Rare Earth Element Patterns Research Articles

Hazard profiles, distribution trends, and sources tracing of rare earth elements in dust of kindergartens in Beijing

Children, the most vulnerable group in urban populations, are susceptible to the effects of pollution in urban environments. It is significant to evaluate the influence of rare earth elements (REEs) from kindergartens dust (KD) in Beijing on children's health. This study collected surface dust from 73 kindergartens in 16 districts of the mega-city of Beijing, and the concentrations of 14 REEs in KD, including La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, were detected. The contamination levels, source apportionment, and health exposure risk of REEs were comprehensively investigated. The results indicate that the contamination levels of 14 REEs are within the acceptable range. Nevertheless, Eu, Ce, La, Pr, Nd, Gd, and Sm show high enrichment due to anthropogenic influence. Besides, KD is rich in light rare earth elements (LREEs) (90.97 mg kg−1) compared to heavy rare earth elements (HREEs) (8.65 mg kg−1). The distribution parameter patterns of REEs suggest that complicated anthropogenic sources influence the enrichment of REEs in KD. The main sources of REEs in KD include natural sources (40.64%), mixed high-tech industries and construction (33.89%), and mixed coal-fired, historical industrial, and transportation sources (26.47%). The primary pathway for daily intake of REEs in children is through ingestion, which presents a low but not negligible health risk. This study provides guidance for the effective risk management of REEs in KD.

Genesis of Carboniferous aluminous-bearing strata in the northern part of the North China Craton: A case study of the Xingxian bauxite deposit

More than five billion tons of karstic bauxites were formed in the North China Craton (NCC) during the Late Carboniferous period. Compared to the bauxite ore, the genesis of the entire aluminous-bearing strata has received less attention. In this study, we conducted geological, mineralogical, and geochemical analyses on core samples from the aluminous-bearing strata located in Xingxian area, situated within the northern NCC, aiming to elucidate the genetic process of these formations. The aluminous-bearing strata consist of a bauxite layer (diaspore–anatase–kaolinite–florencite) sandwiched between the upper sandy claystone horizon (kaolinite–illite–quartz) and the lower berthierine-bearing claystone horizon (berthierine–diaspore–hematite–goethite). Based on the upper continental crust-normalized patterns of rare earth elements and yttrium (REY), immobile trace element ratios, mineral inheritance diagrams, and previous findings, it is suggested that the lower berthierine-bearing claystone was weathered from the impure limestone at the bottom, whereas the upper bauxite and sandy claystone mainly originated from intermediate-felsic igneous rocks of the northern margin of the NCC, granite from the North Qinling Orogenic Belt, and aluminosilicate rocks of the surrounding paleo-uplifts. During the early diagenetic stage, the berthierine was transformed under alkaline and reducing conditions from iron-rich clays (composed of clay minerals, ferric minerals, etc.) formed in acidic and oxidizing conditions from the underlying impure limestone. The coexistence of berthierine with low-temperature stability and diaspore is observed in the berthierine-bearing claystone, which precludes a high-temperature origin of diaspore in the aluminous-bearing strata. Moreover, diaspore is characterized by a small crystal size and is usually poorly crystallized, suggesting a supergene precipitation-diagenesis origin. The paragenetic minerals assemblages (e.g., diaspore, berthierine, goethite, hematite, etc.) suggest that the aluminous-bearing strata primarily formed in a transition zone nearer to the phreatic environment. Large-scale volcanism and warm, humid climatic conditions accelerated the decomposition of allochthonous weathering materials, resulting in the downward migration of metal ions. These ions then precipitated in a reducing and weakly alkaline environment, giving rise to form bauxite ore dominated by diaspore, anatase, and REY minerals.

Mineralogical composition, isotopic and geochemical characteristics of Pleistocene glendonites from the outcrops of Bol’shaya Balakhnya River, Eastern Taimyr, Russia

We present a complex study on mineralogical, U/Th dating, isotopic and geochemical characteristics of Pleistocene glendonites (calcite pseupomorphs after ikaite) from the outcrops of Bol’shaya Bakakhnya valley, Eastern Taimyr, Russia. Based on the U/Th dating of the glendonites (37 ± 7 ka) we propose that the glendonites and host sediments were formed during Karginsky interstadial (22—50 ka) – this data corresponds well with published ages of foraminifers and wood fragments from Karginsky deposits of Eastern Taimyr. The main factors leading to ikaite crystallization was presence of organic matter (δ13C varies from -5 to -40‰ V-PDB) in the host clayey sediments and low temperatures (< 7 ºC) of bottom water. Isotopic (δ18O ratios vary from -8 to -33.9‰ V-PDB) and geochemical (PAAS-normalized patterns of rare earth elements) characteristics of the studied glendonites confirm that ikaite crystallization and transformation was influenced by seawater. Carbon was derived from dissolved inorganic carbon, de composed organic matter, and probably methane. Some glendonites are surrounded by concretions (host rock cemented by calcite). The isotopic characteristics of the host concretions and glendonites are similar, so we assume that glendonites and host nodules were formed by the same processes—sulfate reduction coupled with anaerobic decomposition of organic matter. Nevertheless, geochemical characteristics of the host concretions and glendonites differ: Mg/Ca ratio and values of Fe, Mn, Zn, Cd, and U are higher in host concretion than in glendonite. This may reflect differences in crystalline structure of ikaite and high magnesium calcite.

Geology and genesis of the Aqishan Pb-Zn deposit, NW China: Insights from mineralogy, geochemistry, and in situ U-Pb geochronology

The unique ore-forming processes and the key factors responsible for formation of skarn deposits are still obscure, and challenges exist in the determination of timing of Pb-Zn skarns owing to lacking suitable mineral chronometers. Here we present detailed paragenesis, bulk geochemistry, in situ U-Pb dating of zircon and garnet, and garnet oxygen isotopes together with in situ zircon Hf-O isotopes from the newly discovered Aqishan Pb-Zn deposit in the southern Central Asian Orogenic Belt (CAOB), northwest China. This comprehensive data set revealed a Late Carboniferous subduction-related distal Pb-Zn skarn system associated with the granitic magmatism. Pre-ore stage garnets are generally subhedral to euhedral with oscillatory zoning and show slightly fractionated rare earth element patterns with positive Eu anomalies that point to an infiltration metasomatism origin under high water/rock ratios. The syn-ore stage sphalerite is typically enriched in Mn and Cd and has moderate Zn/Cd ratios (337–482), with a formation temperature of 265 °C to 383 °C, which indicate magmatic-hydrothermal signatures. The isocons defined by P2O5 decipher that the principal factors for skarn formation were elevated activities of Fe, Ca, and Si species, where remobilization of Pb metals, meanwhile, contributed to ore-forming budgets to mineralizing fluids. SIMS U-Pb dating of zircons from granite porphyry that occurs distal to the skarns and Pb-Zn orebodies shows that these intrusions emplaced at ca. 311.3–310.6 Ma, recording the subduction of the Paleo-Tianshan oceanic plate. Hydrothermal garnets in close textural association with Pb-Zn sulfides yield indistinguishable in situ LA-ICP-MS U-Pb ages of 310.5 ± 4.1 Ma. Whole-rock geochemistry and in situ zircon Hf-O isotopes (δ18O = 4.6‰–6.0‰) indicate that the granite porphyry was derived from partial melting of juvenile crust and influenced by subducted oceanic crust. Oxygen isotope compositions of garnets (δ18O = 8.0‰–9.0‰) demonstrate that the equilibrated ore fluids were inherited from fluid-rock interactions between a primary magmatic water and host tuff rocks. Our study highlights the application of garnets as a potential robust U-Pb geochronometer and isotopic tracer of ore fluids in skarn mineralizing systems in subduction-related arc environments.

Garnet and Zircon U‐Pb Geochronology and Geochemistry Reveal Genesis of the Dafang Au‐Pb‐Zn‐Ag Deposit, Southern Hunan

AbstractGarnet is a primary mineral in skarn deposits and plays a significant role in recording copious mineralization and metallogenic information. This study systematically investigates the geochemistry and geochronology of garnet and zircon in the Dafang Au‐Pb‐Zn‐Ag deposit, which represents prominent gold mineralization in southern Hunan, China. Garnet samples with distinct zoning patterns and compositional variations were identified using various analytical techniques, including Backscattered Electron (BSE) imaging, Cathodoluminescence (CL) response, textural characterization, and analysis of rare‐earth elements (REE), major contents, and trace element compositions. The garnet was dated U‐Pb dating, which yielded a lower intercept age of 161.06 ± 1.93 Ma. This age is older than the underlying granodiorite porphyry, which has a concordia age of 155.13 ± 0.95 Ma determined by zircon U‐Pb dating. These results suggest that the gold mineralization may be related to the concealed granite. Two groups of garnet changed from depleted Al garnet to enriched Al garnet, and the rare earth element (REE) patterns of these groups were converted from light REE (LREE)‐enriched and heavy REE (HREE)‐depleted with positive europium (Eu) anomalies to medium REE (MREE)‐enriched from core to rim zoning. The different REE patterns of garnet in various zones may be attributed to changes in the fluid environment and late superposition alteration. The development of distal skarn in the southern Hunan could be a significant indicator for identifying gold mineralization.

Hydrocarbon fluid evolution and accumulation process in ultradeep reservoirs of the northern Fuman Oilfield, Tarim Basin

Marine deep Ordovician reservoirs are significantly controlled by strike-slip fault zones, which govern reservoir fluid evolution during various activity periods. Such fluid evolution elucidates the process underpinning ultra-deep oil and gas accumulation and delineates the pivotal role of strike-slip fault zones in hydrocarbon aggregation. This method can improve the understanding of the mechanism of hydrocarbon accumulation in deep to ultradeep carbonate rocks. The findings indicate that the Ordovician reservoirs in the northern thrust fault zone of the Fuman Oilfield predominantly exhibit two stages of calcite vein formation. The distribution patterns of rare earth elements and Sr isotope characteristics suggest that both stages of vein formation were sourced from Middle to Lower Ordovician marine strata, with no evidence of oxidizing fluid infiltration. This indicates that late-stage oil and gas charging in deep-ultradeep formations has good sealing properties. In these calcite veins, early-, middle-, and late-stage fluid inclusions were primarily entrapped. By examining the development of primary oil inclusions and combining the U‒Pb isotope data of host minerals, this study confirms the occurrence of three stages of oil and gas charging in the deep Ordovician strata of the northern thrust fault zone in the Fuman Oilfield. These stages correspond to approximately 459 ± 7.2 Ma (mid-Caledonian), 348 ± 18 Ma (early Permian), and 268 Ma (late Permian). The key accumulation period of oil and gas reservoirs in the study area is the middle and late Caledonian, and there is a good correspondence between oil and gas charging and fault activity.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

Anthropogenic gadolinium in the Tone River (Japan): an update showing a 7.7-fold increase from 1996 to 2020

BackgroundAnthropogenic gadolinium (Gd), originating from Gd-based contrast agents (GBCAs) used in magnetic resonance imaging (MRI), is widely identified in the aquatic environment with concerns about toxicity and accumulation. We aimed to present new data on anthropogenic Gd in the Tone River, which has the largest drainage area in Japan, and then to compare the current data with those obtained in 1996.MethodsThe water samples were collected on August 9−10, 2020, at 15 different locations of the Tone River in Japan. The concentrations of the rare earth elements (REEs) were measured by inductively coupled plasma-mass spectrometry and normalized to Post-Archean Australian Shale to construct shale-normalized REE patterns. The degree of Gd-anomaly was defined as the percentage of anthropogenic Gd to the geogenic background and used to compare the water samples from different locations. Pearson’s correlation coefficients were calculated.ResultsAll the samples displayed positive Gd anomalies. The Gd-anomaly ranged from 121 to 6,545% and displayed a repeating decrease-and-increase trend. The Gd-anomaly showed strong positive correlations to the number of hospitals (r = 0.88; p < 0.001) and their MRI units (r = 0.89; p < 0.001).ConclusionsOur study revealed notable anomalies of Gd concentrations in river water in Japan, with strong positive correlations to the number of major hospitals and their MRI units. Compared with the previous report in 2000, the Gd-anomaly in Tone River increased from 851% (sampled in 1996) to 6,545%, i.e., 7.7 times, reflecting the increased use of GBCAs in hospitals.Relevance statementNotable Gd concentration anomalies in river water in Japan were observed. This result underlines the importance of more extensive research on anthropogenic gadolinium, and investigations of risks to human health as well as the development of effective removal technologies may be necessary.Key points• All water samples from Tone River displayed positive Gd anomalies.• The Gd anomalies increased to 7.7 times higher over the past 24 years.• Correlations between Gd values and the number of hospitals and MRI units were observed.Graphical

Secondary Enrichment of REE in Weathered Granite, South Bangka, Indonesia

Rare earth elements (REEs) are essential materials for the manufacture of advanced technology. Secondary REE indications were found in alluvial and lateritic tin deposits within Southeast Asia Tin Belt. This study aims at the REE enrichment of weathering profiles underlain by Toboali Pluton of the main range S-type granite of this belt. Granite and weathering samples were collected and analyzed using XRF, ICP-MS/OES, XRD, SEM-EDX, and EPMA. The Chondrite-normalized REE patterns of granite in Toboali showed enrichment in REE with the highest value of 1,126 ppm. The Toboali Pluton is enriched in LREE and depleted in HREE. The enrichment of REE from the upper to lower horizon of weathering profiles was pointed out by the increase in REE values from a range of 156-188 ppm (horizon B) to 196-268 ppm (horizon C) in Toboali, and from a range of 230-330 ppm (horizon B) to 342-450 ppm (horizon C) in Air Gegas. These coincided with the presence of kaolinite with elevated REE and CeO2 in horizon C of weathering profile. Leaching test result proved that kaolinite plays a role in REE enrichment in the weathering profile through ion adsorption mechanisms in the Air Gegas. The weathering process of REE fluoro-carbonate (bastnäsite-(Ce)) and parisite-(Ce) in granite is believed to contribute in enrichment due to its high dissolution rate, which enhances kaolinite adsorption. In contrast, REE phosphates such as monazite-(Ce) and xenotime-(Y), because of their strong resistance and low solubility, are thought to be only slightly soluble, and most of these minerals remain in Toboali weathering products.

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.

A distinctive rare earth element signature for pyrite oxidation and glacial weathering

The application of rare earth elements (REE) and neodymium (Nd) isotopes to authigenic Fe-(oxyhydr)oxide phases leached from marine sediments can be used for reconstructing past ocean circulation and chemical weathering patterns on nearby continental landmasses. To explore the behaviour of REE during chemical weathering in glacial environments, we analyzed the authigenic fraction of glacimarine sediments from the continental shelf off northern Svalbard (Arctic Ocean), where the evolution of ice sheet dynamics since the last deglaciation is well constrained. Our results show that leached authigenic fractions in Svalbard sediments exhibit shale-normalized REE patterns characterized by anomalously high mid-REE enrichment relative to both light- and heavy-REE, as expressed by concavity index values (CI > 2.5) that significantly depart from typical REE signatures for leached fractions in marine and river sediments worldwide. Using a compilation of literature data, we provide compelling evidence that the occurrence of pronounced mid-REE enrichment in authigenic fractions of Svalbard marine sediments links to terrestrial oxidation of pyrite following glacial weathering. While future investigation will be required to further understand the detailed mechanism accounting for the observed REE decoupling and its link to pyrite oxidation, we propose that preferential dissolution of mid-REE-enriched rock-bearing minerals such as apatite following glacial erosion, sulfide weathering and subsequent release of sulfuric acid could release a distinctive REE signature in glacial surface environments. Our findings suggest that the use of authigenic REE in the sedimentary record could provide a means for tracing glacial weathering and associated biogeochemical sulfur and iron cycling across geological times.

Mafic veins in the mantle section of the Oman ophiolite: Petrological and geochronological insights from the Oman Drilling Project cores

The magmatic and tectonic evolution of the Oman ophiolite was investigated using the core samples obtained in the Oman Drilling Project. The core samples were recovered from three drilling sites (BA1B, BA3A, and BA4A) in the mantle section composed mainly of harzburgite and discordant dunite and wehrlite. A large number of mafic veins crosscut the structures of both mantle lithologies, indicating that they intruded after the formation of discordant dunites. The wehrlites include Fe3+-rich and TiO2-poor chromian spinel, suggesting that the discordant dunites and wehrlites were involved in hydrous, Ti-poor arc magmatism. The composition of plagioclase and clinopyroxene and rare-earth element (REE) patterns of clinopyroxene for the mafic veins suggest that the mafic veins were produced from mid-ocean ridge basalt (MORB)-like parental melts. On the other hand, early crystallization of clinopyroxene and Fe3+-rich and TiO2-poor chromian spinel in the mafic veins imply that the parental melts were also hydrous. Zircon UPb dating of the mafic veins yields the igneous age of about 91 Ma, which is younger than the V1 and V2 volcanic sequences. Depending on the distance from the mafic veins, the various REE patterns of clinopyroxene and Ca amphibole in the Oman harzburgites indicate local peridotite metasomatism during intrusion and percolation of late-stage melts that formed the mafic veins. Ca amphibole in the harzburgites and mafic veins lack significant enrichment in fluid-mobile elements, indicating that the hydrous phases were formed by fluids associated with hydrothermal activities in a spreading environment instead of slab-derived fluids. The mafic veins were likely produced in a spreading environment on a supra-subduction zone. As their formation took place after the arc magmatism that formed the Oman V2 lava sequence and discordant dunites, as a result of slab roll-back. This seafloor re-spreading on a supra-subduction zone after the V2 magmatism recorded in the mantle section might have been involved in the formation of the plume-related V3 lava sequence overlying the V2 lavas.

New insights into the origin and depositional setting of the Haerdaban Pb[sbnd]Zn deposit, Chinese western Tianshan: Evidence from geology, chert geochemistry, and detrital zircon U[sbnd]Pb geochronology

The Haerdaban PbZn deposit (with an ore reserve of 10.93 Mt. at 1.0–25.65 % Zn and 0.7–12.29 % Pb) is hosted in weakly metamorphosed clastic‑carbonate rocks from the Proterozoic Haerdaban Group. It represents a significant addition of the sediment-hosted PbZn deposits in the Yili block, Chinese western Tianshan. Currently, there are ongoing debates regarding its genesis, with a particular focus on the crucial metallogenic mechanism (syngenetic sedimentary exhalation or epigenetic reworking) responsible for the primary sulfide mineralization. Mineralization at Haerdaban primarily occurs as banded to stratiform ore layers or lenses conformably sandwiched in their host rocks. Vein and stockwork ores occur locally below the stratiform ore layers. A syn-sedimentary fault trending SN was identified based on abrupt lateral changes in lithofacies and thickness of the stratigraphic units. The ore mineralogy is dominated by sphalerite, galena, quartz, and dolomite, with a small amount of pyrite, barite, and organic matter. Detrital zircon LA-ICP-MS UPb dating of the Haerdaban siltstones obtained a maximum depositional age of about 604 Ma. Their geochemical composition similar to the passive continental margin signatures, with rare earth element (REE) patterns enriched in LREE and negative Eu anomalies (Eu/Eu* = 0.50–1.14). Stratiform beds of chert that host disseminated ores have relatively high contents of hydrothermal components (e.g., Ba, Zn), with apparent positive Eu anomalies (Eu/Eu* = 7.38–49.34) and negligible negative Ce anomalies (Ce/Ce* = 0.85–0.98). They are thus interpreted to be hydrothermal sedimentary rocks (exhalites) deposited in a suboxic-anoxic environment proximal to the hydrothermal vents. Integrated geological and geochemical evidence indicates that the Haerdaban PbZn deposit is a typical vent-proximal sedimentary exhalative (SEDEX) deposit formed in a Neoproterozoic Sinian (Ediacaran) passive continental margin rift basin. Post-depositional metamorphism and deformation in the Paleozoic may have caused partial remobilization of primary ores but did not significantly alter the morphology of the orebodies. Furthermore, establishing a genetic model for the Haerdaban deposit has important implications for the exploration of similar deposits preserved in the equivalent stratigraphy within the Chinese western Tianshan region.

Using Hg isotopes and trace elements to constrain the origin of the Ordovician Xiangquan Tl deposit, South China

Sediment-hosted stratiform sulfide (SHSS) deposits commonly contain large amounts of strategic metals, such as Tl, Hg, Cd, Ge and Ga, however, sources of these metals remain debate. Here we present new elemental and Hg isotopic data to constrain the metal sources for the Xiangquan Tl deposit (South China), a unique SHSS deposit with 250 t Tl at an average grade of 928 ppm. Stratiform pyrite orebodies are hosted in the Ordovician marine sedimentary succession of mostly limestone with minor mudstone. Pyrite, the dominant ore mineral, is rich in Hg (up to 1360 ppm). Bulk ores and pyrite separates from this deposit have significant variations of δ202Hg (−5.48 to −0.65 ‰) and Δ199Hg (−0.01 to 0.36 ‰). The Δ199Hg values are mostly positive, similar to those of seawater and marine sediments. Ore petrography, trace element enrichment coefficients, rare earth element patterns, Re-Os ages (478 ± 33 Ma) and S isotope compositions of pyrite indicate that Hg and other metals were derived from hydrothermal fluids venting at the seafloor. We suggest that the ore-forming fluids of the Xiangquan deposit were predominantly originated from large-scale circulation of evolved seawater, which leached Hg and Tl from the marine country rocks. These metal-rich fluids migrated upward, vented to the seafloor, and mixed with anoxic H2S-rich seawater to precipitate Hg- and Tl-rich pyrite. Our study highlights that the combined application of Hg isotopes and trace elements could be used to trace the sources of metals in hydrothermal ore deposits such as SHSS deposits.

Geologic fingerprints of the Rodinia breakup in the western North China Craton: Constraints from the Early Neoproterozoic (ca. 825–810 Ma) mafic volcanic and intrusive rocks in the Langshan tectonic belt

As an important component of the East Asian continental block, the North China Craton (NCC) is crucial for reconstructing Rodinia in the Neoproterozoic. However, whether the NCC is a component of the Rodinia supercontinent and records its breakup remains enigmatic. Here, we identified Langshan gabbro and mafic dikes with ages of ca. 829–826 Ma and mafic volcanic rocks with ages of 810 ± 3 Ma in the northeastern Alxa Block of the western NCC. The Langshan gabbro shows flat rare earth element (REE) patterns [(La/Yb)N = 1.3–1.5] and slight enrichment in most incompatible trace elements, similar to enriched mid-ocean ridge basalt. The mafic volcanic rocks show the geochemical features of oceanic island basalt, including high total alkaline content (7.86–8.47 wt%), enriched in light REEs (La/YbN = 8.0–9.1), and insignificant Eu anomalies. Together with contemporaneous felsic volcanic rocks identified in previous studies, the mafic volcanic rocks (ca. 810 Ma) define a bimodal association. The mafic intrusive and associated dike swarms from ca. 825–810 Ma along with the coeval Jinchuan ultramafic–mafic intrusions, followed by rifting sedimentary successions, were formed in an extensional rift setting, supporting the geologic fingerprints of the Rodinia breakup in the western NCC. The well-matched mafic magmatic barcodes, similar provenance, and sedimentary successions preserved in the Adelaide superbasin of southeastern Australia and the Langshan rift basin of the western NCC support a possible link between the NCC and Australia during the Early Neoproterozoic.

Nephrite from Xinjiang Qiemo Margou Deposit: Gemological and Geochemical Insights

The nephrite belt in the Altun Mountain–Western Kunlun Mountain region, which extends about 1300 km in Xinjiang, NW China, is the largest nephrite deposit in the world. The Qiemo region in the Altun Mountains is a crucial nephrite-producing area in China, with demonstrated substantial prospects for future exploration. While existing research has extensively investigated secondary nephrite deposits in the Karakash River and native black nephrite deposits in Guangxi Dahua, a comprehensive investigation of black nephrite from original deposits in Xinjiang is lacking. Margou black-toned nephrite was recently found in primary deposits in Qiemo County, Xinjiang; this makes in-depth research on the characteristics of this mine necessary. A number of technical analytical methods such as polarizing microscopy, Ultra-Deep Three-Dimensional Microscope, electron microprobe, back-scattered electron image analysis, X-ray fluorescence, and inductively coupled plasma mass spectrometry were employed for this research. An experimental test was conducted to elucidate the chemical and mineralogical composition, further clarifying the genetic types of the black and black cyan nephrite from the Margou deposit in Qiemo, Xinjiang. The results reveal that the nephrite is mainly composed of tremolite–actinolite, characterized by Mg/(Mg + Fe2+) ratios ranging from 0.86 to 1.0. Minor minerals include diopside, epidote, pargasite, apatite, zircon, pyrite, and magnetite. Bulk-rock rare earth element (REE) patterns exhibit distinctive features, such as negative Eu anomalies (δEu = 0.00–0.17), decreasing light REEs, a relatively flat distribution of heavy REEs, and low total REE concentrations (1.6–38.9 μg/g); furthermore, the Cr (6–21 μg/g) and Ni (2.5–4.5 μg/g) contents are remarkably low. The magmatic influence of granite appears to be a fundamental factor in the genesis of the magnesian skarn hosting Margou nephrite. The distinctive black and black cyan colors are attributed to heightened iron content, mainly associated with FeO (0.08~6.29 wt.%). Analyses of the chemical composition allow Margou nephrite to be classified as typical of magnesian skarn deposits.

Petrogenesis of Miocene volcanism in the Central Anatolia: Geochemical, isotopic and geochronological evidence

This paper presents the first 40Ar/39Ar age data, new bulk-rock major-trace element compositions and NdSr isotope geochemistry, combined with detailed geological mapping of Galatia Volcanic Province (GVP) in the northwest Central Anatolia (Turkey). Here, there are voluminous extrusive rocks in a wide compositional range: a basalt, andesite and trachyte suite, and their pyroclastic equivalents. 40Ar/39Ar dating of two whole-rock samples from the GVP yielded plateau ages of 21.76 ± 0.8 Ma and 20.97 ± 0.5 Ma, constrain the volcanic activity at ca. 21 Ma (Aquitanian). The samples show by sub-parallel light rare earth element (LREE)-enrichment and relatively flat heavy rare earth element (HREE) patterns and moderate fractionation [average (La/Yb)N = 13.5]. Their initial 87/86Sr values vary between 0.704619 and 0.704998, while initial 143/144Nd values lie between 0.512673 and 0.512755. Integration of the geochemical and geochronological with geological data we propose that the volcanic rocks in the northern area of GVP with calc-alkaline affinity were produced by a lithospheric mantle magma in an extensional setting.

Surface water oxygenation and low bioproductivity during deposition of iron formation of the Jacadigo Group (Brazil): Insights from combined cadmium – Chromium isotopes

The Banda Alta Formation (Urucum district, Mato Grosso do Sul, Brazil) comprises ∼600 Ma Fe and Mn deposits, which are among the world's youngest and largest Neoproterozoic sedimentary Fe and Mn formations (IF; MnF). These have been deposited in a redox-stratified, marine sub-basin (Jacadigo Basin), which was strongly influenced by glacial advance/retraction cycles with temporary influx of continental freshwater and upwelling of metal-enriched deep anoxic seawater. Cr and Cd isotopes measured on meticulously separated hematite mesobands from drill core samples are relatively homogenous throughout the ca. 325 m thick sequence sampled in the Banda Alta Fm., with average authigenic δ53Cr values of +0.93 ± 0.24 ‰ (2σ; n = 23) and δ114Cd values of −0.14 ± 0.14 ‰ (2σ; n = 15). The significant enrichment of Cr, in parallel with the strong enrichments of other redox sensitive elements (U, Mo), attests for effective and efficient reduction removal processes in the surface waters during cycles where upwelling Fe2+-rich waters reached the oxygenated surface layer exposed to the atmosphere during episodic glacier retreat stages. Assuming a similar quantitative and efficient removal pathway of dissolved Cd by iron oxyhydroxides, the so-inferred average δ114Cd signature of −0.14 ± 0.14 ‰ in the Jacadigo Basin surface water is significantly lower than signatures of modern ocean surface waters with a range of δ114Cd of ca. ∼0.4 to ∼1 ‰ and even lower than the signature of modern ocean deep waters with δ114Cd of ∼0.3 ‰. It possibly attests to reduced primary production levels and lower nutrient utilization rates during deposition of the Late Neoproterozoic Jacadigo Group, compared to today. This despite the inferred oxidized surface water layer that must have prevailed during this time, as implied by the strongly positively fractionated Cr isotope signatures and pronouncedly negative Ce-anomalies recorded in the seawater-like, shale-normalized Rare Earth Element and Yttrium (REY) patterns exhibited by the hematite mesobands. Data presented herein speak for: (1) a stable, isotopically heavy Cr input to the Jacadigo Basin at the time of deposition, implying high atmospheric O2 levels in the Late Neoproterozoic (2) likely quantitative, reductive incorporation / adsorption processes of dissolved Cr and Cd, respectively, into/onto precipitating iron oxyhydroxides, and (3) the prevalence of low nutrient concentrations and utilization rates in the Jacadigo Basin during glacier retreat cycles. Banded iron formations are considered suitable archives for reconstructing redox and bioproductivity levels in past marine depositional basin, including those prevalent in Neoproterozoic glacial conditions, via employing the CrCd isotope double tracer to iron-rich mesobands.

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

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

Rare earth elements in clay-sized fractions: Implications for weathering fingerprint from parent materials to soils

Rare earth elements (REEs) have gained attention as tracers of pedogenic processes over the last few decades. Clay-sized fractions (CSFs, < 2 μm) may play a crucial role in hosting REEs. To better understand the pedochemical signals of REEs in clay-sized phases, such as iron oxides and phyllosilicates, we analyzed REE speciation in CSFs of carbonate rocks (limestone), clastic rocks (sandstone and shale), and their derived saprolites. Our results quantified the REE content (41.2–144.6 mg kg−1) and speciation in CSFs of parent materials, revealing that REEs were primarily hosted in amorphous iron oxides (Feox1), followed by crystalline iron oxides (Feox2) and phyllosilicates. Compared to parent materials, saprolites derived from carbonate rocks exhibited more than a two-fold enrichment of REEs in major clay-sized phases, confirming the role of CSFs as REE sinks during carbonate rock weathering. Furthermore, the initial REE patterns of CSFs of carbonate rocks underwent alteration throughout the weathering process, likely due to water–mineral interactions. Our findings suggest that REEs in CSFs record the weathering fingerprint for soils derived from carbonate rocks, while they are indicative of provenance for soils originating from clastic rocks.