tracing potential. Health risk assessment using the hazard quotient (HQ) suggested higher HQGd values in groundwater compared to surface water. Residents in the eastern part of Poyang Lake were found to face higher risks associated with Gd in groundwater compared to the western part, with infants and children at greater risk than adult males and females. These findings offer valuable insights into environmental behavior and health risks of REEs in aquatic systems impacted by human activities.

Fluid Inclusion, Rare Earth Element Geochemistry, and Isotopic (O and S) Characteristics of the Ardakan Barite Deposit, Yazd Province, Iran

The stratabound barite mineralization occurs in the Ardakan deposit as patches and veins in the dolomites and limestones of the Middle Triassic Shotori Formation. Rare-earth element (REE) geochemistry, O and S isotopes, and fluid inclusion data were used to identify the mode of barite formation. Barite is associated with subordinate fluorite and quartz and, to a lesser extent, with sphalerite, malachite, chrysocolla, and iron and manganese oxide-hydroxides. Barite contains a very low ∑REE concentration (14.80–19.59 ppm) and is enriched in light rare-earth elements (LREEs) relative to heavy rare-earth elements (HREEs). The low ∑REE content and the Ce/La ratio (4.0–6.5) indicate a hydrothermal (terrestrial) origin of the barite. Similar to barite, the ∑REE content in fluorite is low (0.14–6.52 ppm) and suggests a sedimentary setting. The Tb/Ca versus Tb/La diagram also indicates a hydrothermal origin of fluorite. The δ34S values in the barite (+27.9 to +32.4‰) indicate that the sulfur most likely originates from evaporites and/or connate waters from the Late Precambrian to the Lower Cambrian. The δ18O values (+15.9 to +18.1‰) in the barite show that the oxygen originated either from Late Precambrian–Lower Cambrian evaporites or from basinal brines with slightly higher δ18O values than the evaporites. The salinity and homogenization temperature ranges of the aqueous fluid inclusions in barite, fluorite, and quartz (0.88–16.89 wt% NaCl equivalent and 90–270 °C, respectively) reveal that the mineralizing fluids were formed from basinal brines with the participation of heated meteoric water. From this, it is concluded that the Ardakan barite deposit was formed by the meeting of heated, ascending sulfate-bearing meteoric water and cooler, Ba-bearing connate water trapped in the overlying Middle Triassic dolomites and limestones. The Ardakan deposit belongs to the structure-related class and the unconformity-related subclass of barite deposits.

Mineralogical and geochemical characteristics of mudstones from the Lower Cretaceous Prosopis Formation in the Bongor basin, Chad: Implications for provenance, paleoenvironment and organic matter enrichment

The Cretaceous greenhouse represents the largest global warming event since the Phanerozoic, significantly affecting the provenance, weathering, regional climate, and paleoenvironment of lake basins globally. During the period of global warming, the control of regional paleoenvironment over organic matter enrichment is still unclear. The Lower Cretaceous Prosopis Formation in the Bongor Basin features thick lacustrine organic-rich mudstones as major effective hydrocarbon source rocks with excellent hydrocarbon potential in the basin. However, the provenance, paleoclimate, paleoenvironment and mechanism of organic matter accumulation in this location have not yet been systematically studied. In this study, 22 dark gray mudstone samples were collected from three cored wells. Clay mineralogy, along with organic and inorganic elemental geochemical analyses were jointly carried out to determine the characteristics of the provenance, paleoclimate and paleoenvironment as well as the major controlling factors for organic matter enrichment. The results imply that the Prosopis Formation mudstones are mainly composed of clay minerals such as illite, kaolinite, chlorite, and illite/smectite mixed layers (I/S). Organic geochemistry indicated that all the studied mudstones reached the standard of good to excellent source rocks (the total organic carbon content ranged from 1.27% to 7.41%). Inorganic elemental geochemistry is characterized by high enrichment of Fe, Mg, P, Mn, Ti, Na, Ca, V, Co, Cu, Sr, Ba and B relative to UCC and PAAS, whereas rare earth elements (REEs) show enrichment of light rare earth elements (LREEs) and a deficiency of heavy rare earth elements (HREEs) relative to chondrite. The source composition of the mudstones is predominantly intermediate-felsic igneous rocks that have not undergone sediment recycling. The parent rocks experienced weak to moderate weathering, corresponding to semiarid paleoclimatic conditions of transitional nature. The organic-rich mudstones were deposited in fresh to brackish waters with paleoredox conditions ranging from weakly oxic to anoxic semi-deep to deep lake environments having relatively low initial productivity. Comprehensive study indicates that paleoredox and paleoclimate are important parameters affecting the enrichment of organic matter in lake basins during global warming. The aridification of climate is one of the most important reasons for the high input and efficient preservation of organic matter. The relatively semiarid climate both increased the supply of terrigenous nutrients to the lake basins and provided a driving force for the increase in salinity, thereby providing better sources and preservation conditions for organic matter.

Post-collisional reworking of juvenile mafic lower crust for the petrogenesis of late Triassic adakitic rocks in the East Kunlun Orogen

The East Kunlun Orogen (EKO), a major component of the Greater Tibetan Plateau, provides an excellent natural laboratory to investigate the tectonic evolution of the Paleo-Tethys Ocean (also known as the A'nyemaqen Ocean in the EKO). We present a combined study of in situ zircon UPb ages and LuHf isotopic compositions, and whole-rock major and trace element and Sr–Nd–Hf isotopic compositions of the post-collisional Xiangjia granodiorite at the eastern end of the EKO. Zircon UPb dating indicates that the Xiangjia granodiorites were emplaced at 225.0–217.1 Ma. Relict zircon cores yield ages of 267.5–239.5 Ma. These granodiorites are calc-alkaline to high-K calc-alkaline and metaluminous to weakly peraluminous, enriched in large-ion lithophile elements and light rare earth elements, and depleted in high field strength elements (e.g., Nb and Ta) and heavy rare earth elements. They yield trace element characteristics that are typical of adakitic rocks, including high Sr (493–590 ppm) and low Yb (0.74–1.12 ppm) and Y (8.83–12.24 ppm) contents, high Sr/Y (40.47–63.64) and (La/Yb)N (11.81–30.91) ratios, and positive Eu anomalies. The UPb ages and Hf isotopic compositions of the relict zircon cores and whole-rock SrNd isotopic compositions of the Xiangjia adakitic rocks are similar to those of the mafic arc magmatic rocks formed during the subduction of the Paleo-Tethys Ocean, suggesting they originated from the reworking of juvenile mafic lower crust. Phase equilibrium modelling suggests that the contemporaneous adakitic rocks from Xiangjia and other areas in the EKO are likely the products of partial melting of the juvenile mafic arc rocks under granulite-facies conditions at 10–11 kbar and 934–951 °C, possibly related to slab break-off in a post-collisional setting.

Geochronology, Geochemical Characterization and Tectonic Background of Volcanic Rocks of the Longjiang Formation in the Lengjimanda Plate Area, Middle Da Hinggan Mountains

The Lengjimanda plate is situated in the middle section of the Da Hinggan mountains, in the eastern section of the Tianshan Xingmeng orogenic belt. To determine the formation age of the volcanic rocks in the Longjiang formation in this area, to explore their origin and tectonic background, and to reconstruct the geodynamic evolution of the region, this study conducted petrological, zircon U–Pb geochronological, geochemical, and isotopic analyses of the volcanic rocks in the Longjiang formation. The Longjiang formation’s volcanic rocks are primarily composed of trachyandesite, trachyte trachydacite, and andesite, which are intermediate basic volcanic rocks. They are enriched in large-ion lithophile elements, are depleted in high-field-strength elements, are significantly fractionated between light and heavy rare earth elements, and exhibit a moderate negative Eu anomaly in most samples. The results of the LA–ICP–MS zircon U–Pb dating indicate that the volcanic rocks in this group were formed in the Early Cretaceous period at 129.1 ± 0.82 Ma. The zircon εHf(t) ranges from +1.13 to +43.77, the tDM2 ranges from +655 to +1427 Ma, the initial Sr ratio (87Sr/86Sr)i ranges from 0.7030 to 0.7036, and the εNd(t) ranges from +2.1 to +6.6. Based on the geochemical compositions and isotopic characteristics of the rocks, the initial magma of the volcanic rocks in the Longjiang formation originated from the partial melting of basaltic crustal materials, with a source material inferred to be depleted mantle-derived young crustal. These rocks were formed in a superimposed post-collisional and continental arc environment, possibly associated with the Mongol-Okhotsk Ocean closure and the oblique subduction of the Pacific plate. This study addresses a research gap regarding the volcanic rocks of the Longjiang formation in this area. Its findings can be applied to exploration and prospecting in the region.

Fish 3D Locomotion app: a user-friendly computer application package for automatic data calculation and endpoint extraction for novel tank behavior in fish.

This paper introduces the Fish 3D Locomotion app (F3LA), a Python-based, Graphical User Interface (GUI)-equipped tool designed to automate behavioral endpoint extraction in zebrafish locomotion assays. Building on our previous work, which utilized a specialized aquatic tank with a mirror and a single camera for fish movement tracking in three dimensions, F3LA significantly enhances data processing efficiency. Its accuracy was tested by reanalyzing and comprehensively comparing the calculated data with the previously published data from prior publications. From the comparison results, 90% of endpoints showed a similar statistical difference result. These minor differences were due to the different starting points for the dataset and updated calculation formulas that are implemented in F3LA. In addition, shoaling area or shoaling volume calculations are also included in F3LA as a new feature that can serve as sensitive indicators of social cohesion, group dynamics, or stress responses, offering insights into neuropsychological conditions or the effects of pharmacological interventions. Furthermore, F3LA offers a marked improvement over manual operations, being at least five times faster, while maintaining consistent accuracy as it reduces human-induced errors, ensuring a higher degree of reliability in the results. Finally, the potency of F3LA was tested to evaluate the toxicities of 14 rare earth elements (REEs) to the adult zebrafish behaviors. Based on the results, our findings suggested that each tested REE altered fish behaviors in different patterns and magnitudes to each other. However, among the tested light rare earth elements (LREEs), neodymium was demonstrated to cause more relatively severe behavior alterations than other LREEs, indicated by the statistically higher value of entropy (0.2695 ± 0.04977 (mean with a standard deviation)) than the control group (0.2352 ± 0.05896). Meanwhile, in terms of heavy rare earth elements (HREEs), erbium seemed to lead to more distinct behavior toxicities than other HREEs, which was shown by the statistically lower level of fractal dimension (2.022 ± 0.3412) than the untreated group (2.255 ± 0.1661). Taken together, F3LA's development marks a significant advance in high-throughput toxicological and pharmacological assessments in zebrafish, leveraging three-dimensional locomotion data for a more comprehensive analysis of fish behavior performance, providing a significant contribution to research in various fields.

Impact of particle size and associated minerals on rare earth desorption and incorporation mechanisms in a South American ion-adsorption clay

This research delves into the intricate nexus of particle size, mineralogical composition, surface attributes, elemental mapping, and rare earth element (REE) adsorption mechanisms within an ion-adsorption clay sample from South America. The investigation entails the fractionation of the ion-adsorption clay into three size categories: S1 (< 0.25 mm), S2 (0.25–0.5 mm), and S3 (0.5–2 mm). Each fraction undergoes meticulous characterization to unveil its elemental composition, mineralogical composition, surface area, morphological characteristics, elemental mapping, and the mechanisms governing REE incorporation. The results indicate that S1 has 31% physiosorbed, 8% chemisorbed, and 61% mineralized REEs, while S2 has 40% physiosorbed, 5% chemisorbed, and 55% mineralized REEs, and S3 has 24% physiosorbed, 5% chemisorbed, and 71% mineralized REEs. The physisorbed REEs are attributed to the presence of kaolinite, conducive to mostly physisorption. In terms of grain size and REE content/type relationship, the results show that REE content decreases with increasing grain size; however, there is not a clear trend in terms of REE occurrence modes with grain size. Heavy rare earth elements (HREEs) are discernibly favored in adsorption over light rare earth elements (LREEs). This preference is underpinned by the weathering processes that led to the formation of ion-adsorption clay, which facilitated the transport and accumulation of HREEs. Notably, the ion-adsorption clay encompasses a substantial content of mineralized REEs, necessitating more demanding extraction methodologies, such as acid baking followed by water leaching if complete extraction of all REEs is desired. Among the desorbable REEs, physisorption dominates, encompassing over 80% of the total. Chemisorbed REEs exhibit versatility in association with various minerals, encompassing kaolinite, quartz, and goethite. In essence, this study unveils the intricate interplay between particle dimensions, mineralogical constitution, surface attributes, and REE adsorption modes within this ion-adsorption clay sample. The ion-adsorption clay in this study contains a significant portion of mineralized REEs that cannot be extracted using the mild conditions typically employed for the desorption process. Additionally, the REE concentration in this ion-adsorption clay is notably higher than the average found in clay deposits worldwide, reaching levels comparable to those of regolith deposits in China, which are a major global source of REEs. This remarkable concentration of REEs, along with the unique modes of their occurrence in this deposit, presents a significant interest to the scientific community.

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Rare Earth Element Binding and Recovery by a Beta Roll-Forming RTX Domain.

The Block V of the RTX domain of the adenylate cyclase protein from Bordetella pertussis is disordered, and upon binding eight calcium ions, it folds into a beta roll domain with a C-terminal capping group. Due to their similar ionic radii and coordination geometries, trivalent lanthanide ions have been used to probe and identify calcium-binding sites in many proteins. Here, we report using a FRET-based assay that the RTX domain can bind rare earth elements (REEs) with higher affinities than calcium. The apparent disassociation constants for lanthanide ions ranged from 20 to 75 μM, which are an order of magnitude higher than the affinity for calcium, with a higher selectivity toward heavy REEs over light REEs. Most proteins release bound ions at mildly acidic conditions (pH 5-6), and the high affinity REE-binding lanmodulin protein can bind 3-4 REE ions at pH as low as ∼2.5. Circular dichroism (CD) spectra of the RTX domain demonstrate pH-induced folding of the beta roll domain in the absence of ions, indicating that protonation of key amino acids enables structure formation in low pH solutions. The beta roll domain coordinates up to four ions in extreme pH conditions (pH < 1), as determined by equilibrium ultrafiltration experiments. Finally, to demonstrate a potential application of the RTX domain, REE ions (Nd3+ and Dy3+) were recovered from other non-REEs (Fe2+ and Co2+) in a NdFeB magnet simulant solution (at pH 6).