Rare Earth Element Enrichment Research Articles

Characterization and Origin of Basalt-Derived Carnelian in the Mesozoic Newark Basin, New Jersey, USA

Carnelian occurs locally in New Jersey in the Newark basin as medium- to coarse-size pebbles in fluvial gravel and alluvium and colluvium formed from erosion of Lower Jurassic Preakness Basalt. Vesicles and molds of glauberite are preserved on lower surfaces and botryoidal textures on the upper surfaces of some pieces. The microstructure consists of length-fast chalcedony characterized by parallel fibrous bundles overlain by repetitive, wavy extinction bands. Only peaks of ɑ-quartz and minor moganite are recognized in X-ray diffraction patterns. Carnelian contains 97–98 wt.% SiO2, ~1.0 wt.% Fe2O3, and 1.0–1.4 wt.% LOI; other major elements are <0.1 wt.%. Trace element abundances are low except for Y, Nb, Ta, W, Th, and U. Rare earth element (REE) patterns display heavy REE enrichment and large negative Eu anomalies. Most trace elements were mobilized from Proterozoic sources, whereas Si was likely derived from the alteration of basaltic glass in the Preakness. Carnelian δ18OVSMOW values are high and range from +18.3 to +31.2‰, comparable to global occurrences of volcanic rock-derived chalcedony. We propose that carnelian precipitated in the first Preakness flow from the mixing of hydrothermal fluid with meteoric water under conditions of low temperature (20–80 °C) and neutral to slightly alkaline pH.

Agricultural activity on the Mun River basin: insight from spatial distribution and sources of dissolved rare earth elements in northeast Thailand.

Rare earth elements (REE) are emerging pollutants of concern, impacted by intensive fertilizer use and discharge of human and animal waste into agricultural watersheds. However, the natural values and potential anthropogenic enrichment of REE in aqueous systems of the agricultural basins remain poorly understood. This study investigated the spatial variation of dissolved REE in a predominantly agricultural river (Mun River) in northeast Thailand. Dissolved ΣREE concentrations in the Mun River ranged from 5.08 to 272.91 ng/L, with the highest concentrations observed in the middle reaches where agricultural fertilizers and wastewater increased dissolved REE concentrations. The PAAS-normalized patterns and dissolved Eu anomaly jointly reveal that the dissolved ΣREE mainly originated from local rocks and agricultural fertilizers. The dissolved REE in the Mun River is characteristic of a depleted light REE relative to heavy REE, slightly negative Ce anomaly, positive Eu anomaly, and positive Gd anomaly in a punctate distribution. The correlation analysis of (La/Yb)N with fluvial pH and HCO3- indicates that the water environment characteristics of the Mun River control dissolved REE fractionation. The Ce anomaly is associated with the oxidation environment, whereas the Eu anomaly is linked to the lithologic inheritance. Positive punctate Gd anomalies are influenced by human-caused wastewater discharge and applying fertilizers, raising Gd concentrations beyond natural background levels. This study has suggested that the geochemical characteristics of dissolved REE are affected by agricultural disturbances, and future environmental research on dissolved REE is essential to clarifying the impacts of REE on agriculture, the environment, and human health.

Survived carbonates in orogenic dunites from recycling of subduction-related sediments

The carbon recycling between the Earth's surface and its interior is accomplished through plate subduction and magmatic processes. The orogenic mantle peridotites document multi-stage metasomatism in the subduction zone and play a significant role in revealing the material transportation and migration between the Earth's different spheres. However, how the migration process of carbon-bearing species influenced the subcontinental lithosphere mantle remains a mystery. To address these issues, we conducted detailed petrography, whole-rock and mineral geochemical compositions, and Sr–C–O isotope studies on two types of peridotites (silicate melt pocket-bearing and carbonate melt pocket-bearing dunites) of the Maowu ultramafic massif in the Dabie orogen. The silicate-melt pockets were captured earlier than the carbonate-melt pockets, and were derived from a large proportion of silicate melts during the formation of garnet pyroxenites. The subsequent carbonate metasomatism was mainly divided into two stages: the stage 1 reflects the reaction between dolomite melts and orthopyroxenes to generate clinopyroxenes with high CaO content and Mg# value (> 92); the stage 2 is the injection of Ca-rich fluids into dunites, forming dolomite veins and volatile-rich assemblages of tremolite, barite and monazite. The clinopyroxenes display high 87Sr/86Sr (0.7079–0.7097) and (La/Yb)N ratios, low Ti/Eu ratios, and different enrichment in Th, U, Sr and light rare earth elements (LREEs), indicating a carbonate metasomatic origin. The equilibrium melts of them are similar to sedimentary limestones with positive Sr anomaly and depleted high field strength elements (HFSEs). The Sr-O isotope mixing simulation shows a mixing of 80–90% carbonate sediments with the upper mantle peridotite. The C-O isotopes of the carbonate minerals have similar variation ranges (δ13CV-PDB: 19.7–15.6 ‰, δ18OV-SMOW: 18.1–28.1 ‰) within the range of sedimentary organic carbon. The 87Sr/86Sr ratios of limestone reservoir (0.708–0.709) suggest the addition of sedimentary carbonates into the mantle wedge at ∼370–500 Ma. Therefore, we propose that the sedimentary carbonates and organic carbon migrated into the deep mantle-wedge through the subducted Tethyan-Ocean slab in the Early Paleozoic, which experienced complex metasomatism and formed as carbonate minerals in the Maowu dunites to achieve the carbon recycling between the sedimentary carbon reservoir and the mantle wedge beneath the North China Craton.

Factors controlling rare earth element plus yttrium enrichment in Fe[sbnd]Mn crusts from Canary Islands Seamounts (NE Central Atlantic)

Marine minerals are important because concentrate in their structure high contents of strategic and critical elements as rare earth elements. Forty-two samples from eight seamounts of Canary Islands Seamount Province (CISP) have been analyzed in order to evaluate their rare earth elements plus yttrium contents (REY). Highest contents of REY are related to hydrogenetic minerals and essentially Fe-vernadite (on average 3000 μg/g). Diagenetic minerals, on the other hand, show the lowest REY contents with an average content of 260 μg/g. These differences also depend on the growth rates, hydrogenetic minerals with growth rates between 0.5 and 5 mm/Ma allow the incorporation of more REY in their structure. REY contents in studied samples varies depending several factors associated with depth and location, shallowest samples presumably growth near or within the oxygen minimum zone are the most enriched with up to 3800 μg/g due to local enrichment of these elements and the slowest growth rate promoted by the reduced ambient conditions while deeper samples around 3000 m water depth show 2800 μg/g. Location also has a role in REY contents essentially due to the presence of different currents. Samples faced to north are exposed to the more oxygenated waters of the North Atlantic Deep Water and are depleted in REY if compared with deeper samples facing to south to the more oxic Antarctic Bottom Water. Finally, the case of study made on three different seamounts of the CISP show that FeMn crusts from this area could provide on average 130 tons of hydrometallurgical recovered REY (based on 1 km2 areal crust coverage) together with interesting quantity of several other strategic and base elements as Mn, Co, Ni, Cu, V, Mo between others.

Evaluating the contribution of hydrothermal fluids and clay minerals to the enrichment of rare earth elements and yttrium (REY) in deep-sea sediments

Deep-sea REY-rich sediments have attracted considerable attention in recent studies because of their extremely high REY resource potential. Previous studies highlighted that hydrothermal precipitates (e.g., Fe-Mn (oxyhydr)oxides) have played an important role in REY enrichment in deep-sea sediments by scavenging REY from seawater. However, the exact extent of the contribution of hydrothermal scavenging to the REY accumulation has not yet been evaluated. In addition, REY enrichment generally occurred in the pelagic clays, and whether the clays have played a role in the REY accumulation is poorly constrained. We studied bulk-sediment geochemistry and mineral fractions of sediments from two sites in the Eastern South Pacific Ocean. The results show that both cores contain REY-rich sediments layers possessing average ΣREY contents of 989 ppm and 1563 ppm, respectively. The calculated REY resource amounts in the 1 km × 1 km × optimal recovery depth (m) of the two sites are summed to 4690 t-REO. Carbonate compensation depth is one of the factors controlling the REY contents in the sediments in our study area. The shale-normalized REY patterns and calculated simulation results suggest that direct input of REY from the hydrothermal sources to the sediments was not significant. The evaluation of the contributions of REY scavenged by hydrothermal Fe-Mn (oxyhydr)oxides suggests that for the metalliferous sediments in which Fe-Mn (oxyhydr)oxides are hydrothermal-dominated, the Fe2O3 and ΣREY contents show a pronounced positive correlation for all cores, implying hydrothermal scavenging of REY significantly contributed to the accumulation of REY. However, with the continuous addition of hydrothermal Fe-Mn (oxyhydr)oxides in the pelagic clay sediments, the ΣREY contents in the REY-rich sediments firstly exhibited an increase, and then when the total Fe2O3 components achieved a certain value (∼25 wt% in this study) they started to decline. This finding suggests the appropriate input of hydrothermal Fe-Mn (oxyhydr)oxides into the sediments certainly increases the ΣREY contents through a scavenging mechanism, but that excessive addition of them would, in turn, decrease the ΣREY contents of the sediments. Additionally, the amount of clay minerals exhibited a significant positive correlation with ΣREY contents, therefore, we inferred that clay minerals probably played an important role in REY accumulation in the sediments.

Rare Earth Element Characteristics in Coal Ash from the Jungar Energy Gangue Power Plant, Inner Mongolia, China

The coal and coal-bearing measures in the Jungar Coalfield in Inner Mongolia are characterized by rare earth element (REE) enrichment. Combustion in coal-fired power plants can lead to further enrichment of REEs in coal ash, which serves as a new potential source for REE extraction and smelting. Further, investigating the content, modes of occurrence, and transformation behavior of REEs during coal combustion may help in better understanding REE differentiation during coal combustion and facilitate the development of economically feasible REE recovery technologies. Therefore, in this study, we analyzed coal ash from the Jungar Energy Gangue Power Plant in Inner Mongolia via inductively coupled plasma mass spectrometry, X-ray diffraction, and scanning electron microscopy combined with energy-dispersive spectroscopy. Our results showed that the REE content of the feed coal was 220 μg/g, slightly higher than the average for global coal. Additionally, fly ash had a higher REE content (898 μg/g) than bottom ash, and its rare earth oxide content was approximately 1152 μg/g, which meets the industrial requirements. Bottom and fly ashes contained similar minerals; however, their relative abundances were different. Specifically, mullite, quartz, calcite, and gypsum were slightly more abundant in fly ash than in bottom ash, whereas amorphous solids were slightly more abundant in bottom ash than in fly ash. Furthermore, fly ash, dominated by Si- and Al-rich minerals, was composed of irregular particles of different shapes and sizes. It also contained monazite and REE fluoro-oxides, which possibly originated from the feed coal and had mineral structures that remained unchanged during coal combustion. Thus, the REE fluoro-oxides possibly resulted from the conversion of bastnaesite in the feed coal during combustion and thereafter became attached to the edge of the Si–Al minerals in the fly ash.

Trace element compositions and geochronology of cassiterite from the Bushveld Large Igneous Province, South Africa

This study presents trace element compositions and ages of four representative cassiterite samples from the Zaaiplaats, Union and Rooiberg Sn fields, all spatially associated with the Bushveld Large Igneous Province (LIP), South Africa. The Zaaiplaats Sn field is endogranitic and entirely hosted within the variably-altered Bobbejaankop and Lease granites of the Lebowa Granite Suite. In contrast, the exogranitic Union and Rooiberg Sn fields occur within the Union Tin Member of the Rooiberg Group, and the Pretoria Group of the Transvaal Supergroup, respectively. Collectively, all the cassiterite samples display quasi-parallel chondrite-normalised rare earth element (REE) patterns characterised by relative enrichments in the heavy REE, and yielded ages varying within a relatively restricted interval between 2061 ± 40 Ma and 2054 ± 3 Ma. This age range compares well with those reported from the Bushveld LIP and, when combined with mineral compositions, suggests a common granitic source for cassiterites from all the Sn fields. The exogranitic Rooiberg and Union Sn fields are identified by cassiterites with Zr/Hf of ∼40, whereas the endogranitic Zaaiplaats Sn field is characterised by cassiterites enriched in most incompatible elements (e.g., Nb, Ta, Zr, Hf, In, F and B) and Zr/Hf of ∼10. These Zr/Hf ratios agree with the endogranitic and exogranitic Sn ores from other localities, but are different from the very low Zr/Hf ratios of ∼3 reported for endogranitic cassiterites associated with rare-metal granites. The Zr versus Hf discrimination diagram may therefore be useful for distinguishing the endogranitic and exogranitic origins of cassiterites and for identifying the extent of fractionation of the causative source.

Petrogenesis of the Early Paleoproterozoic Felsic Metavolcanic Rocks from the Liaodong Peninsula, NE China: Implications for the Tectonic Evolution of the Jiao-Liao-Ji Belt, North China Craton

The early Paleoproterozoic (ca. 2.2–2.1 Ga) tectonic evolution of the Jiao–Liao–Ji belt (JLJB) is a continuous hot topic and remains highly controversial. Two main tectonic regimes have been proposed for the JLJB, namely arc-related setting and intra-continental rift. Abundant ca. 2.2–2.1 Ga volcanic rocks were formed in the JLJB, especially in the Liaodong Peninsula. These ca. 2.2–2.1 Ga volcanic rocks therefore could host critical information for the evolution of the JLJB. In this study, we report a suit of ca. 2.2–2.1 Ga felsic metavolcanic rocks in the Liaodong Peninsula of the JLJB to provide new insights into the above issue. Zircon U-Pb dating reveals that the felsic metavolcanic rocks were erupted at 2185–2167 Ma. They have variable εHf(t) values (−0.70 to +9.69), high SiO2 (66.30–75.30 wt.%) and relatively low TiO2 (0.03–0.78 wt.%), tFe2O3 (0.55–5.03 wt.%), MgO (0.17–8.76 wt.%), Cr (9.16–67.30 ppm), Co (2.01–7.00 ppm) and Ni (3.90–25.70 ppm) contents with enrichments in light rare earth element (REE) and large ion lithophile element (LILE), and depletions in heavy REE and high field strength element (HFSE). Geochemical and isotopic results indicate that the felsic metavolcanic rocks were sourced from partial melting of ancient Archean TTG rocks and juvenile lower crustal materials. Combined with coeval A-type granites, bimodal volcanic rocks and the absence of typical arc magmatism, the most likely tectonic regime at ca. 2.2–2.1 Ga for the JLJB is an intra-continental rift.

Formation of barite in the Ab Torsh deposit, Kerman province, Iran: Insights from rare earth elements, O and S isotopes, and fluid inclusions

Barite can form in a variety of geological environments, as it occurs in a wide range of mineral deposits. To determine the origin and physicochemical conditions under which the Ab Torsh barite deposit formed, an extensive study was conducted using petrographic, Rare Earth Element (REE) geochemical, O and S isotopic, and fluid inclusion methods. Barite mineralization occurs at Ab Torsh as a stratabound vein in the Senonian carbonate rock units. Barite-quartz is accompanied by subordinate malachite, chrysocolla, Fe-Mn oxide-hydroxides, galena, azurite, fluorite, pyrite, and bornite. The ∑REE values are very low in barite (5.32–14.56 ppm), with chondrite-normalized patterns showing enrichment of Light Rare Earth Elements (LREE) relative to Heavy Rare Earth Elements (HREE). The low ∑REE content and REE element ratios (Ce/La, (La/La*)N, and (Gd/Gd*)N) indicate that seawater with a highly altered geochemical signature (connate water) acted as a Ba ore-forming fluid. The δ18O and δ34S values in barite (+10.4–+11.1 ‰ and +27.3–+27.8 ‰, respectively) and the δ34S values in galena (+6.3 and + 7.9 ‰) indicate that the sulfate (and thus sulfur) originated from sulfate-bearing connate waters and/or evaporites. Thermochemical Sulfate Reduction (TSR) was the most likely mechanism for the formation of the reduced sulfur in galena. The salinity and homogenization temperatures in the aqueous fluid inclusions of barite and quartz (2.7–19.3 wt% NaCl equivalent and 110–275 °C, respectively) indicate that basinal fluids containing a meteoric water component were the source of the mineralizing solutions. The fluid inclusion data demonstrate that two fluid mixing have occurred: one between the hot basinal brines and cold meteoric waters, and another between heated and cold meteoric waters. It is estimated that the hot fluids derived from a maximum depth of about 9 km. The Ab Torsh deposit is classified here as a structure (unconformity)-related barite deposit. It is concluded that intense faulting and brecciation of the host rocks caused by post-Cretaceous compressional tectonics probably provided the channels necessary for the upward migration of deep mineralizing fluids from a basinal brine source. Barite formed where these ascending hot, Ba-bearing hydrothermal fluids encountered cooler, sulfate-bearing connate waters trapped in the overlying Senonian strata and/or the descending cold meteoric waters that dissolved evaporite-bearing rock units.

Refertilized continental root controls the formation of the Mianning–Dechang carbonatite-associated rare-earth-element ore system

Rare earth element ore deposits associated with carbonatite derived from Earth’s mantle supply half of the world’s rare earth element. However, the formation of carbonatite and initial enrichment and transport of rare earth element in the mantle, is unclear. Here, we image the lithospheric architecture of a Cenozoic rare earth element ore belt in southwestern China by integrating seismic tomography with geochemical data. The subduction of the Indian continent caused vertical upwelling and lateral flow of the asthenosphere, which triggered the melting of the overlying subcontinental lithospheric mantle to generate carbonatites. Such a mantle source that previously metasomatized by fluids from recycled marine sediments is a precursor process critical for forming a giant rare earth element system. For the studied ore belt, three key factors are prerequisites to generating ore-forming carbonatites: thick lithosphere with a continental root; prior fertilization of the subcontinental lithospheric mantle; and trans-lithospheric weakness for magma ascent.

Tonian Continental Arc Magmatism of the Porongos Complex, Dom Feliciano Belt, Southern Brazil

This study provides new information on the deformation, metamorphism, and tectonic setting of the metavolcanic rocks of the southern portion of the Porongos Complex, southern Brazil. The structural analysis enabled the identification of three deformational phases, formed under ductile to semi-ductile conditions. D1 progressed through deformation partitioning, comprising closed to isoclinal folds and an axial plane foliation. Then, simple shear prevailed, resulting in isoclinal folds, sigma-type porphyroclasts, foliation transposition, and mylonitic rocks. D2 comprises open to gentle folds and an axial plane cleavage. The formation of shear bands is ascribed to the semi-ductile D3. The mineral assemblage represented by phengite + chlorite + clinozoisite-epidote + actinolite + albite + quartz associated with the temperatures obtained through the chlorite geothermometer (316°C) indicates greenschist facies conditions. The protoliths of these metavolcanic rocks are geochemically discriminated as calc-alkaline, dacite-to-rhyodacite, with peraluminous compositions. The bulk trace element compositions show enrichment in large-ion lithophile elements and light rare-earth elements and depletion in heavy rare-earth elements. Also, negative Nb, P, Ti, and Ta anomalies are observed in the multielement diagram. All these geochemical features are typical of rocks formed in continental magmatic arcs. Geochemical comparison with other pre-collisional Tonian orthometamorphic rocks from the Dom Feliciano Belt demonstrates strong similarities, which corroborates the prior interpretation of a continental arc setting for the origin of these Tonian rocks.

Large Si isotope fractionation reveals formation mechanism of quartz in silicon-poor carbonatite

Abstract Carbonatites, the most silica-poor igneous rocks, have a close relationship with rare earth element (REE) ore deposits, where low SiO2 activity is considered to contribute to economic REE mineralization. However, a paradox is raised by quartz, commonly regarded as a Si-saturation proxy, which occurs in some giant carbonatites or carbonatite-related REE deposits such as those at Bayan Obo, China, and Mountain Pass, California, USA. A unique perception for the origin of quartz in carbonatites is provided here using Si isotope analysis. Quartz grains from the Bayan Obo carbonatite and REE ores commonly occur as inclusions in fluorite, or they coexist with fluorite, thus implicating the importance of fluorine in their hydrothermal origin. The quartz grains have remarkably large variations in δ30Si values, ranging from −4.55‰ to 1.71‰ in secondary ion mass spectrometry analyses, which have not been documented elsewhere in high- to medium-temperature magmatic-hydrothermal processes. Theoretical calculations demonstrate that such large Si isotopic fractionation can be generated during the formation and breakdown of Si-O and Si-F bonds due to their difference in bond strength. These results imply the presence of silicon fluoride species in the fluid and highlight the role of fluorine in quartz formation in silicon-poor carbonatite. The exsolved fluids from carbonatite magmas containing silicon fluoride species may decrease silica activity, which has the potential to impede incorporation of REEs into magmatic apatite, and thus facilitate late-stage hydrothermal REE enrichment and formation of REE orebodies.

Late Paleozoic Tectonic Evolution of the Northern Great Xing’an Range, Northeast China: Constraints from Carboniferous Magmatic Rocks in the Wunuer Area

Northeast China composes the main part of the Central Asian Orogenic Belt. Traditionally, Northeast China has been considered a collage of several microcontinental blocks. However, the tectonic evolution of these blocks remains uncertain. Igneous rocks can be used to infer the magmatic histories of the blocks and thus help reconstruct their evolution. In this study, we present new zircon U–Pb and whole-rock geochemical data for Carboniferous igneous rocks from the Wunuer area, northern Great Xing’an Range, Northeast China, to constrain the Carboniferous amalgamation of the united Xing’an–Erguna and Songnen–Zhangguangcai Range massifs. On the basis of zircon U–Pb dating results, we identify two main stages of magmatism, i.e., early Carboniferous (332–329 Ma) and late Carboniferous (312–310 Ma). The early Carboniferous igneous rocks include diorites and granodiorites, with the former being classified as calc-alkaline to tholeiitic and the latter as tholeiitic. Both rock types are enriched in Th and U and depleted in Nb and Ti. The rocks display slightly fractionated rare earth element (REE) patterns, with an enrichment in light REEs and a depletion in heavy (H)REEs. The geochemical characteristics of the early Carboniferous rocks indicate that they formed in a subduction-related continental-arc setting. The late Carboniferous igneous rocks include monzogranites and syenogranites, both of which are classified as high-K calc-alkaline rocks and show enrichment in Th, U, and Rb and depletion in Nb and Ti. The rocks display strongly fractionated REE patterns, with an enrichment in light REEs and a depletion in HREEs. The geochemical characteristics of the late Carboniferous rocks indicate that they formed in a syn-collisional tectonic setting. Combining the new geochronological and geochemical results and inferred tectonic settings with regional magmatic data, we propose a new three-stage model to interpret the late Paleozoic tectonic evolution of the united Xing’an–Erguna and Songnen–Zhangguangcai Range massifs of Northeast China: (1) early Carboniferous (360–340 Ma) subduction of the Paleo-Asian oceanic plate beneath the united Xing’an–Erguna Massif and formation of the Wunuer oceanic basin in the Yakeshi area; (2) early to late Carboniferous (340–310 Ma) sustained subduction of the Paleo-Asian oceanic plate beneath the united Xing’an–Erguna Massif and initiation of subduction of the Wunuer oceanic basin; and (3) late Carboniferous–early Permian (310–275 Ma) syn-collisional to post-collisional tectonic transition between the united Xing’an–Erguna Massif and the Songnen–Zhangguangcai Range Massif.

Distribution, source and contamination of rare earth elements in sediments from lower reaches of the Xiangjiang River, China

Rare earth elements (REEs) are emerging micropollutants in aquatic environments. In this study, concentrations of REEs and major elements, and mineralogical compositions of sediments from lower reaches of the Xiangjiang River (China) were analyzed using ICP-MS technique. The results suggested that sediments were characterized by terrigenous compositions TiO2, SiO2, Al2O3, K2O, Na2O and P2O, and contained high concentrations of REEs with mean total REE concentrations (∑REE) of 318.7 mg/kg. REEs were moderately enriched in upper river sediments, and slightly or less enriched in downriver sediments. The normalized REE distribution pattern for sediments was characterized by flat shalelike and Eu depleted V-shape REE patterns, which indicated REEs in sediments were lithologically contributed from sedimentary rocks and granites distributed in the watershed respectively. REEs in sediments were hosted mainly in Fe–Mn oxides, and sulfide and organic matters that were characterized by middle REEs (MREE) enrichments relative to light REEs (LREE) and heavy REEs (HREE), and the distribution and differentiation of REEs in sediments were controlled by clays, Fe–Mn oxides, organic matters and finer grains; and also by accessory minerals (e.g., zircon) from granite. The distribution features of REEs in sediments and BCR extraction results suggested that the sediment REE enrichment resulted from additional REE input from anthropogenic sources, including those in discharges from sulfide-ore smelting industries at Zhuzhou city and from phosphate fertilizer plants at Xiangtan city along the river. Thus, sediments were contaminated with REEs in moderate degree in upper river area, and REE contamination was then formed by superimposing anthropogenic REEs on lithological residues. Finally, concentrations of Ce > 100 mg/kg, Gd > 8.12 mg/kg, ∑REE >274.9 mg/kg, ∑LREE >252.3 mg/kg and ∑HREE >28.8 mg/kg here were recommended as the REE contamination levels that represented as REE indices for identifying and rating REE contamination in this mining impacted river.

Origin of carbonate minerals and impacts on reservoir quality of the Wufeng and Longmaxi Shale, Sichuan Basin

The Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin were studied to understand the genesis and diagenetic evolution of carbonate minerals and their effects on reservoir quality. The results of geochemical and petrological analyses show that calcite grains have a negative Ce anomaly indicating they formed in the oxidizing environment of seawater. The high carbonate mineral contents in the margin of basin indicate that calcite grains and cores of dolomite grains appear largely to be of detrital origin. The rhombic rims of dolomite grains and dolomite concretions with the δ13C of –15.46‰ and the enrichment of middle rare earth elements were formed during the sulfate-driven anaerobic oxidation of methane. The calcite in radiolarian were related to the microbial sulfate reduction for the abundant anhedral pyrites and δ13C value of –11.34‰. Calcite veins precipitated in the deep burial stage with homogenization temperature of the inclusions ranging from 146.70 °C to 182.90 °C. The pores in shale are mainly organic matter pores with pore size mainly in the range of 1–20 nm in diameter. Carbonate minerals influence the development of pores through offering storage space for organic matter. When calcite contents ranging from 10% to 20%, calcite grains and cement as rigid framework can preserve primary pores. Subsequently, the thermal cracking of liquid petroleum in primary pores will form organic matter pores. The radiolarian were mostly partially filled with calcite, which combining with microcrystalline quartz preserved a high storage capacity.

Bioconcentration and translocation of rare earth elements in plants collected from three legacy mine sites in Portugal

Rare earth elements (REE), a group of emerging contaminants with commercial and technological applications, share many physical and chemical characteristics and have thus been used as accurate tracers of various environmental samples. They have been shown to increase in receiving waters following the dissolution of host-rock material during mining activities. In this study, spontaneous vegetation and related media were collected from three Portuguese legacy mine sites in November 2020 to evaluate the phytoavailability and fate of REE. Water, soil and plant data were analyzed in the context of the 1) prevailing geochemical context, 2) the mining context, and 3) plant effects. This study presents the REE signatures for different plant species and links the signatures to a potential source of bioavailable REE. The REE accumulated in plant tissue seems to reflect the REE signature of surface waters in the mining areas, showing enrichment in middle REE. Although the soils, sediments, and waters in this study had similar features, certain plants seemed better adapted to translocating Light REE and Eu over others. Given that REE are readily available within the field conditions of a mining site, this study shows how plant physiology and biologic preference towards particular REE contribute to the fractionation of REE and create a unique signature dependent on plant type.

Analysis of enrichment, correlation, and leaching patterns of rare earth elements in coal fly ash assisted by statistical measures

Coal fly ash (CFA) is a typical industrial solid waste, which has recently been reported to contain rare earth elements (REEs). REEs are important materials in many industrial fields. Therefore, extracting REEs from CFA becomes a win-win strategy to both make full use of CFA and reclaim REEs. However, the stable crystalline structure of CFA is hard to break, which limits the extraction of REEs. The inter-correlation and the leaching patterns of the REEs in CFA also remain unclear. In this work, REEs were enriched by desilication, and the correlation and the influences of multiple acids of the leached REEs were investigated. It was found that desilication could increase the leachable amount of REEs from 137.37 ppm to 346.12 ppm. The light rare earth elements (LREEs) were less inter-correlated than heavy rare earth elements (HREEs) and desilication enhanced the leaching of LREEs more than that of HREEs. The ratio and type of the leaching acids both influenced the extraction of REEs from CFA: HCl and HF played important roles in the extraction from the untreated CFA while HNO3 and HF were more decisive for the desilicated CFA. In addition, we used statistical analysis to quantificationally confirm that desilication and acids both significantly influenced the extraction of REEs. This work provides evidence for the enrichment of REEs in CFA and acid choosing when leaching REEs from CFA.

Can temperature rise change the impacts induced by e-waste on adults and sperm of Mytilus galloprovincialis?

Nowadays, it is of utmost importance to consider climate change factors, such as ocean warming, since the risk of negative impacts derived from increased surface water temperature is predicted to be high to the biodiversity. The need for renewable energy technologies, to reduce greenhouse gas emissions, has led to the increasing use of rare earth elements (REEs). Dysprosium (Dy) is widely used in magnets, motors, electrical vehicles, and nuclear reactors, being considered a critical REE to technology due to its economic importance and high supply risk. However, the increasing use of this element contributes to the enrichment of anthropogenic REEs in aquatic systems. Nevertheless, the information on the potential toxicity of Dy is limited. Moreover, the effects of pollutants can be amplified when combined with climate change factors. Thus, this study aimed to assess the effects of Dy (10 μg/L) in the species Mytilus galloprovincialis under actual (17 °C) and predicted warming conditions (21 °C). The Dy concentration in contaminated mussels was similar between temperatures, probably due to the detoxification capacity in individuals under these treatments. The combined stressors affected the redox balance, but higher impacts were caused by Dy and warming acting alone. In terms of cellular damage, although Dy acting alone was prejudicial to mussels, warming and both stressors acting together induced higher levels of LPO and PC. The histopathological effects of Dy in the digestive tubules were independent of the temperature tested. Regarding effects on sperm, only warming induced cellular damage, while both stressors, alone and together, impaired sperm movement. Overall, this study highlights that warming might influence the effects induced by Dy, but greater impacts were caused by the element. Eventually, the tested stressors may have consequences on mussels' reproduction capacity as well as their growth, abundance, and survival.

Geological and geochemical characteristics of shallow-buried ferromanganese crusts from Weijia Guyot and their resource potential

Numerous buried ferromanganese (Fe-Mn) crusts covered by surface sediments, such as foraminifera ooze, were found on the platforms of certain guyots in the Western Pacific Ocean. To examine the origin of these shallow-buried (<100 cm below the seafloor) Fe-Mn crusts and evaluate their resource potential, we conducted mineralogical and geochemical studies on seven drill cores from the Weijia Guyot(Ita Mai Tai Guyot), which is in the Co-rich Fe-Mn crust contract area of the China Ocean Mineral Resources Research and Development Association (COMRA).The buried Fe-Mn crusts exhibit multilayer structures and are composed of disordered vernadite, similar to the exposed Fe-Mn crusts. Moreover, they show comparable contents of major metallogenic elements (e.g., Mn, Cu, Co, and Ni) and platinum group elements when compared to exposed Fe-Mn crusts. However, they have much higher contents of rare earth elements (REEs) than those of exposed Fe-Mn crusts, indicating a comparable resource potential. The high P contents and collophanite observed in the petrographic microscope indicate that an evident phosphatization event occurred. Based on the tectonic evolution and sedimentation rate, we infer that the phosphatization event mainly took place before the crusts were buried. The phosphatization of shallow-buried Fe-Mn crusts results in an enrichment of REEs and their fractions. This process can also modify the sedimentary environment for Ce precipitation, which may, in turn, alter the diagenetic microenvironment of the shallow-buried Fe-Mn crusts. The mineralogical and geochemical results reveal that burial doesn't cause a significant difference between shallow-buried and exposed Fe-Mn crusts from Weijia Guyot, and they are still of hydrogenetic origin. The findings and research on shallow-buried Fe-Mn crusts indicate that they have comparable resource potentials with exposed Fe-Mn crusts. These results will influence future decisions related to the exploration, exploitation, and utilization of Co-rich Fe-Mn crusts in the contract area of COMRA. Furthermore, it could provide valuable insights for other contractors investigating the platform.

Geochemistry and petrogenesis of late Neoproterozoic Nuweibi and Atawi rare metals bearing granites, central Eastern Desert, Egypt

Nuweibi albite granite (NAG) and Atawi two feldspar granites (AG) are silica rich, highly evolved intrusions and rare metals-bearing in the Central Eastern Desert of Egypt exhibiting different stages of magmatic-late magmatic evolution. Both are evolved from low-P2O5 metaluminous to peraluminous granitic magma resulting from partial melting of crustal source. The chemical features of both of NAG and AG as Na2O + K2O, FeOt/MgO, Ga, Nb and Ta high concentrations are compatible with an anorogenic within plate tectonic setting. However, NAG have higher concentration of Al2O3, Na2O, MnO, Ga, Rb, Hf and Ta and lower concentrations of SiO2, TiO2, Fe2O3t, MgO, CaO, K2O, P2O5, Ba, Zr, Y, Sn, W, F and REEs. NAG shows obvious enrichment of heavy rare earth elements (HREEs) relative to light rare earth elements (LREEs), negative Eu anomaly and tetrad effect. On the other hand, AG has higher concentration of REEs and its pattern is slightly enriched in LREEs relative to HREEs with negative Eu anomaly. For NAG, the fluid-mobilization of REEs and other trace elements is supported by very low ratios of Eu/Eu* (0.17–0.3), (La/Yb)n (0.06–0.4), Nb/Ta (0.44–1.09), Zr/Hf (1.84–2.61), K/Rb (66.8–109.9) and Y/Ho ratios (2.9–6.3) together with high Sr/Eu (160–440). On the other hand, AG represents moderately fractionated granitic melt in regard to chondrites still showing chondritic or almost chondritic Nb/Ta (5.5–15.9), Zr/Hf (14.8–28.6), Y/Ho (26.2–45), K/Rb (99.24–346.28) and Sr/Eu (56.6–520) ratios indicating the lower effect of late magmatic fluid-rock interaction compared to NAG. Fluid phase enriched in alkalis from a nearly solidified granite causes local albitization in Atawi and Nuweibi areas where Nuweibi granite is more albitized. Moreover, greisenization (decomposition of feldspar and Fe-mica) is also more common in NAG.