Rare Earth Element Enrichment Research Articles

A comprehensive study of apatite grains in Ryugu rock fragments

AbstractApatite is present as an accessory phase in many meteorites and is often formed as a secondary product of aqueous alteration. Its propensity to incorporate rare earth elements (REE) results in apatite usually being the main REE‐bearing phase in hydrously altered meteorites. Asteroid Ryugu is thought to have experienced pervasive aqueous alteration and material collected from the surface of Ryugu is expected to provide insight into asteroidal aqueous alteration processes without influence by terrestrial weathering. Morphologies and mineral associations of apatite grains from five rock fragments collected from the asteroid Ryugu by the Hayabusa2 spacecraft were examined and their REE concentrations were measured by synchrotron X‐ray fluorescence (SXRF) spectroscopy. The main minerals associated with apatite are dolomite, magnetite, and pyrrhotite. Grain boundary corrosion of the interfaces between apatite assemblages and the surrounding matrix suggest that paragenetic formation on the asteroid was followed by a later episode of hydrous alteration. Light REE (LREE) concentration levels recorded at 20–150 times those of bulk CI levels together with a steady increase from LREE toward enrichment of medium REE (MREE, up to Er) at 50–400 times bulk CI levels may suggest postgenetic removal of LREE from Ryugu apatite grains by late‐stage circulation of a hydrothermal fluid.

Age and petrogenesis of ore-bearing porphyry from the Houyu Mo-polymetallic deposit, central North China Craton

Porphyry-related molybdenum deposits formed within the plate's interior are unique, yet the understanding of the magmatic hydrothermal Mo system remains limited. Houyu is a typical porphyry-related Mo-polymetallic deposit situated in the inner region of the North China Craton (NCC). The ore bodies are found in Archean biotite plagioclase gneiss and diorite, followed by Early Cretaceous quartz porphyry, granite porphyry, and brecciated porphyry. Zircon U-Pb dating reveals that the biotite plagioclase gneiss, quartz porphyry, and granite porphyry were formed at 2499.2 ± 7.8 Ma, 135.19 ± 0.67 Ma, and 137.65 ± 0.84 Ma, respectively. Molybdenite Re-Os dating indicates a mean age of 134.94 ± 0.76 Ma and an isochron age of 134.7 ± 1.5 Ma, linking the Mo-polymetallic mineralization closely to the Early Cretaceous porphyry. The Houyu Cretaceous porphyry exhibits enrichment in light rare earth elements (LREEs), depletion in heavy rare earth elements (HREEs), and distinct positive Eu anomalies. Additionally, they are enriched in fluid-mobile large-ion-lithophile elements (LILEs) and significantly depleted in high-field-strength elements (HFSEs). These geochemical attributes suggest that the Cretaceous porphyry belongs to I-type adakitic granites. All samples exhibit consistently negative εNd(t) values ranging from −15.76 to −14.87 and εHf(t) values between −20.69 and −14.78, along with restricted 206Pb/204Pb (16.557–16.663), 207Pb/204Pb (15.262–15.300), and 208Pb/204Pb (36.601–36.747) ratios, indicating that they were derived from an ancient thickened lower continental crust (LCC). The Cretaceous magmatism and mineralization of the Houyu Mo-polymetallic deposit could be closely linked to the lithospheric thinning and destruction of the NCC triggered by the Paleo-Pacific or Izanagi Plate.

Eocene mafic alkaline volcanism in north Central Iran; Signatures of development and subsequent melting of a pyroxenite mantle source

Volcanic rocks from the Miami-Davarzan area are basalts to trachyandesites interlayered with fossiliferous beds and bear significant implications on the Eocene geodynamic evolution of northern central Iran. The rocks constitute two distinct groups, a low-Nb and a high-Nb suite. The least evolved low-Nb suite includes clinopyroxene-olivine phyric samples and is characterized by higher CaO and lower Al2O3 as compared to peridotite partial melts. The high-Nb suite includes more evolved plagioclase-clinopyroxene phyric samples. Fractional crystallization modeling using least-squares mass balance calculations for major elements suggests that the high-Nb suite was formed from a low-Nb parental melt by differentiation of a clinopyroxene-dominated mineral assemblage. The Miami-Davarzan volcanic rocks are characterized by significant large ion lithophile elements (LILE) and light rare earth elements (LREE) enrichment and high field strength elements (HFSE) depletion, which are typical signatures of subduction-related settings. Immobile, highly to moderately incompatible elements such as NbTa, LaCe, PrNd are higher in the Miami-Davarzan volcanic rocks as compared to the typical magmatic arcs, which is an indication of slab melt involvement and metasomatism of the mantle source. The Sr-Nd-Pb isotopic data also confirm a common mantle source involving the addition of subducted sediments into a depleted mantle source for both the low-Nb and high-Nb suites. The geochemical characteristics such as high CaO, low Al2O3, and the isotopic data can be best explained by derivation of the low-Nb suite parental melt from a pyroxenite mantle source. The pyroxenite mantle source was probably developed as a result of interaction between shallow depleted mantle and slab plus sediment-derived melts. It is suggested that the extensional phase that dominated the northern central Iran during the Eocene prompted partial melting of a pyroxenite mantle source.

Tectono-metamorphic evolution of the Central Bundelkhand Craton, India from geochemistry and bulk composition modelling of amphibolite enclaves

The Bundelkhand Craton (BuC) represents a significant Archean terrane within the northern Indian Craton and yet its tectono-metamorphic evolutionary history remains relatively understudied. Our investigation involves detailed petrography, geochemistry, and bulk composition modeling of both garnet-bearing and garnet-absent amphibolites with a two-fold objective: (i) to constrain the protolithic nature and tectonic settings involved in the genesis of these rocks, and (ii) to propose a tectono-metamorphic evolutionary history for the BuC. The BuC amphibolites originate from basalt and andesitic-basalt protoliths. Their trace element compositions reveal negative anomalies in Nb, Ta, and Ti, while their rare earth element (REE) normalized patterns indicate enrichment in light REEs over heavy REEs. The basaltic protolith is interpreted to have formed during orogeny in a compressional tectonic regime at the active margins of island arcs in a subduction-related setting. This interpretation is supported by various discrimination plots for amphibolites, such as Nb/Th vs Zr/Nb, Zr vs Zr/Y, and Th/Nb vs Ce/Nb, as well as high Th/Yb and low Nb/Yb contents— all of which suggest an island arc setting influenced by subduction. These amphibolites have undergone three distinct phases of metamorphism, as evidenced by petrography, mineral chemistry, and bulk composition modeling. This interpretation is further supported by geochemical discrimination diagrams which indicate that a subduction tectonic setting was active during peak metamorphism. During the pre-peak phase, the garnet-bearing amphibolites experienced pressure and temperature conditions ranging from 6.25 to 6.5 kbar and 580 to 590ºC, while the garnet-absent amphibolites underwent conditions from 5.0 to 5.8 kbar and 400 to 450ºC. Peak metamorphism was observed at pressures ranging from 6.8 to 7.4 kbar and temperatures from 760 to 805ºC for the garnet-bearing amphibolites, and at pressures from 7.0 to 7.4 kbar and temperatures from 785 to 810ºC for the garnet-absent amphibolites. The metamorphic retrograde conditions for the garnet-bearing amphibolites are defined by P-T conditions ranging from 4.45 to 4.75 kbar and 585 to 615ºC, while for the garnet-absent amphibolites, it ranges from 3.1 to 4.0 kbar and 620 to 710ºC. The mineral assemblages and P-T conditions delineate a clockwise P-T path for both, garnet-bearing and garnet-absent amphibolites from the Babina and Mauranipur regions. This suggests that the rocks underwent a burial process amid subduction tectonic settings in an arc-related environment, followed by a decompression stage that brought them to the surface.

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.

Membrane pre-concentration as an efficient strategy to enhance the enrichment of rare earth by MgO precipitation

Taking advantage of the environmentally-friendly properties of a magnesium salt leaching agent, magnesium oxide (MgO) was used as a precipitant to enrich rare earth (RE) from leaching liquor in the magnesium salt system. This approach not only tackles the issue of ammonia–nitrogen pollution but also enables efficient magnesium recycling. However, due to the high concentration of magnesium ions and the low concentration of RE ions in the leaching solution, the precipitation kinetics of RE concentrates are sluggish, leading to low RE purity in the resulting precipitated product. In this work, we proposed a novel strategy that combines complexation-ultrafiltration (UF) pre-concentration with subsequent MgO precipitation to enhance the hydrolysis of MgO, promoting the precipitation of RE. We further improved the RE enrichment efficiency by optimizing membrane type, complexing agent selection, concentration levels, precipitation temperature, and MgO dosage. Under the conditions of concentrating the leaching solution using optimal UF membrane and employing glyphosate as the complexing agent, the RE ions concentration increased from 101 to 3940 mg/L, and we successfully separated magnesium ions with a separation factor of 36.4. A comparison between direct MgO precipitation and the pre-concentration approach revealed an 80 % reduction in precipitation time and an 80 % decrease in MgO usage with pre-concentration. Furthermore, this combined process led to an 8 % increase in RE recovery and a 2.8-fold enhancement in RE purity, and similar results were obtained when using actual mine leaching solutions. Additionally, the glyphosate present in the UF permeate and the precipitated mother liquor can be efficiently reclaimed through resin adsorption. This proposed process holds significant potential for engineering applications aimed at enriching RE.

Rare earth element enrichment in coal and coal-adjacent strata of the Uinta Region, Utah and Colorado

This study aims to quantify rare earth element enrichment within coal and coal-adjacent strata in the Uinta Region of central Utah and western Colorado. Rare earth elements are a subset of critical minerals as defined by the U.S. Geological Survey. These elements are used for a wide variety of applications, including renewable energy technology in the transition toward carbon-neutral energy. While rare earth element enrichment has been associated with Appalachian coals, there has been a more limited evaluation of western U.S. coals. Here, samples from six active mines, four idle/historical mines, four mine waste piles, and seven stratigraphically complete cores within the Uinta Region were geochemically evaluated using portable X-ray fluorescence (n = 3,113) and inductively coupled plasma-mass spectrometry (n = 145) elemental analytical methods. Results suggest that 24%–45% of stratigraphically coal-adjacent carbonaceous shale and siltstone units show rare earth element enrichment (&amp;gt;200 ppm), as do 100% of sampled igneous material. A small subset (5%–8%) of coal samples display rare earth element enrichment, specifically in cases containing volcanic ash. This study proposes two multi-step depositional and diagenetic models to explain the enrichment process, requiring the emplacement and mobilization of rare earth element source material due to hydrothermal and other external influences. Historical geochemical evaluations of Uinta Region coal and coal-adjacent data are sparse, emphasizing the statistical significance of this research. These results support the utilization of active mines and coal processing waste piles for the future of domestic rare earth element extraction, offering economic and environmental solutions to pressing global demands.

Rare earth elements reveal the human health and environmental concerns in the largest tributary of the Mekong river, Northeastern Thailand

The widespread application of rare earth elements (REEs) in contemporary industries and agriculture, has caused emerging contaminant accumulation in aquatic environments. However, there is a limited scope of risk assessments, particularly in relation to human health associated with REEs. This study investigated the provenance, and contamination levels of REEs, further evaluating their environmental and human health risks in river sediments from an agricultural basin. The concentrations of REEs ranged from 30.5 to 347.7 mg/kg, with showing an upward trend from headwater to downstream. The positive matrix factorization (PMF) model identified natural and anthropogenic input, especially from agricultural activities, as the primary source of REEs in Mun River sediments. The contamination assessment by the geoaccumulation index (I-geo) and pollution load index (PLI) confirmed that almost individual REEs in the samples were slightly to moderately polluted. The potential ecological risk index (PERI) showed mild to moderate risks in Mun River sediment. Regular fertilization poses pollution and ecological risks to agricultural areas, manifesting as an enrichment of light REEs in river sediments. Nevertheless, Monte Carlo simulations estimated the average daily doses of total REEs from sediments to be 0.24 μg/kg/day for adults and 0.95 μg/kg/day for children, comfortably below established human health thresholds. However, the risk of REE exposure appears to be higher in children, and sensitivity analyses suggested that REE concentration contributed more to health risks, whether the adults or children. Thus, concerns regarding REE contamination and risks should be raised considering the wide distribution of agricultural regions, and further attention is warranted to assess the health risks associated with other routes of REE exposure.

Geochemical Evidence of Plume Sources for High-MgO Lavas in the Western Kunlun Orogenic Belt

Abstract Plume-derived high-MgO lavas provide important information on the lithological, thermal and chemical variations of Earth’s deep mantle. Here we present results from detailed field, mineralogical and geochemical studies of Late Permian–Late Triassic high-MgO lavas near the Chalukou area in the Western Kunlun (WK) orogenic belt, NW China. The major element compositions of the lavas show extremely high MgO contents (26.6–33.8 wt %) in accordance with olivine accumulation. The parental magma is inferred to be picritic in composition with MgO of 17.2 ± 0.9 wt %. Olivine Zn/Fe and Mn/Zn ratios suggest a peridotite-dominated source with a minor fraction of pyroxenite. The temperature and oxygen fugacity estimates based on multi-methods including olivine-melt Mg–Fe equilibria, Al-in-olivine and olivine–spinel thermometry and oxybarometer yield a mantle potential temperature of 1522–1556 °C and high oxygen fugacity of FMQ (fayalite-magnetite-quartz) + 0.93. The H2O contents in the picrite flows are estimated as 3.67 ± 1.0 wt %, indicating the volatile-rich nature of parental magma and its mantle source. The immobile trace element features show that the WK picrites are OIB (oceanic island basalt)-like, with the enrichment in light rare earth elements and positive Nb, Ta, Zr and Hf anomalies. Furthermore, the Nd–O–Os isotopes display typical mantle values without involvement of recycled materials. Our results suggest the high-MgO volcanism in the WK orogenic belt originated from a volatile-rich plume source.

Rare Earth Element Adsorption to Clay Minerals: Mechanistic Insights and Implications for Recovery from Secondary Sources.

The energy transition will have significant mineral demands and there is growing interest in recovering critical metals, including rare earth elements (REE), from secondary sources in aqueous and sedimentary environments. However, the role of clays in REE transport and deposition in these settings remains understudied. This work investigated REE adsorption to the clay minerals illite and kaolinite through pH adsorption experiments and extended X-ray absorption fine structure (EXAFS). Clay type, pH, and ionic strength (IS) affected adsorption, with decreased adsorption under acidic pH and elevated IS. Illite had a higher adsorption capacity than kaolinite; however, >95% adsorption was achieved at pH ∼7.5 regardless of IS or clay. These results were used to develop a surface complexation model with the derived binding constants used to predict REE speciation in the presence of competing sorbents. This demonstrated that clays become increasingly important as pH increases, and EXAFS modeling showed that REE can exist as both inner- and outer-sphere complexes. Together, this indicated that clays can be an important control on the transport and enrichment of REE in sedimentary systems. These findings can be applied to identify settings to target for resource extraction or to predict REE transport and fate as a contaminant.

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

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

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

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

Silicate melt immiscibility as the cause of large-scale rare-metal mineralization in a peralkaline granite system: The case of the Baerzhe deposit in NE China

The Early Cretaceous peralkaline Baerzhe pluton hosts a potentially large REE-Nb-Zr-Be deposit in inner Mongolia, northeastern China. The mechanism responsible for the extreme enrichment of rare metals and rare earth elements in the pluton is still ambiguous. This study presents new evidence for silicate melt immiscibility as the key mechanism at Baerzhe using amphibole-group minerals from spherulite granite, which contains spherulites with abundant REE- and HFSE-bearing minerals. The spherulite from the transsolvus granite is composed of two distinct zones, i.e., a dark-colored core consisting of arfvedsonite aggregates and a light-colored rim consisting mostly of quartz and feldspar, rare amphibole, and abundant HFSE- and REE-bearing minerals. Four types of amphibole (AmpI, Amp-IIa, Amp-IIb and Amp-III) from the transsolvus granite and one type (Amp-IV) from the subsolvus granite are recognized, and all of them are magmatic fluoro-arfvedsonite. The earliest phase consists of euhedral inclusions of Amp-I within quartz or feldspar. They show an enrichment in HREEs relative to LREEs and a depletion in medium REEs, consistent with the REE pattern controlled by the mineral lattice. This implies that Amp-I likely formed in an initial homogeneous mel relatively depleted in REEs; thus, the mineral structure played a dominant role in REE partitioning. Compared with other types of amphiboles, Amp-IIa and Amp-IIb from the spherulite phase display the highest REE contents, with flat LREEs and MREEs and a slight upward HREE pattern. Combined with the significant accumulation of REE- and HFSE-bearing minerals in the rim zone, differences in REE patterns among different amphibole types imply that the spherulite crystallized in a volatile-rich silicate melt and was probably the product of silicate melt immiscibility. Interstitial Amp-III with lower REE contents from the matrix phase crystallized in the separate volatile-poor silicate melt. The Amp-IV from the subsolvus granite has the lowest CaO content, with strong depletion in LREEs relative to HREEs, suggesting a more evolved melt composition. It is concluded that silicate melt immiscibility may serve as an important key mechanism that occurred in the early stage of magmatic evolution, resulting in the enrichment of REEs and HFSEs, which played a critical role in the formation of large to giant ore deposits such as the Baerzhe deposit.

Geochemical characteristics of rare earth elements in late Palaeozoic coals from North China

Introduction: China is a large country of REE resources and production, supplying more than 90% of the world’s rare earth consumption market, China’s traditional REE resources, although rich, but reserves are also declining, in recent years, scholars have shown that the REEs in the specific geological conditions in the coals can be enriched, and even reach the industrial grade, the search for more REE mineral resources will be of great strategic significance.Methods: The article has selected the Zibo, Taozao, Huainan, Datong, Huozhou, Jungar, and Weibei coalfields in North China as the research objects. Based on inductively coupled plasma mass spectrometry (ICP-MS) analyses, the study provides a detailed analysis of the enrichment rules and distribution patterns of rare earth elements (REEs) in coal under different geological conditions.Results: The REE distribution patterns in Late Palaeozoic coals in North China are characterized by enrichment of LREEs, deficit of HREEs with gentle changes, and obvious negative anomalies of Eu, the enrichment of REE in coal is controlled by provenance and volcanism, and is related to distance of transport terrigenous material and the sedimentary environment. The REEs concentrations in North China indicates that Late Palaeozoic coals in the mining areas of the north, northwest, and western parts of North China are significantly enriched in REEs. In addition, REEs in Late Palaeozoic coals in the southeastern mining areas are relatively enriched, and the central and eastern regions are significantly depleted.Discussion: Large coal-type rare earth deposits are expected to be developed in North China, particularly the Datong coalfield, Jungar coal mine and the Weibei coal mine in the eastern margin of the Ordos Basin, and the Zibo coalfield.

Heterogeneity of the late Mesozoic lithospheric mantle beneath the Jiaodong Peninsula, eastern North China Craton: a synthesis from geochemistry and Sr-Nd-Pb isotopes of mafic dykes

ABSTRACT The Late Mesozoic lithospheric mantle evolution of the Jiaodong Peninsula is crucial for understanding the destruction of the eastern North China Craton (NCC) and large-scale gold mineralization, but it still remains highly controversial. Here, we comprehensively compiled published Late Mesozoic mafic dyke magmatism data from the Jiaodong Peninsula to provide key constraints on the nature and evolution of the lithospheric mantle. Mafic dykes are widely emplaced in the Jiaodong Peninsula and have been divided into two groups (Jiaobei terrane and Sulu orogenic belt); they mainly comprise lamprophyre, dolerite, and gabbro. The ages of the mafic dykes in the Jiaobei terrane are predominantly between 120 and 125 Ma, and those of the Sulu orogenic belt are between 110 and 120 Ma. The Jiaobei and Sulu mafic dykes both have high contents of Mg and compatible elements (Cr, Ni), as well as low SiO2 content; they are characterized by arc-like mafic magma, including enrichment in Large Ion Lithophile Elements and Light Rare Earth Elements, depletion in High Field Strength Elements, high (87Sr/86Sr)i, and low εNd(t), implying a metasomatized lithospheric mantle source. However, the Jiaobei mafic dykes have relatively higher (87Sr/86Sr)i, lower εNd(t), and a larger range of (206Pb/204Pb)i, (208Pb/204Pb)i, and (207Pb/204Pb)i compared with the Sulu mafic dykes. The Jiaobei and Sulu mafic dykes exhibit Ba/Rb ratios of 1.29‒64.39 (average 29.3) and 6.61‒108.28 (average 33.1), respectively, indicating the presence of hornblende in the melts. The high Fe/Mn (>60) and Zn/Fe (>12) ratios of Jiaobei and Sulu mafic dykes indicate the mixed mantle source of peridotite and pyroxenite. But the content of pyroxenite in the mantle source of Jiaobei terrane is higher with wider range of Fe/Mn and Zn/Fe ratios. These features indicate the heterogeneity of the mantle sources of the mafic dykes in the Jiaobei and Sulu regions. It is suggested that both regions originated from the partial melting of hornblende-bearing peridotite, with the addition of more pyroxenite to the mantle source of the Jiaobei terrane compared to Sulu orogenic belt. The mafic dykes have the low Nb/Zr (Jiaobei: 0.024–0.229; Sulu: 0.030–0.166) and Th/Zr ratios (Jiaobei: 0.017–0.081; Sulu: 0.010–0.068), and the high Rb/Y (Jiaobei: 0.347–12.162; Sulu: 0.224–9.600) and low Nb/Y ratios (Jiaobei: 0.202–1.486; Sulu: 0.140–1.322). It implies that the mantle source area in both regions was metasomatized by subducted slab-derived fluids. The increase in (La/Yb)N and decrease in Hf/Sm implies carbonate metasomatism in both regions. In addition, some Jiaobei and Sulu mafic dykes have high Ti/Eu ratios, implying that the silicate metasomatism occurred in the mantle source of both regions. Based on the regional evolution, the lithospheric mantle source in the two regions beneath Jiaodong Peninsula experienced carbonated fluid metasomatism resulting from the subduction of the Palaeo-Asian Ocean plate beneath the northern NCC (ca. ~250 Ma), silicate melt-related metasomatism from subduction of the Yangtze Craton plate beneath the southern NCC (ca. 240‒220 Ma), and oceanic slab-derived fluid metasomatism from the subducted Palaeo-Pacific plate (at 180‒110 Ma). It is believed that the mantle source of Jiaobei terrane had undergone stronger carbonated fluid metasomatism and silicate melt-related metasomatism, compared to Sulu orogenic belt. Moreover, the continental fluid-related metasomatism only occurred in the Sulu orogenic belt. During the Late Mesozoic, the eastern NCC experienced large-scale lithospheric thinning, leading to upwelling of the asthenospheric mantle. The mafic dykes in Jiaobei and Sulu, show different geochemical features, were derived from partial melting of the metasomatized lithospheric mantle through upwelling of the asthenospheric mantle.

Petrogenesis and REE mineralogical characteristics of Shitouping granites in southern Jiangxi Province: Implication for HREE mineralization in South China

The enrichment of heavy rare earth elements (HREE) in the granitic host-rocks is crucial for generating ion-adsorption HREE deposits in South China. The Shitouping pluton, located in the southern part of Jiangxi Province, South China, develops large-scale HREE deposits in its weathering profile identified by recent geological surveys. These granites can be divided into medium to coarse-grained biotite monzogranite (MGBG), medium to coarse-grained syenogranite (MGSG) and fine-grained alkali feldspar granite (FGAG) based on field observations and mineral assemblages. New geochronologic results show that this composite pluton intruded during the Early Cretaceous (ca. 140 Ma). Three granitic units displaying comparable whole-rock Nd [εNd(t) = −4.5 to −3.4] and zircon Hf compositions [εHf(t) = −4.4 to +1.2], combined with mineral association, hydrothermally altered zircon and whole-rock geochemistry, indicate they were derived from partial melting of hybridized crustal source, followed by intense fractional crystallization and fluid metasomatism in the highly evolved granitic system. The MGSG and FGAG have higher Rb, Nb, HREE contents and Rb/Sr ratios, as well as lower Nb/Ta, K/Rb ratios in comparison with the MGBG, implying they are more evolved units. The overlapping magmatic zircon trace element compositions between MGBG and MGSG, coupled with the subvertical contact boundary between the FGAG and the MGBG, suggest that the generation of Shitouping pluton should be attributed to the periodic magma replenishment, remobilization, and differentiation process in the long-lived magmatic system rather than simple fractional crystallization from a single parental magma. Hydrothermally altered zircon with elevated concentration of HREE and the paragenetic relationship between LREE-phosphate and HREE minerals in the MGSG suggest that the fluid metasomatism promotes the migration and accumulation of HREE. This is consistent with the high HREE concentration recorded in the MGSG, which contains abundant HREE minerals associated with fluorites. Thus, this study highlights that magma differentiation and fluid metasomatism during the late magmatic stage could achieve the relatively high HREE contents in granites to favor the formation of ion-adsorption HREE deposits.

Distinct mafic magmatism of the northeastern Longgang Block: Evidence for coexisting mantle plume and subduction during the Neoarchean North China Craton

The question of which specific tectonic regimes played an essential role in shaping the Neoarchean evolution of the North China Craton (NCC) has been a contentious and controversial topic. Mafic rocks, containing valuable geochemical information from the mantle and deep crust, serve as an important source of data to provide essential constraints on above issue. This study presents bulk-rock geochemistry, zircon U-Pb geochronology and Hf-Nd isotopes for the Neoarchean mafic rocks in the core area of the Longgang Block of the NCC. Petrographically, these mafic rocks are composed of the amphibolite and metadiabase. Zircon U-Pb dating results revealed that they were synchronously emplaced at ca. 2.5 Ga. Geochemically, the amphibolites belong to subalkaline tholeiite series, exhibiting enrichment in light rare earth elements (LREEs), intensely negative Nb, Ta and Ti anomalies, and slightly enriched Nd and relatively variable zircon Hf isotopic compositions. These geochemical and isotopic features show large affinity to arc-like magmatism, implying that they were derived from subduction-related metasomatized lithospheric mantle. In contrast, the metadiabases exhibit high-Ti alkaline basalt affinities, OIB-like REE, and trace element patterns. They also show clearly positive Nb, Ta and Ti anomalies, indicating that they originated from a mantle plume-related tectonic environment. The new geochemical and isotopic data reveal that these Neoarchean mafic rocks could have resulted from coexisting mantle plume and subduction processes. Combined with available regional structural, geochemical, and metamorphic data, it is likely that during the Neoarchean, both a mantle plume and subduction jointly controlled the crustal growth and tectonic evolution of the Longgang Block in the eastern NCC.

Petrogenesis of the eudialyte-bearing syenite and indication for Nb-Zr-REE mineralization in Bashisuogong, Northwest China

The Bashisuogong alkaline igneous intrusion is located between the South Tianshan Orogenic Belt and the Kepingtage foreland thrust belt at the northern margin of the Tarim Craton and hosts economically significant Nb–Ta–Zr–rare earth element mineralization. Eudialyte has recently been discovered in the syenite unit of this intrusion, which is the primary host mineral for high-field-strength and rare earth elements. Based on detailed petrographic investigations, this study investigated the behavior of trace elements during magma evolution and the enrichment of ore-forming elements using whole-rock geochemical analyses of eudialyte-bearing syenite and compositional analyses of aegirine–augite and different types of eudialyte. We also undertook in situ titanite UPb dating. The Bashisuogong syenite comprises aegirine–augite and aegirine–augite–eudialyte syenite, the latter of which have higher total rare earth element contents. Both types of syenite exhibit slight enrichments in light rare earth elements, significant enrichments in high-field-strength elements (Nb, Ta, Zr, Hf, and Th), depletions in large-ion lithophile elements (Ba and Sr), and large negative Eu anomalies. There are two types (I and II) of eudialyte. Eudialyte I has higher Mn/Fe, Zr/Hf, and Nb/Ta ratios but lower Th/U ratios compared with eudialyte II but similar Y/Ho ratios. Eudialyte II crystallized earlier than eudialyte I, and aegirine–augite, titanite, and apatite crystallized earlier than eudialyte I. Both aegirine–augite and eudialyte have similar trace element characteristics to the host rocks, exhibiting enrichments in highly incompatible high-field-strength and rare earth elements, as well as marked negative Eu anomalies and depletions in Sr. These characteristics suggest that the Bashisuogong alkaline rocks formed by low-degree partial melting of geochemically enriched, metasomatized lithospheric mantle, which formed an alkaline basaltic parental melt that then underwent protracted magma evolution and fractionation in the shallow crust. The eudialyte syenite yield a titanite UPb age of 277.3 ± 1.2 Ma, which is consistent with the ages of different types of alkaline igneous rocks in the study area, indicating they were the products of the same magmatic event. Temporally and spatially, the Bashisuogong ore-bearing alkaline rocks were associated with the Tarim mantle plume, and the mantle plume provided the heat for their formation.

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

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

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.