Heavy Rare Earth Research Articles

Transport Model of Rare Earth Elements in Weathering Crusts during Electrokinetic Mining

Electrokinetic mining (EKM) is a novel method for rare earth element (REE) mining that can achieve green and efficient recovery of REEs. However, as yet, there is no accurate model for describing the electrokinetic transport of REEs in weathering crusts, and this hinders the wider application of EKM. The conventional model fails to capture the microscale transport physics occurring in the nanochannels that exist ubiquitously in weathering crusts. Consequently, the existing models cannot distinguish the mobilities of different REEs. Here, we report a new model for a more faithful description of the electrokinetic transport of REEs in weathering crusts that considers the ionic size, which has previously been neglected. We reveal that the electrokinetic transport of heavy REEs (HREEs) is faster than that of light REEs (LREEs) in weathering crusts, which is contrary to the predictions of conventional models. Our model was validated experimentally by measurements of the electrokinetic transport of two LREEs (La and Sm) and an HREE (Er) in weathering crusts. The speed of electrokinetic transport follows the order Er > Sm > La. Our findings suggest that the ionic size is a non-negligible factor affecting the electrokinetic transport of REEs in weathering crusts containing nanochannels. This work offers a constitutive model to describe the electrokinetic transport of REEs in weathering crusts, which promotes both theoretical developments and practical applications of EKM.

Diffusion behavior of heavy rare-earths for grain boundary engineering of sintered Nd-Fe-B-based permanent magnets produced by the 2-powder method

The 2-powder method (2PM) for the production of high-performance Nd2Fe14B-based sintered magnets consists of blending a coarser heavy rare-earth (HRE) free main phase powder (here D50 = 5.3 µm) and a finer HRE-containing anisotropy powder (here D50 = 2.6 µm) of Dy content of 10 wt.%. The development of the core-shell structure was observed for different sintering conditions, namely at 1090 °C for 5, 10, 30, 60, and 120 min. The diffusion behavior of the 2PM was investigated and the diffusion coefficient for the heavy rare-earth element dysprosium of D = (1.83 ± 0.54) x 10−11 cm2/s was determined. Magnets containing 0, 1, 2, and 3 wt.% Dy were produced by the 2PM and magnetic properties were analyzed in detail. A constant coercivity gain of around 120 kA/m per added Dy contents was reached. Dy was obtained without a significant decrease in remanence. Finally, the 2PM was compared with the conventional powder metallurgical production process. The enormous potential for decreasing the amount of critical HREs in Nd-Fe-B–based sintered magnets is demonstrated, especially in large volume magnets as 2PM is not restricted to 5 mm thick pieces, but can be applied to large scale.

Petrologic relationship between lamprophyres, carbonatites, and heavy rare‐earth element enriched breccias at Hicks Dome

AbstractNew petrological, geochemical, and P–T modelling results from igneous samples clarify how carbonatite‐lamprophyre magmatism, fluorite and rare earth element (REE) enrichment are petrogenetically related in southern Illinois. P–T modelling reveals that igneous rocks derive from a deep mantle carbonated source, that is consistent with trace element signatures for a fluorine‐rich transition zone origin. Major element systematics suggests liquid‐immiscibility with lamprophyric melts as the origin for Ca‐carbonatites. Heavy REE (HREE) enrichments in Hicks Dome breccias likely formed through preferential partitioning and transport of HREE by brine‐melts, exsolved from a deep carbonatite body. Brine‐melts redistributed HREEs throughout the system along brecciated pathways where they reprecipitated as HREE‐rich phosphate/fluorcarbonate minerals (e.g. xenotime, florencite, synchesite) in host bedrock. The diversity of igneous rocks in southern Illinois highlights the area as an excellent natural laboratory to study carbonated melt petrogenesis and evolution.

Carboniferous–Early Permian volcano-sedimentary units from the northern margin of the North China Craton recorded subduction initiation in the Paleo-Asian Ocean

The precise timing of subduction initiation of the Paleo-Asian Ocean (PAO) in the northern margin of the North China Craton (NCC) remains controversial. In this study, we have conducted zircon UPb dating, whole-rock major and trace elements, and zircon Hf isotope analyses on metadacites and metamorphic greywackes from the Changde volcano-sedimentary rocks, feldspar quartz sandstones and argillaceous siltstones from the Luquantun Formation and the Sidao sedimentary rocks in central-eastern Jilin Province (NE China), to constrain the initial closure of the PAO. We obtained Early Carboniferous zircon UPb ages (345 ± 2 Ma and 351 ± 7 Ma) from the Changde volcano-sedimentary rocks. The metadacites are characterized by the enrichment in light rare earth elements and large ion lithophile elements, depletion in heavy rare earth elements and high field strength elements, and rare earth element ratios similar to those of the continental crust, indicating that these rocks originated from crustal melting. The metadacites exhibit affinity with the peraluminous A-type granite, with high zircon εHf(t) values (+3.46 − +12.21) and TDM2 of 1132–571 Ma, suggesting that they formed in a post-collisional extensional setting. Detrital zircon UPb ages from the Luquantun Formation and Sidao sedimentary rocks constrain their maximum depositional ages to the Late Carboniferous (319 ± 5 Ma) and Early Permian (284 ± 4 Ma), respectively. Most detrital zircons have age peaks at 1800 Ma with negative zircon εHf(t) values, and 2500 Ma with positive zircon εHf(t) values, suggesting that the Carboniferous–Early Permian sediments from these two formations were mainly sourced from the NCC. Moreover, the chemical index of alteration, index of compositional variability, and plagioclase index of alteration values suggest that the sediments of the Changde volcano-sedimentary rocks originated from a mafic igneous source with a low degree of weathering and a sedimentary recycling history, while the samples from the Luquantun Formation and Sidao sedimentary rocks were sourced from an intermediate-felsic igneous rock with a moderate to intense degree of weathering and mainly influenced by source composition. The crystallization age curves and summary plots of detrital zircons indicate that the Early Carboniferous metamorphic greywackes from the Changde Formation were mainly deposited in a passive margin, while the Carboniferous–Early Permian sediments of the Luquantun Formation and Sidao sedimentary rocks were mainly deposited in an active margin. We suggest that the tectonic transition from passive to active margin occurred at ∼333 Ma, marking subduction initiation in the PAO close to the northern margin of the NCC.

Toward the Improvement of the Short‐Loop Recycling of Dy‐Rich Nd–Fe–B Permanent Magnets: Experimental and Numerical Approaches

The method of short‐loop recycling of Nd–Fe–B magnets is implemented, with end‐of‐life (EoL) magnets used as a source of heavy rare earth (HRE). Partially recycled magnets are fabricated by co‐sintering HRE‐free powders obtained from strip casted alloys, blended with HRE‐rich powders obtained from EoL magnets. The impact of several process parameters (blending ratio, sintering cycle, and HRE‐rich recycled particle sizes) on the microstructure and magnetic properties is discussed. A coercivity gain up to 160 kA m−1 wt%−1 of Dy with respect to the HRE‐free magnets is reported, even though impurities are incorporated. Microstructural characterizations show a heterogeneous Dy localization in core–shell/anticore–shell structures, and thus a nonoptimal use of HRE. The experimental results are compared with finite element simulations of the Dy diffusion transport performed using existing data of bulk Dy diffusion coefficients. The simulation model consists of a network of square grains separated by a liquid phase, whose fraction is based on the ternary Nd–Fe–B phase diagram. Results show similarities with the observed microstructures, and point to the interest of reducing the Dy‐rich particle size with respect to the main powder. This study provides new insights into the Dy transport mechanisms at stake in an efficient short‐loop recycling of HRE.

Formation mechanisms of fluvial residues from eastern watersheds of China: Insights from corrected weathering process and sediment provenance

Investigating the weathering process and provenance of fluvial residues plays a crucial role in revealing superficial circulation on earth. Although the transfer and inheritance processes have been well elaborated for intra-watersheds, the limitations and applications of geochemical proxies need to be further explored for cross-watersheds. Geochemical analysis was performed on 541 surficial sediment samples from 12 intertidal zones in China, combined with traditional weathering indices, mass transfer coefficients, and rare earth element parameters, to gain a better understanding of their geochemical behavior. Based on the interactions of lithology, hydrodynamic sorting, and sedimentary recycling on various weathering indices, the metamorphic and succession processes of the residues were fully characterized during the source-to-sink process. The weathering index of Parker (3.9–66.2) was more susceptible to the hydrodynamic sorting effect, whereas the chemical index of alteration (45.8–83.9) was heavily influenced by the sedimentary recycling process. In comparison, the mass transfer coefficient of Na provides better performance in the early weathering stage and is optimally protected from the effects of hydrodynamic sorting and sedimentary recycling. As confirmed by the corrected mass transfer coefficients and weathering indices, regional temperature and precipitation co-dominated the weathering heterogeneity. Parameters excluding heavy rare earth elements were hardly affected by the weathering process and grain-size effect, and were the most sensitive geochemical proxies for tracing the provenance of fluvial residues. This could provide a scientific basis for cross-watershed research, source apportionment, and regional geological background.

Magnetothermal properties including magnetocaloric performance of the ternary rhombohedral Laves phase of Pr2Rh3Ge

The article presents the study of the magnetocaloric effect (MCE) for the rhombohedral Laves phase of Pr2Rh3Ge, which shows a magnetic order below TC=8.5 K. We have established that the compound exhibits a continuous second-order type of transition which was demonstrated and confirmed by several different techniques, mainly by analyzing universal curves of normalized entropy change as a function of scaled temperature. The observed MCE, in our opinion, is a consequence of an indirect exchange coupling between the magnetic sublattices of the rare earth ions, which, however, does not exclude the potential contribution of sublattice-containing transition metals. In this paper, the procedure to evaluate the MCE from magnetization and specific heat data is described. As a result, important parameters such as the isothermal magnetic entropy change (ΔSM), adiabatic temperature change (ΔTad), relative cooling power (RCP), and the temperature averaged entropy change (TEC) were determined. The highest values of −ΔSM, ΔTad, and RCP for a field change (Δμ0H) of 5 T at TC are 5.96 J/kgK, 3.87 K, and 72.62 J/kg, respectively. These results obtained for Pr2Rh3Ge seem to be, however, low compared to the values obtained for the rhombohedral Laves phases, belonging to the group of ternary germanides RE2Rh3Ge containing heavy rare earth metals (RE = Gd, Tb, Ho, and Er). Nevertheless, we believe that the results presented in this work extend and complement the current knowledge on the magnetocaloric properties of this family of materials.

Dissolved rare earth elements in the North Pacific Subtropical Gyre: Lithogenic sources and water mass mixing control

In the North Pacific Subtropical Gyre, which is one of the largest oligotrophic regions, there is a lack of information regarding the sources and transport of trace metals through water mass mixing. Rare earth elements (REEs) are essential for tracing lithogenic sources and water mass transport. In this study, we present dissolved REE concentrations and the factors controlling their distributions in the northwest Pacific during a GEOTRACES cruise (GP09). In the surface water along 11°N, we observed input signals from the Philippine and the Hawaiian Islands, characterized by positive Eu anomalies and slightly elevated REE concentrations. By incorporating our data and published REE data from the northwest Pacific to the southeast Pacific (40°N–40°S), we demonstrated that the REE concentrations and Yb/Nd ratios can distinguish North Pacific Intermediate Water (NPIW), Antarctic Intermediate Water (AAIW), and modified AAIW. By estimating the ratio of water mass mixing, we suggest that heavy REEs are predominantly contributed by water mass mixing (e.g., 93 % ± 4% for Yb) and can be used as semi-conservative tracers to quantify the mixing of NPIW and modified AAIW at the potential density of 27.2 kg/m3. At ∼800 m depth at stations K12, K13, and K14, weak negative Ce anomalies (>0.1) were observed, indicating the lateral transport of water masses imprinted with sediment signals from the Philippine Islands. In the deep waters (>1500 m) at the Luzon Strait (station K1), we propose that the weak Ce negative anomalies (>0.08) and low Yb/Nd ratios (<5), combined with the low beam transmission, are the result of particle resuspension and release. In deep water (>2000 m), combining high-resolution REE measurements with water mass analysis, our research reveals that dissolved REEs (except Ce) are dominantly controlled by water mass mixing (e.g., 80 %∼100 % for Yb and 70 %∼100 % for Nd). For the non-conservative behavior, which is not explained by water mass mixing, the residual fraction of heavy REEs (<20 % for Yb) originates from release of sinking particles (organic matter and siliceous particles), while the remaining concentrations of light REEs (<30 % for Nd) may be influenced by a combination of particle release and scavenging processes. These findings highlight valuable information about lithogenic sources and the proportions of REE distributions that are controlled by physical and biogeochemical processes. Moreover, it emphasizes the applicability of heavy REEs as effective tracers for understanding basin-scale water mass mixing in the northwest Pacific.

Closed-loop purification process of industrial phosphoric acid: Selective recovery of heavy metals and rare earth elements via solvent extraction

Phosphate fertilizers are produced using phosphoric acid as a vital chemical component. This essential ingredient is typically derived from phosphate rock, through a wet process phosphoric acid (WPPA). However, the WPPA contains impurities, including heavy metals (HMs) like cadmium (Cd), zinc (Zn) and copper (Cu), as well as unwanted elements like iron, and other valuables elements, notably rare earth elements (REEs) such as yttrium (Y), holmium (Ho) and ytterbium (Yb). The current study aims to develop a novel process for a simultaneous and selective recovery of HMs and REEs through solvent extraction from WPPA. Single-stage extraction, cascade extraction and synergistic extraction were explored to gain a deeper understanding of the mechanisms and identify the most efficient process. 90, 80 and 99 % for Y, Ho and Yb, respectively, were extracted using D2EHPA. While 89 % for Zn, 99 % for Cu and Cd were removed using Cyanex 301. On the other hand, 60 % of Yb, 74 % of Y and 78 % of Ho were stripped using H2SO4, while 98 % of Cd and 99 % of Zn were stripped using HCl. The organic phase can be successfully reused with an effective extraction and stripping. Oxalic acid (C2H2O4) was employed to precipitate REEs. However, sodium carbonate (Na2CO3) was used to precipitate HMs. Finally, solvent extraction was carried out on WPPA solution to ensure the extraction performance under industrial conditions.

Source and geological significance of Jurassic asphalt in the Ruoqiang Sag of Southeast Depression, Tarim Basin, Northwestern China

The Southeast Depression of the Tarim Basin has a very low petroleum exploration degree, and currently, no industrial oil and gas have been discovered. Many hydrocarbon shows exist in the Ruoqiang Sag, where hydrocarbon sources and accumulation processes are unclear. Only two potential Jurassic hydrocarbon source rocks developed in the Ruoqiang Sag, the Yangye (J2y) lacustrine mudstone of the Middle Jurassic and the Kangsu (J1k) coal-bearing mudstone of the Lower Jurassic. In this study, the Jurassic asphalt found in the QD1 well, combined with the source rocks of drilling cores and outcrops, was used to explore the possible hydrocarbon source and forming process in the Ruoqiang Sag using oil-source correlation and hydrocarbon accumulation geochronology methods. The asphalts have lower light and heavy rare earth fractionation than the J2y mudstone, and the total rare earth element (ΣREE) content, chondrite-normalized curves, and δEu and Y/Ho values are similar to those of the J1k mudstone, especially for the J1k coal. The n-alkane ratios of the carbon preference index and the odd-to-even preference (OEP) of Jurassic asphalts are greater than 1.0, indicating that its source rock has experienced low thermal evolution. All Jurassic samples have similar source-related biomarkers but different maturity-related parameters, and the thermal evolution degree of asphalt is close to the J1k mudstone and coal but slightly higher than the J2y mudstone. Meanwhile, rhenium–osmium isotopes show the asphalts are formed in 192+30/−45 Ma, which is similar to the J1k sedimentation time. The asphalts contain coal macerals and probably derived from the asphaltene precipitated by the J1k coal during the early coalification. The low abundance of 25-norbornanes with a non- or slight petroleum biodegradation degree indicates the asphalt was generated relatively late and migrated into the J2y formation along the faults, possibly accompanied by the striking activities of the Altyn Tagh Fault during the Neotectonics movement. This study provides evidence for the J1k coal-bearing strata serving as the effective source rock in the Ruoqiang Sag and increases confidence for Jurassic petroleum exploration in the Southeast Depression of the Tarim Basin. The structural and lithological traps near hydrocarbon source stoves, where Jurassic strata were deeply buried and far from the Altyn Tagh Range, are favorable oil and gas exploration targets.

Understanding the coercivity enhancement mechanism of grain boundary diffused Nd-Fe-B magnets by comparing with commercial equivalent coercivity magnets

The grain boundary diffusion (GBD) technology effectively utilizes heavy rare earth (HRE) elements to improve the coercivity of sintered Nd-Fe-B magnet. Significantly, clarifying its coercivity improvement mechanism is essential for further optimizing the process and performance. Through comparative analysis with commercial conventional magnets (CSH) processing equivalent coercivity, this study investigated the specific mechanism by which the GBD method enhances the coercivity of HRE elements in an efficient manner. To achieve the same coercivity (∼21.4 kOe), GBD magnets contained only 0.25 wt% Tb, whereas CSH magnets had 1.17 wt% Dy and 1.18 wt% Tb. The microstructure analysis revealed that the Tb element in the GBD magnet was concentrated in the outer layer of the grain, constituting 17.37 wt% of the total rare earth content. While, in CSH magnets, the HRE element in the main phase grains accounted for only 9.58 wt% of the total rare earth elements, including Dy (3.83 wt%) and Tb (5.75 wt%). The characteristic core-shell structural grains in GBD magnet also endowed it with an uneven magnetic domain structure and a more concentrated “abrupt” magnetization reversal. Based on the characterization results the nucleation positions of the two types of magnets were analyzed by fitting Hci/Ms and Ha/Ms. The results can serve as a guide for enhancing coercivity in grain boundary diffusion sintered Nd-Fe-B magnets, aiding in process and property optimization, and advancing the understanding of nucleation type mechanisms.

Relationship between the genesis of Changlinggang alkaline rocks and uranium mineralization in the 414U-Th deposit, Jianshui County, Yunnan Province, China

Alkaline rocks identified in the 414 U-Th deposit in Jianshui County, Yunnan Province, exhibit intense spatial correlation with uranium mineralization. However, limited investigations into their genesis have had an adverse impact on our understanding of uranium mineralization. Analyses of major and trace elements, U-Pb chronology, and petrography were conducted on alkaline rocks. The results indicate that anorthosite, which is rich in alkalis, high in potassium, peraluminous, enriched in rare earth elements (U, Th, Rb, and Zr) and deficient in Sr, Ba, Ti, and P, predominates the lithology. The light and heavy rare earth fractionation of the material is readily apparent (LREE/HREE=7.89–46.72), and the presence of Eu negative anomalies (δEu=0.65–0.81) suggests that the region from which the magma originated is a metasomatism-enriched mantle where the source material originates from the transition zone between garnet-lherzolite and spinel-lherzolite in the EMII-enriched lithospheric mantle. This area underwent metasomatization by subduction material from the Paleo-Pacific Ocean and during the ascent process, magma experienced a certain degree of partial melting and a significant degree of crystallization differentiation. The diagenesis of the syenite (186.64 ± 3.76 Ma) occurred after the closure time of the Paleotethys Ocean (237 Ma) in a dynamical context of an intra-terrestrial rift environment following subduction of the oceanic plate. In summary, the U and Th present in the 414 U-Th deposits underwent isomorphism within biotite and feldspars during the hydrothermal mineralization stage of magma evolution, where they were enriched in minerals through the separation and crystallization of alkaline magma.

Influence of goethite nanophase on rare-earth element patterns and enrichment in marine phosphates during early diagenesis

Although rare-earth elements (REEs) in authigenic phosphates and carbonates derived from marine sediments are potential proxies (e.g., REE patterns) for reconstructing paleoenvironmental conditions, the REE patterns appear to be inconsistent. Some marine authigenic phosphates show a “bell-shaped” pattern with an enrichment of the middle REEs (MREEs; NdHo), while others exhibit a “modern seawater-like” pattern characterized by a strong depletion in cerium and an enrichment in heavy REEs (ErLu, Y, and Sc). Although the origin of the “bell-shaped” pattern in phosphates has been extensively debated, the evidence is often ambiguous; therefore, the origin of the pattern remains unclear. In this study, we investigate the microscale and nanoscale mineralogical and geochemical characteristics of the REE-enriched Early Cambrian phosphorites. In situ elemental analyses reveal that the codeposited phosphates (“bell-shaped” REE pattern) and carbonates (“modern seawater-like” pattern) have different REE patterns. A microscale investigation shows that phosphate grains contain some dispersed goethite nanophase, and a nanoscale investigation using transmission electron microscopy coupled with electron energy-loss spectroscopy shows that Fe2+ is distributed along the rim of the goethite nanophase, indicating that the goethite were reduced. These findings suggest that the REE pattern and concentration in phosphates could have been influenced by the release of REEs during the reduction of Fe (oxyhydr)oxide in the early diagenetic process before the final deposition. Although additional evidence is required, our results are important for understanding the effects of Fe redox cycling on the REE pattern and enrichment in marine authigenic phosphates. In addition, our results suggest that compared with authigenic phosphates, authigenic carbonates would provide a more reliable reconstruction of paleoenvironmental conditions.

Adsorption and desorption characteristics of rare earth ions on halloysite surfaces

Rare earths (REs) are primarily adsorbed in ionic form on the surface of clay minerals such as halloysite in ionic rare earth ores. As a result, understanding the adsorption and desorption behaviors of RE ions on the surface of the halloysite may contribute to clarifying the mineralization process of ionic rare earth ores and provide a theoretical framework for the optimization of the extraction process. The adsorption and desorption characteristics of light (Nd&lt;sup&gt;3+&lt;/sup&gt;), medium (Eu&lt;sup&gt;3+&lt;/sup&gt;), and heavy (Lu&lt;sup&gt;3+&lt;/sup&gt;) RE ions on the surface of halloysite-10 Å were comprehensively examined in this study. Because REs are more inclined to form an outer layer and inner layer adsorption when halloysite is protonated and deprotonated with the range of pH, respectively, pH has a significant impact on how halloysite adsorbs and desorbs. The experiment findings indicate that RE concentration, duration, and pH all increased the adsorption capacity of light, medium, and heavy REEs, and exhibited some selectivity for heavy REEs. Nd&lt;sup&gt;3+&lt;/sup&gt;, Eu&lt;sup&gt;3+&lt;/sup&gt; and Lu&lt;sup&gt;3+&lt;/sup&gt; ions adsorption processes on the surface of Halloysite-10 Å are consistent with the Langmuir isothermal adsorption model and pseudo-second-order kinetic equations. The desorption efficiency of Lu&lt;sup&gt;3+&lt;/sup&gt; decreases dramatically with increasing pH due to hydrolysis and more inner layer adsorption than that of Nd&lt;sup&gt;3+&lt;/sup&gt; and Eu&lt;sup&gt;3+&lt;/sup&gt;.

Trace elements in coralline algae as a new proxy for seawater chemistry and metal pollution

The abundances of some macronutrients, and trace elements (K, Al, P, V, Mn, Co, Ni, Cu, Zn, Rb, Sr, Mo, Cs, Ba, Pb, Th, U, Y and REE) were determined in a series of coralline algae (Lithothamnion corallioides) samples (n = 101) collected alive in the Bay of Brest and the Iroise Sea (Western Brittany, NW France), in order to assess the potential of these algae as archives of seawater chemistry and potential metal pollution. REE and Y (REY) patterns are similar in shape to those of local seawater, exhibiting similar La, Ce and Y anomalies, but with abundances ranging between 4 and 5 orders of magnitude higher than seawater values. Variations in La anomalies (La/La* = 1.29–2.08), Y anomalies (Y/Ho = 38.6–55.8), and heavy rare earth enrichments (Prsn/Ersn = 0.22–0.52) are consistent with mixing of seawater with rivers flowing into the Bay of Brest. The behavior of other trace elements, such as Al and Cs, also reflects this mixing. Other parameters and processes can control the abundances of the other elements measured. For example, the presence of organic matter in studied samples controls the abundances of K and Rb. The abundances of base metals (e.g., Co, Ni, Cu) are highly sensitive to the various pollutants present in the Bay of Brest. In particular, the Pb content of coralline algae clearly reflects the pollution caused by mining of a nearby Pb deposit from the 18th to the early 20th century. Our results demonstrate the potential of coralline algae not only for tracing water masses, but also for studying metal pollution.

Continental subduction in Paleoproterozoic: Insights from ∼ 1.9 Ga nepheline syenite in the North China craton

Subduction of continent is known as a feature of modern plate tectonics, and it is still unclear whether such a process also occurred in the early Precambrian. Despite of ultra-high pressure metamorphism of terrestrial rocks as a proxy of continental subduction, magmatism produced during continental subduction is also a potential alternative. The North China craton is well-known for the occurrence of 1.9 Ga retrograde eclogite, which was likely originated from the subducting oceanic crust along the Trans-North China Orogen (TNCO). Here a nepheline syenite (the Aohu pluton), the first of the kind from the TNCO, is discovered in Yunzhong Mts. It comprises nepheline (∼20 vol%), albite (50–55 vol%), K-feldspar (5–10 vol%), biotite (∼10 vol%), and calcite (∼5 vol%), with minor accessory minerals. No associated mafic or silicic rocks are outcropped in the pluton. SHRIMP zircon U-Pb analyses yield a crystallization age of 1893 ± 13 Ma and a metamorphic overprinting of 1871 ± 17 Ma. The rocks have medium SiO2 contents (51.9–58.9 wt%), low MgO (0.6–1.6 wt%) and Mg# (24–34), but high Al2O3 (20.0–22.9 wt%) and extremely high K2O + Na2O contents (10.0–13.6 wt%; Na2O/K2O = 1.3–2.6). They are enriched in light rare earth elements (REEs) and large ion lithophile elements, but relatively depleted in heavy REEs and high field strengthen elements. They have extremely low compatible elements (e.g., Ni and Cr). They show high (87Sr/86Sr)i ratios (0.706–0.707) but low εNd(t) values (−5.3 to −6.0; Nd T2DM = ca. 2.7 Ga). Their zircon in-situ εHf(t) values have a wide range (0 to −5.7; Hf T2DM = 2.5–2.85 Ga). The absence of mafic component and the extremely low-Mg feature, as well as their trace element patterns and initial Sr-Nd isotopes being compatible with melts derived from the Archean mafic crustal enclaves in the region, support a continental crust origin for the Aohu nepheline syenite. Based on comparison and modeling, we suggest that its generation was most likely under ultra-high pressure condition. It is thus proposed that continental subduction (into the mantle) might have occurred in the TNCO during the Paleoproterozoic.

Features of rare earth elements geochemistry in coals of Central Kazakhstan

AbstractThis research presents the results of a comprehensive study of mineralogical and geochemical features of REE distribution in coals of Central Kazakhstan deposits—Karaganda coal basin and Shubarkol deposit, which have large hard coal reserves and are industrially important for the coal industry of Kazakhstan; the research is based on 205 samples of clayey interlayers and coal seams. It shows basic patterns of distribution and features of concentration for impurity elements, gives an estimate of the impurity elements concentration, including REE, defines conditions and factors of their accumulation, and studies features of their forms in coal and coal-bearing rocks, which allows estimating the mechanisms of their migration and conditions of accumulation. According to the results of geochemical indicators, the article establishes the factors of REE dislocation, reveals the composition of margin rocks that have influenced REE concentration in coal seams, and the presented latest data on mineralogy allowed to establish the ways of their transportation to the paleobasin during the syn- and epigenetic periods of formation of the coal deposits of Central Kazakhstan being researched. It was found that the coals are insignificantly enriched with heavy lanthanides from Ho to Lu. The distribution curves of UCC normalized REE values in the coals are similar and coincide, but they are less than the average value for world coal, and amount to only one-third of the UCC. It was found that the highest concentrations of all REE are characteristic of clayey interlayers and oxidized coals. The La/Yb ratio in this case increases upwards along the section, indicating mainly clastogenic mechanism of REE delivery to the coals. In coal and clay samples, the predominant mineral form of REE is light lanthanide phosphates. Identified particles of REE from minerals and their composition peculiarities suppose autigene nature of their formation. The formation of the bulk of autigene minerals occurred during the maturation of brown coals and their transformation into hard ones.

The enrichment and separation of lanthanides ions from wastewater using solvent sublation coupled with high speed countercurrent chromatography

Rare earth elements are non-renewable resources. During their processing, a lot of wastewater are produced, which poses a danger to human beings and the environment. Herein, the enrichment method of solvent sublation for La (III), Ce (III), Gd (III) and Er (III) was designed and established. Enrichment parameters pH, flotation time, extractant concentration and air flow rate were optimized. The result showed that the highest recovery of La (III) reached up to 92.33 % under the optimized conditions of pH 8, 10 min of flotation time, 0.15 mol L-1 of the extractant 2-ethylhexyl phosphate acid-2-ethylhexyl ester and 30 mL min−1 of air flow rate. The light rare earth element Ce (III) and heavy rare earth elements Gd (III) and Er (III) were also examined and obtained with maximum recovery. The stability of the extractant complexation with rare earth ions and the mechanism of competitive extraction were studied by density functional theory calculations. The extraction ability was following sequence of La (III) < Ce (III) < Gd (III) < Er (III). The enrichment of rare earth elements from real water samples was investigated and obtained result was consistent with the experiment result of synthetic solutions. The established high speed countercurrent chromatography method was used to successfully separate La (III), Ce (III), Gd (III) and Er (III) from the solution of rare earth ions enriched by solvent sublation.

Efficient separation for yttrium and heavy rare earth elements using functionalized quaternary ammonium ionic liquids

Given the similar ionic radii of heavy rare earth elements (HREEs), sixteen functionalized ionic liquids (FILs) with potential extraction and separation properties were designed and prepared, also their feasibilities for yttrium (Y) separation from HREEs were evaluated. The results show that [N16MOP][HDA] is the optimal extractant for Y separation from other HREEs, achieving a Ho/Y separation factor of 2.82. The extraction reaction is based on an ion pair mechanism, where a HoCl3 molecule is extracted by two [N16MOP][HDA] molecules. Complete stripping of the loaded rare earth elements (REEs) can be achieved using 0.1 mol/L hydrochloric acid. Deionized water is used as a scrubbing agent, the average separation coefficient between Y and other HREEs during the scrubbing process is 2.5. After six cycles of continuous operation for 15 h, the organic phase maintains stable extraction and separation capabilities, demonstrating good recyclability and periodic stability. This study introduces a sustainable method for separating Y from HREEs using novel FILs, which is more efficient and consumes fewer chemical reagents. The results of this study indicate that the introduction of functionalized cation in FIL enhances the affinity and selectivity of HREEs. This provides valuable insights into the design of FIL-based extractents and their potential applications in sustainable rare earth separation.

Linkage between Granite Weathering and Gully Erosion in Subtropical Region

Granites, widely distributed in the Earth’s crust, undergo pedogenic processes, shaping diverse soil-mantled landscapes influenced by climatic factors in different regions. Investigating the geochemical signatures in granite weathering profiles across varying climatic conditions provides valuable insights into the intricate interplay between weathering and landscape evolution. In this study, the geochemical features, particularly major and rare earth elements, and the weathering degree of granites across temperate to subtropical regions in China were examined. The results indicated significant variations in the geochemical characteristics of granite weathering profiles, both at a pedon and regional scale (p &lt; 0.01). With increasing hydrothermal conditions from north to south, soil pH shifted from neutral to acidic, accompanied by the leaching of major elements (K2O, Na2O, CaO, and MgO) and the enrichment of Al and Fe. The total rare earth elements (∑REEs) ranged from 75 to 352 ppm, and light rare earth elements (LREEs) from 71 to 317 ppm, exhibiting less significant variations across the study area, while heavy rare earth elements (HREEs) showed higher concentrations in the subtropical region (3 to 35 ppm). Plagioclases dominated the weathering process in temperate regions, with K-feldspar progressively increasing and, eventually, dominating from temperate to subtropic regions, resulting in a shift in clay minerals from 2:1-type in the temperate to 1:1-type in the subtropic. The chemical index of alteration (CIA) and comprehensive weathering index (W) increased from fresh rock to residual soils along the weathering profiles and from north to south across the study area, ranging from 50.72 to 97.44 and 35.11 to 70.62, respectively. The intensified granite weathering degree was significantly influenced by climatic conditions (p &lt; 0.05), especially the multi-year average precipitation (22.4%) and relative humidity (9.1%) (p &lt; 0.01). Gully erosion on the granite weathering mantle was concentrated in granites with a comprehensive weathering index exceeding 52.51, and the spatial variation of the granite weathering degree aligned with the spatial distribution of gully density across the study area.