Rare Earth Element Abundances Research Articles

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

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

Distribution analysis of rare earth elements in fine‐grained CAIs of the Allende meteorite using multiple‐spot femtosecond LA‐ICP‐MS

ABSTRACTCalcium–aluminum‐rich inclusions (CAIs) in chondrites are one of the oldest materials in the solar system. Presence of refractory minerals in CAIs suggests that they formed thorough a condensation process from nebular gas of solar composition. In particular, fine‐grained CAIs (FGs) have escaped melting after condensation, and thus, the elemental distribution of rare earth elements (REEs) in FG minerals provides key information for elucidating the condensation processes. Although the REE abundances of FG fragments have been investigated in previous studies, the distribution of REEs in individual FG constituent minerals remains poorly explored. Here, we demonstrate the utility of laser imaging of REE distribution in CAIs by analyzing five FGs found in the Allende CV3 chondrite using multiple‐spot femtosecond laser ablation (msfsLA)‐ICP‐MS. The msfsLA‐ICP‐MS imaging system allows for a rapid acquisition of a wider range of REE distributions than previously achieved by Secondary ion mass spectrometry‐based imaging techniques. Out of the five FGs examined in this study, three showed the homogeneous REE patterns, while the other two indicated variable REE patterns within each FG. These observations presumably reflect differences in the chemical processes experienced by the FGs, and indicate that multi‐step chemical processes were recorded in some of the FGs. The msfsLA‐ICP‐MS imaging technique can characterize the elemental distribution of individual FGs under the comparable spatial resolution with high‐analysis throughput, and thus, it is an effective new method for advancing the taxonomy of FGs, which will improve our understanding of the physicochemical conditions that prevailed in the early solar system.

Study on the adsorption/desorption characteristics and dynamic diffusion mechanism of rare earth hydrated ions on the kaolinite (001) surface

Coal gangue (CG) contains abundant rare earth elements (REEs), which is a potential REE resource. REEs are mainly present in clay minerals as hydrates. The adsorption, desorption, and diffusion of REEs-hydrates on the surface of clay minerals are the key to regulating the leaching effect of REEs. The paper focuses on the typical clay minerals kaolinite and REEs-hydrates and combines quantum mechanics and molecular dynamics methods to systematically study the adsorption, desorption, and dynamic diffusion behavior of REEs-hydrates in acid solution. The research results indicate that stable REEs-hydrates La(H2O)9 and Y(H2O)7 are formed, with ion bonds between REEs and water molecules. La(H2O)9 and Y(H2O)7 mainly interact with the kaolinite (001) surface through hydrogen bonding. Competitive adsorption is formed between water molecules, hydrated hydrogen ions, and REEs-hydrates. Water molecules and hydrated hydrogen ions occupy the adsorption active sites of REEs-hydrates and form a dense water molecular layer on the surface. The distance between H3O+ and REEs-hydrates and the number of H3O+ in the solvent layer affect the desorption and diffusion behavior of hydrates. The bonding law, dynamic desorption, and diffusion mechanism of REEs-hydrates can provide meaningful references for selective leaching of REEs from CG.

Oxygen Isotopic Variations in the Calcium, Aluminum-rich Inclusion–forming Region Recorded by a Single Refractory Inclusion from the CO3.1 Carbonaceous Chondrite Dar al Gani 083

Calcium, aluminum-rich inclusions (CAIs) are the oldest solids dated that formed in the solar system. Most CAIs in unmetamorphosed chondritic meteorites (chondrites; petrologic type ≤3.0) have uniform solar-like 16O-rich compositions (Δ17O ∼ −24‰) and a high initial 26Al/27Al ratio [(26Al/27Al)0] of ∼(4–5) × 10−5, consistent with their origin in a gas of approximately solar composition during a brief (<0.3 Ma) epoch at the earliest stage of our solar system. The nature of O-isotope heterogeneity in CAIs (Δ17O range from ∼−24 up to ∼+5‰) from weakly metamorphosed chondrites (petrologic type >3.0) remains an open issue. This heterogeneity could have recorded fluctuations of O-isotope composition of nebular gas in the CAI-forming region and/or postcrystallization O-isotope exchange of CAI minerals with aqueous fluids on the chondrite parent asteroids. To obtain insights into possible processes resulting in this heterogeneity, we investigated the mineralogy, rare-earth element abundances, and O- and Mg-isotope compositions of a CAI from the CO3.1 chondrite Dar al Gani 083. This concentrically zoned inclusion has a Zn-hercynite core surrounded by layers of (from core to edge) grossite, spinel, melilite, and Al-diopside. The various phases have heterogeneous Δ17O (from core to edge): −2.2 ± 0.6‰, −0.9 ± 2.1‰, −13.7 ± 2.1‰, −2.6 ± 2.3‰, and −22.6 ± 2.1‰, respectively. Magnesium-isotope compositions of grossite, spinel, melilite, and Al-diopside define an undisturbed internal Al–Mg isochron with (26Al/27Al)0 of (2.60 ± 0.29) × 10−6. We conclude that the variations in Δ17O of spinel and diopside recorded fluctuations in O-isotope composition of nebular gas in the CAI-forming region prior to injection and/or homogenization of 26Al at the canonical level. The 16O depletion of grossite and melilite resulted from O-isotope exchange with asteroidal fluid, which did not disturb Al–Mg isotope systematics of the CAI primary minerals.

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.

Levels of rare earth elements on three abandoned mining sites of bauxite in southern Italy: A comparison between TXRF and ICP-MS

The essential utilization of rare earth elements (REEs) for the production of several electronic devices is making the demand for them being increased all the time. This extensive use of these elements has also increased concern about human and environmental health. Previous studies have shown that REE levels are higher in environmental samples near mining sites, and they are highly possible to be transferred to biota. In this study, REE levels were determined in environmental samples collected from three abandoned mining sites of bauxite (Gargano, Otranto, and Spinazzola) in the region of Puglia, Southern Italy. The samples were digested and analyzed by two different techniques, Total X-Ray Fluorescence (TXRF) and Inductively Coupled Plasma – Mass Spectroscopy (ICP-MS) to investigate which technique is the most suitable for analysis of the REE content in samples from abandoned mining sites of bauxite. Only 6 REEs could be detected by TXRF, while all REEs were detected in all the samples by ICP-MS. Spinazzola is the richest site and Ce the most abundant REE in all three regions. REE levels are correlated between the soil and biota samples in many cases, although the calculation of the bioconcentration factor showed that REEs are not bioaccumulative. ICP-MS seems to be a more suitable technique for analysis of the whole REE content in environmental samples from abandoned mining sites of bauxite.

Abundance, distribution, and ecological/environmental risks of critical rare earth elements (REE) in phosphate ore, soil, tailings, and sediments: application of spectroscopic fingerprinting

Abstract Purposes This research focuses on the characterization of phosphate ore, its solid effluents, and nearby contaminated soils in the southwest Tunisia (Gafsa-Metlaoui Basin). It aims also at evaluating the vertical distribution and abundance of critical rare earth elements (REE) in the different materials and their ecological and environmental risks. Materials and methods The sampled materials went through physical, chemical, and mineralogical characterization which involved XRF, XPS, XRD, and ICP-MS analyses. The REE anomalies and the environmental and ecological indices were calculated. Results and discussions Results show relatively high concentrations of nine rare REEs, following the sequence La &gt; Ce &gt; Nd &gt; Y &gt; Gd &gt; Eu &gt; Sm &gt; Yb &gt; Tb and trace metal elements (TME) such as Cd, Cr, Mn, Zn, Co, Fe, Sr, Cu, Ni, Pb, Ba that surpass, in some cases, international standards. The vertical distribution of the studied elements within a sediment, tailings, and soil profiles (beyond 20 cm of depth) indicates their likely in-depth migration. TME- and REE-bearing phosphate samples reflect mostly oxic conditions in the southern area with high positive Eu anomalies signifying possible mixing of sources. The environmental assessment indicate no contamination and a moderate enrichment of REEs, except for Eu, which displays significant contamination and extreme enrichment. Whereas, a deficiency of Y has been detected in most of the studied samples except for sludge sample which was also found significantly enriched with REE. Conclusions There are fundamental similarities between the different studied samples with high carbonate mineral concentrations. Statistical analysis confirmed the spectroscopic fingerprints demonstrating that the different materials share a similar composition. All of these similarities are most likely linked to the impact of mining activities on sediments and soils. Overall, our findings highlight the global effect of ore processing in determining the geochemical and the mineralogical characteristics of the surrounding environments of mines.

Impacts of aluminum-cerium alloy deployment on different cerium commodities

An imbalance problem exists in the rare earth element (REE) market with cerium and lanthanum being more abundant and less valuable than REEs used in permanent magnets such as neodymium, praseodymium, and dysprosium. Research has been conducted on new applications for abundant REEs to improve mining economics. However, potential market impacts of these applications on individual REE commodities are unknown. A system dynamics model was built to investigate the impacts of a new aluminum-cerium (Al–Ce) alloy that can theoretically utilize three separate cerium forms: cerium carbonate, cerium oxide, or cerium metal. Cerium carbonate currently possesses the lowest price of the three available forms making it initially the most favorable choice. However, model results showed that cerium oxide could provide the best economics for future Al–Ce alloy deployment because its larger market size buffers major shocks to price.

Controls on apatite compositional variations in magmatic rocks: A case study of Mesozoic mafic–felsic intrusions from the eastern North China Craton

Compositional variations of apatite are mainly determined by parameters such as partition coefficients and the composition of parental magma. However, the relative importance of these parameters in relation to apatite geochemistry in different lithologies of magmatic rocks is not well constrained. In this study, six Mesozoic (219–154 Ma) mafic–felsic intrusions from the eastern North China Craton, were selected for detailed apatite microanalyses (trace elements and Nd isotopes). Apatite from the studied intrusions has uniform textures in the cathodoluminescence image. They exhibit high abundances of rare earth elements (REE) and are characterized by light REE enriched patterns, indicative of a magmatic origin. Alongside compiled apatite data, these findings suggest that compositional variations of REE + Y in apatite from mafic to felsic magmatic rocks are controlled primarily by elemental partitioning between apatite and melts. The competitive crystallization of other accessory minerals prior to apatite can be responsible for compositional variations of Sr, Pb, Th, and U. New Nd isotope data for apatite are discussed and compared with whole-rock Nd and zircon Hf isotope data for the same sample. The Nd isotopic compositions between the whole-rock and apatite are identical. The integrated dataset provides an alternative interpretation for the isotopic decoupling between apatite Nd and zircon Hf isotope systems. In conclusion, apatite REE concentrations and Nd isotopes have the potential to serve as geological indicators.

Giant Rare Earth Element Accumulation Related to Voluminous, Highly Evolved Carbonatite: A Microanalytical Study of Carbonate Minerals From the Bayan Obo Deposit, China

Abstract The giant Bayan Obo deposit in China represents the largest rare earth element (REE) resource in the world, but the mechanisms for its highly anomalous REE enrichment have long been controversial. The central debate concerns the nature and origin of the ore-hosting dolomite. In this study, a texturally constrained microanalytical study of carbonate minerals from the Bayan Obo ore-hosting dolomite is presented to resolve this controversy. The dolomite rocks contain two major components: the early-stage coarse-grained dolomite (CD) and the late-stage fine-grained dolomite (FD). The CD dolomite grains have C-O isotope ratios (δ13CVienna-PeeDee Belemnite (V-PDB): –4.8 to –3.3‰; δ18OVienna-standard mean ocean water (V-SMOW): 7.1 to 11.9‰) plotting in or adjacent to the primary igneous carbonatite field, with a narrow range of low 87Sr/86Sr ratios (0.70262–0.70327). The mantle-like C-O and Sr isotopes indicate that the coarse-grained dolomite rocks are magmatic in origin. Dolomite grains from the FD have experienced extensive hydrothermal alteration related to both REE mineralization and post-ore metamorphism of the Bayan Obo deposit. The domains of primary unaltered dolomite have high SrO and MnO contents that clearly distinguish them from sedimentary carbonates. The 87Sr/86Sr ratios of unaltered dolomite domains range from 0.70271 to 0.70473, with the majority lower than 0.7035, contrasting with higher 87Sr/86Sr ratios of Mesoproterozoic sedimentary carbonates globally. Thus, the primary unaltered fine-grained dolomite, the precursor to the FD, is also proposed to be a carbonatite. Compared with dolomite grains from the CD, most of the unaltered dolomite domains within the FD are more enriched in FeO and MnO and have higher δ13CV-PDB (-4.9 to 0.3 ‰) and δ18OV-SMOW (9.4 to 17.1 ‰) values. In addition, the FD contains abundant REE- and volatile-rich hydrothermal minerals and Fe-Mg carbonates, which are rare in the CD. The geochemical and mineralogical data in conjunction indicate that the melts forming the late-stage FD were much more evolved than those forming the early-stage CD. It is noteworthy that the unaltered dolomite domains within the FD have a wider range of 87Sr/86Sr ratios than those within the CD, which implies that the CD and FD, at least a proportion of them, are unlikely to have crystallized from the same progenitor magmas. Some FD was possibly the product of fractionation of less-evolved carbonatitic magma that generated the CD, whereas other FD crystallized from new pulses of magmas that were highly fractionated at depth. When compared with other carbonatite complexes, the Bayan Obo carbonatite suite is notable for having a large surface area (~48 km2 in outcrop) and containing an anomalously large proportion of highly evolved components. The voluminous evolved carbonatite clearly provided a basis for the accumulation of significant ore metals. Therefore, the giant-sized REE deposit is proposed to be associated with large-volume, highly evolved carbonatite at Bayan Obo.

The Paleoecological Environment during the Ediacaran–Cambrian Transition in Central Guizhou Province, China: Evidence from Zn Isotopes

During the Ediacaran–Cambrian transition, a series of stratal continuous and well-preserved siliceous rock and phosphorite assemblages developed in Qingzhen, Guizhou Province, China, facilitating research on the biological evolution, marine chemistry, and palaeoecological environment of this period. Therefore, we investigated the paleontology, trace and rare earth elements, total organic carbon, total sulfur content, and Zn isotopes of the phosphorus-bearing rock series in the Taozichong Formation of the Cambrian period in Qingzhen. Geochemical analysis reveals that the sedimentary rocks in this area were formed in the oxygen-rich seawater environment and were not affected by high-temperature hydrothermal activity. The upwelling ocean current provided abundant rare earth elements and other nutrient elements, as well as conditions for the prosperity of biota in Qingzhen. In addition, the δ66Zn value (−0.21‰–0.41‰ range and 0.17‰ mean) in the Qingzhen phosphorous rock series was much lower than that in seawater, indicating a strong level of biological productivity. The variation trend of δ13C, δ18O, and δ66Zn exhibited four stages and three obvious drift events. The results suggest that climate change during this period led to the intermittent flourishing and extinction of organisms, which triggered the negative drift of δ13C and δ18O in the ocean, resulting in a coordinated response of δ66Zn. The unique ecological environment of the Taozichong Formation in Qingzhen also provides favorable conditions for the population continuation of Ediacaran-type benthic soft-bodied metazoon dominated by discoid fossils, Shaanxilithes, worm fossils, and sponge fossils in the Cambrian strata, as well as participation in the global biological explosion events. The study area provides new insights for rebuilding the global Ediacaran–Cambrian ecosystem during the transition period.

Microdistribution and Mode of Rare Earth Element Occurrence in the Zhijin Rare Earth Element-Bearing Phosphate Deposit, Guizhou, China

Rare-earth elements (REEs) are often highly concentrated in sedimentary phosphate deposits, and the microdistribution characteristics and occurrence state of rare earth in these deposits play a crucial role in the overall development and utilization of mineral resources. This study aims to analyze the microdistribution of REEs in REE-bearing phosphate deposits in the Zhijin region of Guizhou at the microstructural level and investigate their occurrence modes. Specifically, rock and mineral identification, X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM-EDS), and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) were utilized to analyze the samples. The correlation between the distribution of REEs and phosphorus was examined. In addition, the microdistribution of REEs in specific mineral phases and the locations of their occurrence were investigated. The analysis revealed that no REEs existed independently in the deposit. Instead, the distribution of REEs was highly consistent and significantly positively correlated with that of phosphorus. In the microarea structure, REEs were predominantly found both in particles, such as bioclasts, sand debris, and agglomerates, and in phosphate cement, where the main mineral components were collophane and apatite. Conversely, the content of REEs in dolomitized sand debris edges, sparry dolomitic cement, and siliceous cement was considerably lower. Based on these findings, it is speculated that REEs primarily occur within the lattice defects of apatite or on the surface of collophanite. There is a notable contrast in the REE content between the unaltered sand debris at the periphery and the dolomitized sand debris, indicating that the dolomitization in the diagenetic stage resulted in a depletion of REE abundance in the ore. Obviously, the dominant gangue mineral, dolomite, does not serve as the primary host for REEs. Furthermore, the highest concentration of REEs was inside organisms. This finding suggests that the high content of REEs in biological soft tissue may remain under the influence of waves and tides, and REE-bearing apatite may be preferentially separated and fill the cavities of deceased organisms. The second highest content of REEs was found in the shells of organisms, indicating that small shelly organisms absorb phosphorus materials through their life activities to construct their shells, resulting in REE enrichment. Quantitative analysis through sequential extraction procedures displayed that most REEs were present in the residual state, with a smaller portion combined with organic matter. These results confirm that REEs in the Zhijin phosphate deposits primarily exist as isomorphic substitutions in the lattice defects of apatite, with a secondary occurrence as organic matter-bound REEs.

Using machine learning to identify indicators of rare earth element enrichment in sedimentary strata with applications for metal prospectivity

Rare earth elements (REE), classified as critical minerals which are crucial for clean energy technologies, face soaring demand. While economic deposits are found in limited geologic environments including carbonatites and ion-adsorption clays, unconventional, secondary sources such as those from sedimentary basins could hold potential to meet this increased demand. Coal and its associated combustion by-products, phosphorites, oil sands tailings, and formation waters have all garnered interest for REE recovery, yet they remain significantly underexplored. Accordingly, new tools for data analysis and optimization such as machine learning can assist in mineral prospectivity, with these tools being subject to rapid proliferation in the Earth sciences.This work leverages compositional data analysis principles and machine learning to probe geochemical relationships and predict REE abundances in sedimentary lithologies using unsupervised (correlation, principal component, and cluster analysis) and supervised (regression, support vector machine, random forest, and boosting) machine learning models. These three unsupervised models display similar results, with REE typically being associated with incompatible elements (e.g., Th, Nb, and Hf). Gradient boosting, Adaboost, and Random Forest had the highest performance for predicting REE concentrations, with Th and P commonly being the most important predictor variables. Identifying geochemical indicators of REE enrichment that may be used to assist in discovering potentially exploitable REE resources based on existing data, as well as increasing the understanding of metal behaviour in sedimentary systems, is a step forward in understanding novel secondary and unconventional REE sources. Although REE concentrations from these sources are generally lower than primary ore deposits, the amount of available feedstock, potentially simpler, cheaper, and less environmentally taxing extraction processes, and the added benefit of remediating waste streams and contributing to the circular economy make these sources alluring.

Passive surveillance of wild fauna in northwestern Italy: a possible cognitive approach through geographical district study and fur elementary analysis.

The analysis of animal hair is a useful and non-invasive investigation method for monitoring metal content, whose beginning dates to a few decades ago. This study addresses the issue of wildlife mortality in Piedmont and Aosta Valley by linking the evidence to the characteristics of the territories and to hair elemental profile. The considered animal species were badger, fox, marten, and wolf. The quantitative data for 11 trace metals and 16 lanthanides were evaluated considering animal location and death causes regarding impacts, whose relevant number was confined to the Turin province and to the badger and fox species. The evaluation of the analytical results was performed after the out of bounds sample identification by mean of statistics. For trace metals, some areas have thus been identified, mainly in Turin province, in which the large excess of As, Cd, and Pb was related to district pollution. Moreover, the lower contents of Fe, Mn, and Al in Aosta Valley badgers' hair seem influenced by the different characteristics of the subsoil, in comparison to Piedmont, and a relationship with the living environment and the habits was suggested. Regarding lanthanides, Biella province represents an area in which environmental contamination and abundance of rare-earth elements was recorded.

Depositional condition of Paleoproterozoic Francevillian carbonate rocks revisited from rare earth element contents

The Paleoproterozoic Francevillian Group in the eastern Gabonese Republic has been recently attracting increasing attention because it includes distinctive macroscopic structures interpreted as eukaryotic fossils. Therefore, its depositional setting and associated redox conditions need to be clearly understood. To clarify these, petrological studies and rare earth element (REE) abundances of carbonate rocks of the Francevillian Group in the Lastoursville basin were determined with ICP-MS coupled with a laser ablation sampling technique. Detailed microscopic observations indicate that dolostones in this basin underwent the complicated diagenetic history, including sparitization, decomposition of organic matter, reduction of ferromanganese oxides, silicification, and later calcification. The dolostones of lower Francevillian B (FB) Formation show heterogeneous textures formed by alterations during diagenesis. By the alterations, changes of REE abundances and degrees of positive Y anomalies appear to have occurred. This indicates that REE signatures in carbonate rocks can vary during diagenesis. Characteristically high Mn contents in the dolostones of upper FB Formation were derived from the reduction of ferromanganese oxides in sediments. The signatures of REE abundance in dolostones can be explained by the mixing of seawater and ferromanganese oxide components. In that sense, the dolostones inherited the trace element characteristics of precursor ferromanganese oxides even after the diagenesis. Y/Ho values of the most primary parts of each sample exceed 33, the newly determined threshold value for marine carbonate rocks based on our compilation. The magnitude of the La anomaly values also falls within the range of that of Holocene reefal microbialites. These indicate that a precursor of the dolostone of the Francevillian Group was deposited in a marine environment. In addition, presence of Ce anomalies in the upper FB Formation suggests that the Paleoproterozoic ocean was oxidized to such an extent as for Ce to be preferentially absorbed by ferromanganese oxides.

Urea-Assisted Synthesis of Microspherical Hollow CeO2 Nanostructures for Supercapacitor Applications

In the present work, cerium oxide (CeO2), the most abundant and least expensive rare earth metal oxide with the capability of rapid conversion between the oxidation states of Ce+3 and Ce+4, is synthesized via a urea-assisted solvothermal method in methanol. Along with its role as a precipitating agent, urea reacted with methanol and thus initiated a series of organic reactions which are responsible for the formation of spherical layered assembly of cerium oxide leading to a multi-layered structure with high porosity. The morphology and chemical structure of the material are investigated using SEM, TEM, XRD, and FTIR spectroscopy. The porous and spherical architecture achieved here enhanced the surface area, active sites, and electrical conductivity and also introduced more diffusion pathways at the electrode/electrolyte interface, which collectively improved the performance of CeO2 as a supercapacitor electrode material. The outstanding redox characteristics of CeO2 are explored in supercapacitor applications, and the electrode exhibited a specific capacitance of 319.68 F/g at a current density of 0.5 A/g in a three-electrode configuration which proved the excellence of the present CeO2 microspheres in the field of energy storage applications.

Garnet versus amphibole: Implications for magmatic differentiation and slab melting

The garnet signature in the rare earth element (REE) abundances in adakites has been considered a key genetic indicator of these controversial rocks, whose proposed origins include direct melting of subducted oceanic crust (“slab melts”). We show that the garnet signature may be quantified using the shape coefficients of chondrite-normalized REE patterns. We applied this method to a global data set of Cenozoic and Quaternary volcanic samples described as “adakites.” The results indicate that many, but not all, suites of rocks labeled as adakites have undergone fractional crystallization of garnet, starting from parental melts attributable to partial melts of garnet-bearing sources. The extreme garnet signatures seen in many examples require hybrid sources, consisting of subducted sediment as well as igneous oceanic crust; however, extensive deep-crustal differentiation obscures the major and trace-element characteristics of these sources, casting doubt on their identification as primitive slab melts.

Melting processes, cooling rates, and tectonic settings of the Neo-Tethyan mantle: the in-situ mineral chemical record

Peridotites in the Yarlung Zangbo ophiolite (YZO) have the potential to elaborate the mantle dynamics that operated below the Neo-Tethyan oceanic crust. Here, we measured major and trace element concentrations of minerals (e.g., clinopyroxene, orthopyroxene, olivine, and spinel) in YZO harzburgites and lherzolites to trace the origin and evolution of the YZO. The rare earth element (REE) patterns of clinopyroxenes in lherzolites and harzburgites plot within the field of abyssal and forearc peridotites, respectively, indicating that the latter experienced a higher degree of partial melting. Based on the relative extents of light (LREE) and heavy (HREE) REE depletions in clinopyroxene, we classified the lherzolites into two groups (I and II). The group I clinopyroxenes are depleted in HREEs and enriched in LREEs and MREEs compared to those of group II. Meanwhile, the REE patterns of harzburgite clinopyroxenes are identical to that of group II, although they display lower REE concentrations. Models based on REE abundances in clinopyroxene suggest that group I lherzolites experienced ~8–11% partial melting in the spinel domain, whereas group II lherzolites formed after 5% melting in the garnet domain followed by 6–9% and 9–16% partial melting in the spinel domain, respectively. These high degrees of melting may suggest that the harzburgites formed in a supra-subduction zone (SSZ) setting. Surprisingly, the REE-in-two-pyroxenes thermometer (TREE) shows that the YZO peridotites record high-temperature cooling at 991–1218 °C which is lower than the conditions below mid-oceanic ridges (MORs), but compatible with recent reports of high closure temperatures in forearc environments. Furthermore, our TREE results constrain the cooling rate of the YZO peridotites to ~0.01–0.5 °C/yr, overlapping with rates reported for SSZ, MOR, and abyssal peridotites. By integrating the petrological, geochemical, and thermal features, we tentatively interpret the group I lherzolites accreted in an Early Cretaceous forearc during subduction initiation, whereas the group II lherzolites and the harzburgites formed by further melting of the earlier lherzolites in a SSZ setting.

How does weathering influence geochemical proxies in Paleoproterozoic banded iron formations? A case study from outcrop samples of 2.46 Ga banded iron formation, Hamersley Basin, Western Australia

Trace metal and rare earth element (REE) abundances in banded iron formations are critical for assessing the chemical composition of ancient seawater and the long-term evolution of the ocean-atmosphere system. Recent studies, however, have highlighted the potential effects of outcrop weathering, raising concerns about whether banded iron formation samples are suitable proxies for ancient redox conditions or if exposure to surficial weathering regimes may have altered key geochemical signals. Here, we present a detailed, high-resolution study of several banded iron formation outcrop samples from the Hamersley Basin, Western Australia, to investigate microscale differences in composition between banded iron formation and weathered surfaces (i.e., weathered crusts). Elemental mapping and bulk-rock geochemical analyses reveal that weathered crust is more enriched in most elements than the banded iron formation, except for silica, which is significantly depleted. There is also a significant loss of redox-sensitive elements (RSEs) in the weathered surface, which suggests that outcrop samples have been affected by higher degrees of chemical leaching than physical erosion. These results are significant, because we clearly show that the geochemical characteristics of the weathered surface—irrespective of how it formed—are distinct from those of the remainder of the sample. This means that with sufficient screening of samples for obvious signs of alteration, banded iron formation outcrop samples may indeed be used as a reliable proxy for the evolution of Earth’s coupled ocean-atmosphere system. This increases the volume of easily accessible Precambrian sample material, so that researchers no longer solely need to rely on core recovered through costly drilling programs.

Petrogenesis of Eocene Lamprophyre Dykes in Northern Qiangtang Terrane, Tibetan Plateau: Implications for the Tethyan Mantle Metasomatism and Tectonic Evolution

Post-collisional (ultra)potassic lamprophyre dykes are the key probes for understanding mantle metasomatism and reconstructing tectonic evolution. In this study, we present new petrological, geochronological, geochemical and zircon Lu-Hf isotopic data for lamprophyre dykes in the northern Qiangtang terrane (central Tibet), aiming to constrain their petrogenesis and geodynamic setting. The studied lamprophyres are minettes with phenocrysts of siderophyllite and phlogopite, which intrude into Triassic granite of 236.9 Ma. These lamprophyres yield zircon U-Pb ages of 39.7–40.9 Ma. They exhibit high contents of K2O (7.61–8.59 wt.%) and ultrapotassic features with high K2O/Na2O (11.43–14.38) ratios. They are characterized by increased values of Mg# (69.1 to 72.1) and high concentrations of compatible elements (e.g., Cr = 277–529 ppm, Ni = 232–322 ppm), which are diagnostic of mantle-derived primitive magma. The studied lamprophyres have a high abundance of rare earth elements (∑REE = 902–1061 ppm) with significantly fractionated REE patterns ((La/Yb)N = 66.3–100.6), and they are enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE), but depleted in high field strength elements (HFSE) (e.g., Nb, Ta and Ti) and heavy rare earth elements (HREE) with enriched zircon Hf isotopes (εHf(t) from −6.40 to 3.80). This indicates their derivation from an enriched mantle source which was metasomatized by subduction-related fluids and sediment-derived melts. A petrogenetic study suggests that the lamprophyres were generated by the partial melting of a phlogopite-bearing lherzolite within the garnet stability field. We propose that the Cenozoic ultrapotassic mafic rocks in the central Tibetan Plateau originated in the lithospheric mantle metasomatized by the subduction-related components, and are the magmatic response to the detachment of the subducted Tethyan slab.