Middle Rare Earth Element Enrichment Research Articles

Processes controlling rare earth element distribution in sedimentary apatite: Insights from spectroscopy, in situ geochemistry and O and Sr isotope composition

ABSTRACTIn phosphorites, the content and distribution of rare earth elements are linked to the environment of phosphogenesis. This paper focuses on the question of sources and processes controlling the rare earth element content of apatite from Belgian phosphorites formed during three major phosphogenic events in the Lower Palaeozoic, Late Cretaceous and Cenozoic. To constrain sources and processes, new data include petrological, mineralogical (including cathodoluminescence and Raman spectroscopy) and in situ trace element and Sr and O isotope analyses of apatite. Fluorapatite from Lower Palaeozoic P‐rich conglomerates has the greatest rare earth element enrichment. It is affected by metamorphism that led to deformation of apatite nodules and formation of garnet porphyroblast inclusions. The role of Fe‐oxyhydroxides in element scavenging is highlighted by some apatite nodules that maintain their primary middle rare earth element enrichment, while others are characterized by altered rare earth element patterns resulting from competition for these elements between co‐crystallizing minerals during deformation. A systematic shift towards lower δ18O and radiogenic Sr isotopic composition compared to contemporaneous seawater indicate interaction with 18O‐depleted meteoric fluids and a crustal component. By contrast, carbonate‐rich fluorapatite from the Late Cretaceous phosphatic chalk mostly keeps its primary trace element and isotopic signatures (close to seawater), although an external rare earth element addition is noted, as well as rare earth element redistribution induced by diagenetic alteration. Cenozoic carbonate fluorapatite nodules mostly present flat rare earth element patterns that are indicative of a detrital influence. Slight changes in rare earth element distribution are assigned to post‐depositional alteration, which also led to an increase in radiogenic Sr, with unchanged δ18O compared to seawater. The methodology followed here efficiently helps in deciphering the processes that modified the chemistry of apatite in the frame of major phosphogenic events.

The seasonal variations in the interactions between rare earth elements and organic matter in tropical rivers

The escalation of global demands for critical minerals to facilitate the green energy transition creates emerging needs to better understand their environmental behaviours. Several nations recognize rare earth elements (REEs) as priority critical minerals and emphasize the necessity to evaluate their environmental mobility and potential effects on natural ecosystems and human health. Here, we investigated the seasonal variations in dissolved concentrations of REEs and their leachable fractions from suspended particles in samples collected bi-weekly from the Sai Gon and Dong Nai Rivers in Southern Vietnam. The investigation period extended over sixteen months, including a transition from wet to dry seasons. We reported significant mobility of REEs in the river waters during the wet season due to watershed runoff, especially in Sai Gon River with the occurrence of acid-sulphate soils. Dissolved REE concentrations in the dry season were significantly lower because of the interactions with organic-rich particles (up to 13% of particulate organic carbon, POC) mainly derived from phytoplankton materials. The conditional distribution coefficients (logKD from 5 to 7 for Pr) were proportional to POC content. The scavenging capacity of particulate organic matter also led to affect the fractionation between light REEs and heavy REEs in solution, and the characteristic Middle REE-enrichment patterns for the leachable REEs fraction. We also reported significant Eu anomalies (Eu/Eu* up to 7) in the Dong Nai River during the dry season and associated this observation with the decomposition of organic matter that previously accumulated Eu. However, further studies are required to confirm this hypothesis because of small reservoir effects; elevated Eu anomalies were observed in water samples with low dissolved Eu concentrations.

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.

Early diagenetic mobilization of rare earth elements and implications for the Ce anomaly as a redox proxy

The Rare Earth Elements (REE) archived in carbonate rocks retain a wealth of information on paleo-seawater chemistry and local-regional redox conditions. However, interpretations are often ambiguous due to the potential for REE remobilization in marine environments. In this regard, many carbonate rocks that retain primary seawater isotopic signatures exhibit non-seawater-like REE patterns, implying either unusual REE behaviour in seawater or diagenetic overprinting of otherwise well-preserved rock samples. Here, we apply sequential leaching to constrain the possible effects of different REE-bearing phases on measured carbonate REE patterns in order to address this quandary. Our results show that the exchangeable phase contains negligible REE, but could be an important host phase for other elements such as Sr, Ba and K. The acidified hydroxylamine hydrochloride leach is shown here not only to dissolve Fe–Mn oxides but also phosphate minerals, which induces middle REE enrichment in corresponding leachates of dolostone samples in our study. The demonstrable Fe–Mn oxide phase in limestone samples is characterized by middle and/or light REE enrichment and positive Eu anomalies, which are attributed to hydrothermal processes and continuing exchange with marine fluids after initial precipitation. The non-seawater-like REE patterns observed in the carbonate phase of otherwise well-preserved limestones resemble those of the co-existing Fe–Mn oxide fraction, and are interpreted to reflect the dissolution of REE carrier phases during early diagenesis. This view is supported by fluid-rock interaction modelling, which shows how REE can be mobilized at relatively low fluid/rock ratios in shallow porewaters. Non-seawater-like REE patterns may therefore be caused by the incorporation of REE from shallow porewaters before final lithification due to an elevated flux of particulate REE carrier phases, e.g. Fe–Mn oxides and organic matter, to the seafloor. In spite of the sensitivity of carbonate REE patterns to early diagenetic exchange, the co-occurrence of non-seawater-like patterns with primary strontium and carbon isotope values suggests that REE should not be viewed as a general indicator for the preservation of other geochemical proxies. Importantly, Ce anomalies of the carbonate phase will also be affected by porewaters, masking primary seawater values. Our results favour a reevaluation of redox interpretations by taking into account REE patterns as a whole.

Monazite-(Gd), a new Gd-dominant mineral of the monazite group from the Zimná Voda REE–U–Au quartz vein, Prakovce, Western Carpathians, Slovakia

AbstractMonazite-(Gd), ideally GdPO4, is a new mineral of the monazite group. It was discovered near Prakovce-Zimná Voda, ~23 km WNW of Košice, Western Carpathians, Slovakia. It forms anhedral domains (≤100 μm, mostly 10–50 μm in size), in close association with monazite-(Sm), Gd-bearing xenotime-(Y), Gd-bearing hingganite-(Y), fluorapatite and uraninite. All these minerals are hosted in a REE–U–Au quartz–muscovite vein, hosted in phyllites in an exocontact to granites. The density calculated using the average empirical formula and unit-cell parameters is 5.55 g/cm3. The average chemical composition measured by means of electron microprobe is as follows (wt.%): P2O5 29.68, As2O5 0.15, SiO2 0.07, ThO2 0.01, UO2 0.04, Y2O3 1.30, La2O3 3.19, Ce2O3 6.93, Pr2O3 1.12, Nd2O3 10.56, Sm2O3 17.36, Eu2O3 1.49, Gd2O3 22.84, Tb2O3 1.57, Dy2O3 2.27, CaO 0.21, total 99.67. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.30Sm0.24Nd0.15Ce0.10La0.05Dy0.03Y0.03Tb0.02Eu0.02Pr0.02Ca0.01)0.98P1.01O4. The ideal formula is GdPO4. The monazite-type structure has been confirmed by micro-Raman spectroscopy and selected-area electron diffraction. Monazite-(Gd) is monoclinic, space group P21/n, a = 6.703(1) Å, b = 6.914(1) Å, c = 6.383(1) Å, β = 103.8(1)°, V = 287.3(1) Å3 and Z = 4. The middle REE enrichment of monazite-(Gd) is shared with the associated Gd-bearing xenotime-(Y) to ‘xenotime-(Gd)’ and Gd-bearing hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing mineral assemblage is a product of selective complexing and enrichment in middle REE in low-temperature hydrothermal fluids by alteration of primary uraninite, brannerite and fluorapatite on a micro-scale. The new mineral is named as an analogue of monazite-(La), monazite-(Ce), monazite-(Nd) and monazite-(Sm) but with Gd dominant among the REE.

Rare earth element signatures of Doushantuo cap dolostones capture an increase in oxygen in the anoxic Ediacaran ocean

The Rare Earth Element (REE) systematics of the post-Marinoan cap dolostones reflect the marine redox conditions and chemistry in the immediate aftermath of the snowball Earth. Rare earth elements and yttrium (REY) compositions in the Doushantuo cap dolostones that directly overlie Nantuo glacial diamictites in south China are determined from the inner shelf to the slope. In general, shale-normalized REY patterns (REYSN) of the cap dolostones show significant fractionations that are characterized by light REE depletion, slight middle REE enrichment relative to the light and heavy REEs, positive Eu anomalies, and slightly super-chondritic Y/Ho ratios. These dolostones, however, show no significant shale-normalized negative Ce anomalies. Such REYSN patterns are consistent with an extensive anoxic Ediacaran ocean in the shallow-to-deep water columns. The REE concentrations and normalized patterns in the cap dolostones vary spatially and stratigraphically. When compared to the shelf edge and the slope, cap dolostones from the inner shelf are distinguished by uniformly less fractionated REYSN patterns with an absence of Eu anomalies, and suppressed light REE depletion and MREE enrichment. These marked differences in the REYSN patterns indicate significant continental influences on the seawater chemistry within the restricted inner shelf (lagoon) during glacial meltdown. The temporal trends in the REY dataset of the Doushantuo cap dolostone reflect shifts in marine redox conditions. Dolostones from two thick shelf margin sections (5 m and 7 m thick, respectively) show almost identical stratigraphic trends in the REY concentrations, and the Ce, Y, and middle REE anomalies. The overall stratigraphic decrease in the Ce anomaly, accompanied by the increase in the Y anomaly and decrease in the middle REE anomaly towards the top of the rock unit, suggests that dissolved oxygen was increasing in the shallow water column during the deposition of the cap dolostones. The REE data in this study reveal that the oxygenation of the Ediacaran oceans started in the immediate aftermath of the snowball Earth (635–632 Ma).

Dissolved rare earth element and neodymium isotope distributions in the South China Sea: Water mass source versus particle dissolution

Dissolved rare earth elements (REEs) and neodymium isotopes (ϵNd) have been jointly used to evaluate water mass mixing and lithogenic inputs in the ocean. As the largest marginal sea of the West Pacific, the South China Sea (SCS) is an ideal region for reconstructing past hydrological changes. However, its REE and ϵNd distributions and underlying controlling mechanisms remain poorly understood. On the basis of four seawater profiles spread across the SCS, this study presents dissolved REE concentrations and ϵNd data under summer condition to better understand the processes that potentially influence changes in these parameters and their marine cycling. The results show high concentrations of REEs and large variations in ϵNd (−6.7 to −2.8) in surface water, likely caused by the dissolution of riverine and marine particles. Comparison with published data from samples taken during the winter of different years in this and previous studies suggests a possible seasonal variability of middle REE enrichment. The SCS deep water shows a narrow ϵNd range from −4.3 to −3.4, confirming the dominant presence of the North Pacific Deep Water in the deep SCS. The intermediate water in the central SCS is characterized by a more negative ϵNd signal (–4.2 to –3.4) than that found in its counterpart in the West Pacific (–3.5 to –2.8), indicating alterations by deep water through three-dimensional overturning circulation from the northern to southern SCS below ~500 m. The contributions of external sources could be quantitatively estimated for the SCS in terms of Nd. The dissolution of particles from the SCS surrounding rivers (0.26–1.3 tons/yr in summer; 5.6–29 tons/yr in winter) and continental margins (2–12 tons/yr in summer; 23–44 tons/yr in winter) may play an important role in providing additional Nd to the SCS surface water.

Rare earth element uptake mechanisms in plankton in the Estuary and Gulf of St. Lawrence

The global shift toward green energy alternatives escalates demands for new resources, including rare earth elements (REEs), as per their implications in various green innovations. However, our understanding of their environmental cycle, especially the interactions with aquatic organisms, remains deficient, ultimately hindering environmental protection efforts. Here, we investigate the accumulation of REEs and 18 other elements in bulk and sorted plankton collected with different net mesh sizes (30, 63, 200, 333, 500 μm) in the Estuary and Gulf of St. Lawrence in the summer and winter of 2020. We observed significant correlations between the concentrations of REEs and elements of different charge numbers and ionic radii (Ba, Co, Cs, Fe, Mn, Pb, Rb and V), indicating non-selective uptake of REEs into plankton. All these elements have their highest concentrations in the fluvial corridor and upper estuary, with more significant enrichment in phytoplankton ([La] = 26.4 ± 4.8 mg kg−1) than zooplankton ([La] = 11.6 ± 8.3 mg kg−1). Their concentrations decrease to the minimum in the Gulf of St. Lawrence, especially in zooplankton ([La] = 4.8 × 10−2 ± 3.2 × 10−2 mg kg−1). We also assessed REE patterns to identify differential REE fractionation processes and anomalies. The freshwater plankton exhibits enrichment of middle REEs (MREEs) relative to the light and heavy REEs (LREEs and HREEs), potentially because of the higher binding affinity of MREEs on cellular surface transporters and metal loading effects. In estuarine and marine settings, the REE patterns in biological samples align with suspended particles, exhibiting a linear trend with LREE enrichment. This process is more noticeable in sorted macrozooplankton, which have significant Eu anomalies (Eu/Eu* up to 2), indicating differential incorporation of REEs into the chitin shells. This study highlights the significant enrichment of REEs into freshwater primary producers and the accumulation pathway similar to other inorganic elements.

Rare Earth Element (REE) and Critical Mineral Fractions of Central Appalachian Coal-Related Strata Determined by 7-Step Sequential Extraction

Rare earth elements (REEs) and critical minerals (CMs) are used in many modern industries, including the automotive sector, generation and storage, clean energy, and defense. The demand for REEs is increasing, and the REE supply chain is unpredictable. The US has driven to assess non-conventional sources of REE (such as coal underclay) to identify domestic resources to stabilize this uncertainty in supply. Knowledge of the minerology, distribution, and modes of occurrence of REEs is integral to the assessment of non-conventional sources. Additionally, extraction techniques can be optimized and targeted when REE distribution in different solid fractions from source material is understood. In this study, four bituminous coal-related samples associated with the Lower and Middle Kittanning coal seams in the Appalachian Basin (US) underwent a seven-step sequential extraction procedure, primarily targeting the water-soluble, exchangeable, acid soluble, mildly reducible, moderately reducible, strongly reducible, and oxidizable fractions. The REE and other elements of interest from each extraction step were analyzed, and the percentages of element extracted from raw solids were calculated. REEs extracted from the total seven steps were reported as the extractable fraction, whereas the fractions in the residual solids were reported as the non-extractable fraction. Less than 6% of REE were extracted from three samples. Twenty-one percent of REE was extracted from the fourth sample, mainly from the steps targeting oxidizable and exchangeable phases. Co-extraction of critical metals (Co, Ni, Cu, and Zn) occurred during the oxidizable, exchangeable, acid soluble, and water-soluble steps for the four samples. In the extracted fractions, the four samples all exhibited a middle and heavy REE enrichment relative to light REE. The mobility of major cation (e.g., Ca, Fe, and P) and REE is associated with exchangeable, oxidizable, and acid soluble fractions. Non-extractable REE is likely held in refractory apatitic phases, and/or primary REE-phosphates (e.g., monazite and xenotime).

Nature and evolution of diagenetic fluids in the deeply buried Cambrian Xiaoerbulake Formation, Tarim Basin, China

Significant amounts of petroleum are found in the deeply buried Cambrian Xiaoerbulake Formation in the Tarim Basin. However, limited understanding of origin of diagenetic fluids hampers petroleum exploration. In this study, petrological and high-resolution geochemical methods have been performed to understand the origin and evolution of diagenetic fluids, and their effects on the formation of dolostone reservoir. The Xiaoerbulake Formation is characterised by microbialites. The matrix is characterised by modern seawater-like rare earth element and yttrium (REY) patterns and δ18O values of −6.02 ± 2.11‰ Vienna Pee Dee Belemnite (VPDB). Fine-crystalline dolomite cements have similar δ13C values and heavy rare earth element enrichment patterns to that of matrix dolomite, yet with lower δ18O values of −7.47 ± 1.2‰ VPDB. In the deep-burial regimes, medium- to coarse-crystalline dolomite cements and saddle dolomites were precipitated at temperatures of 90–120 and 130–190 °C, respectively, lower δ18O values, distinct middle rare earth element enrichment, and high Fe and Mn contents compared with matrix and fine-crystalline dolomite cements. These imply thermochemical reduction of Fe- or Mn-rich oxides and/or hydrothermal fluids. Compared with other types of dolomite cements, calcite cements are characterised by low δ13C values (as low as −6‰ VPDB), light rare earth elements enrichment and significantly elevated Y/Ho ratios (86 ± 59.3), likely related to the oxidation of organic matter during thermochemical sulfate reduction (TSR). Consequently, diagenetic fluid may have evolved from: Cambrian seawater, meteoric water, shallow-buried seawater-dominated pore water, medium-deep-buried ferrous-rich pore water, lately high-salinity hydrothermal fluid-dominated pore water and finally to acidic fluids related to TSR dissolution. Reservoir quality is enhanced by hydrothermal pulses and TSR in deep-burial settings. This study is significant for those concerned with the formation of deep-buried carbonate reservoirs.

Rare earth elements - Source and evolution in an aquatic system dominated by mine-Influenced waters

Acid mine drainage (AMD), formed by the instability of sulfides, typically generates acidity and releases potentially toxic elements and sulfate to the environment, among other pollutants. An example is the group of rare earth elements (REE) that may have high toxic behavior. This toxicity leads to degradation of soils, water reservoirs and rivers, promoting serious risks for the ecosystems. So, the main goal of the present work is to study the hydrochemical properties of a system with mine-influenced waters during the rainy season, focusing on the origin, evolution/behavior, and concentration of REE. The study area is the São Domingos mining complex, located in one of the largest metallogenetic provinces in the world (Iberian Pyrite Belt), known by the evidences of AMD contamination. The obtained results reveal extraordinarily low pH (0.4), high electrical conductivity, reaching 26,200 μS/cm, and high values of sulfate and acidity. Regarding the REE, the determined concentration exceeded that observed in normal pH of neutral freshwaters by 2–3 times the order of magnitude. The results revealed that Y and Ce are distinguished in practically all sampled sites, due to its higher concentrations, with maximum values of 221.8 and 166.9 μg/L. In general, the concentrations increase as the water pH decreases. The statistical analysis indicates that REE elements may have a common origin, mutual dependence, and similar behavior during transport with typical AMD elements and composition of host rocks. Most samples show enrichment in middle REE (MREE) (Gdn/Lun), like the classic signature of AMD. In turn, colloids and AMD-precipitates may be participating in the incorporation of these elements. Therefore, due to potential risk of impacts on ecosystems, REE are a topic of relevant interest for future studies in order to assist monitoring processes and help government decisions related to water quality management.

Paleoceanographic reconstruction of the Ediacaran Dengying Formation, Sichuan Basin, Southwest China: Implications for the origin of Precambrian microbial carbonates

Abundant microbial carbonates with well-preserved primary textures occur in the upper Ediacaran Dengying Formation in the Sichuan Basin, southwest China, providing an opportunity to study the paleoceanographic conditions and the origin of Precambrian microbial carbonates. However, paleoenvironmental studies of these microbial carbonates are relatively rare, especially with respect to the comparison between the upper and lower parts of the Dengying Formation. In this paper, we present new analyses of carbon and oxygen isotopes and major, trace, and rare earth elements (REEs) for carbonate rocks from the Dengying Formation, in order to reveal the paleoceanographic redox and salinity conditions of the seawater from which these rocks were deposited. These rocks have shale-normalized REE and Y patterns that display weak negative Ce anomalies, weak positive Eu anomalies, and moderate middle REE enrichment, indicating the suboxic seawater for their deposition. From the lower to upper parts of the Dengying Formation, negative Ce anomalies become more prominent, while positive Eu anomalies and middle REE enrichment weaken, suggesting a gradual increase in the seawater oxygen concentration. The heavier oxygen isotopes of the carbonate matrixes and fibrous cements in the second member of the lower part of the Dengying Formation reflect a higher seawater salinity, conforming to the thick evaporates in the second member. The elevated oxygen content and decreased salinity in the seawater promoted the emergence of metazoans that inhibited the growth of microbes, causing the decreasing development of microbial carbonates in the upper part of the Dengying Formation compared to the lower part.

The mobility of thorium, uranium and rare earth elements from Mid Ordovician black shales to acid waters and its removal by goethite and schwertmannite

Previous studies have addressed the occurrence of Acid Rock Drainage (ARD) affecting La Silva stream due to the generation of large dumps of Middle Ordovician black shales during the construction of a highway close to El Bierzo (León, Spain). This ARD was characterized by sulphated acid waters with high concentration of heavy metals and anomalies in dissolved thorium (Th) and uranium (U). In the present study, we analyse in depth black shales and water, streambed sediments and precipitates of La Silva stream and its tributaries using different petrographic, mineralogical and geochemical approaches. Black shales, with average Th and U contents of 20 and 3 μg/g respectively contain disseminated detritic micro-grains of high weathering-resistant minerals, such as monazite and xenotime, that present smaller amounts of yttrium and rare earth elements (REY) and other elements as Ca, U, Th, Si and F. Results of the affected waters by ARD show an enrichment in dissolved Th, U and REY of several orders of magnitude with respect to natural waters. Sampled precipitates were mainly schwertmannite (Fe8O8(OH)8-2x (SO4)xO16•nH2O) and goethite (α–Fe3+O(OH)) that showed an enrichment of Th (up to 798 μg/g) and REY, due to the presence of dissolved anionic species (e.g. Th(SO4)32−, REY(SO4)32−) that enables their adsorption. Furthermore, these black shales show a clear enrichment in REE (Rare Earth Elements) with respect to NASC (North American Shales Composite) normalized REE patterns. Likewise, normalized REE patterns of stream waters and precipitates clearly show convex curvatures in middle-REE (MREE) with respect to light- and something less than heavy-REE, indicating the trend towards MREE enrichment. These findings are essential to evaluate the impact of ARD of Mid Ordovician shales in the surrounding environment, and to start considering these site as potential source of REE and critical raw materials, activating a Circular Economy.

Rare earth element geochemistry of Middle Devonian reefal limestones of the Dianqiangui Basin, South China: implications for nutrient sources and expansion of the reef ecosystem.

The Givetian Age witnessed the greatest expansion of stromatoporoid-coral reefs from low to higher latitudes of the Phanerozoic. Multi-proxy seawater surface temperature reconstruction suggests the establishment of a super-greenhouse climate as a major reason for reef expansion, yet many questions remain. This article presents the results of a rare earth element and yttrium (herein referred to as REY, derived from REE + Y) geochemical study as well as mineralogy and oxygen isotope values of two well-documented Middle Givetian reefal carbonate sections (Jiwozhai and Buzhai) of the Jiwozhai Formation of South China. The nearshore Jiwozhai patch reef succession displays greater biodiversity and more abundant coral than the marginal platform Upper Buzhai reef. Reefal and micritic carbonates of the Jiwozhai section are characterized by shale-like post-Archean Australian Shale (PAAS)-normalized REY patterns, by very weak negative Ce anomaly values (Ce/Ce* 0.80–0.96; average = 0.89), slightly elevated Y/Ho values (28.9–39.1; average = 34.1), and near-unity values of (Pr/Yb)N (average = 0.87), (Pr/Tb)N (average = 0.80), and (Tb/Yb)N (average = 1.09). Moreover, REY patterns of deposits of the Jiwozhai section differ markedly from those of modern seawater. The described geochemical aspects of the Jiwozhai section and the positive correlation of REY and Th contents displayed by the section point to a terrestrial siliciclastic contribution contemporaneous with reef-building. In contrast, REY patterns of the Upper Buzhai reef section samples are similar to those of modern seawater characterized by light rare earth element (LREE) depletion (average (Pr/Yb)N = 0.76), negative Ce anomalies (average Ce/Ce* = 0.88), and average super-chondritic Y/Ho ratios (average = 45.4)). Slightly positive Eu anomalies (Eu/Eu* = 0.93–1.94; average = 1.36) of the Upper Buzhai reef section samples are attributed to the negligible effect of hydrothermal fluids. Middle REE (MREE) enrichment (average (Tb/Yb)N = 1.48) of Buzhai section carbonate samples and positive correlation of REY and Th suggest a riverine input. Combined with siliciclastic mineralogy, oxygen isotope values, and reef-building biota morphology of the studied two sections, we suggest that terrestrial nutrients delivered by rivers far outweighed upwelling as a source of nutrients supplied to the Givetian reef ecosystem of South China. Coral and stromatoporoid in tropic oceans thrived in turbid water containing abundant terrestrial sediment and the nutrient-laden water helped expand reef-builder habitats during the Givetian time.

Dynamics of rare earth elements and associated major and trace elements during Douglas-fir (Pseudotsuga menziesii) and European beech (Fagus sylvatica L.) litter degradation

Abstract. Given the diverse physico-chemical properties of elements, we hypothesize that their incoherent distribution across the leaf tissues, combined with the distinct resistance to degradation that each tissue exhibits, leads to different turnover rates among elements. Moreover, litter layers of varying ages produce diverse chemical signatures in solution during the wet degradation. To verify our hypothesis, Na, K, Mg, Mn, Ca, Pb, Al and Fe were analysed together with the rare earth elements (REE) in the solid fractions and in the respective leachates of fresh leaves and different litter layers of two forested soils developed under Pseudotsuga menziesii and Fagus sylvatica L. trees. The results from the leaching experiment were also compared with the in situ REE composition of the soil solutions to clarify the impact that the litter degradation processes may have on soil solution chemical composition. Both tree species showed similar biogeochemical processes dominating the element dynamics during litter degradation. REE, Al, Fe and Pb were preferentially retained in the solid litter material, in comparison with the other cations, and their concentrations increased over time during the degradation. Accordingly, different litter fractions produced different yields of elements and REE patterns in the leachates, indicating that the tree species and the age of the litter play a role in the chemical release during degradation. In particular, the evolution of the REE patterns, relative to the age of the litter layers, allowed us to deliver new findings on REE fractionation and mobilization during litter decay. Specifically, the degradation of the litter was characterized by a decrease in the Y/Ho ratio and an increase in the LaN/YbN ratio. The relationship between these ratios provided information on the litter species-specific resistance to degradation, with Douglas-fir litter material showing a lower resistance. During the litter degradation of the two tree species, two main differences were highlighted with the help of the REE: (i) in Pseudotsuga menziesii the behaviour of Eu appeared to be linked to Ca during leaf senescence and (ii) species-specific release of organic acids during litter degradation leads to a more pronounced middle REE (MREE) enrichment in the Fagus sylvatica leachates. Finally, we showed the primary control effect that white fungi may have in Ce enrichment of soil solutions, which appears to be associated with the dissolution and/or direct transport of Ce-enriched MnO2 accumulated on the surface of the old litter due to the metabolic functioning of these microorganisms. Similar MREE and heavy REE (HREE) enrichments were also found in the leachates and the soil solutions, probably due to the higher affinity of these elements for the organic acids, which represent the primary products of organic matter degradation.

A Reconnaissance Study of Rare Earth Elements Systematic in Phosphate Coprolites: Comparison between Continental Shelf and Intracontinental Basin Deposits

The behavior of rare earth elements (REE) in phosphate coprolites; deposited in marine upwelling shelf system (Iraq) and a condensed section of the intracontinental basin (Czech Republic) is compared and discussed in the present study. The eight coprolite samples show that the REE incorporated in the apatite of these phosphatized faecal trace fossils have significantly different behavior in the two sedimentary regimes and hold the REE source’s signature in the local sedimentary conditions. The behavior of heavy REE, light REE, Ce-anomaly and shale-normalized ratios of Ce/La, Sm/Yb and Pr/Ce can be mainly attributed to REE fractionation at the source. In contrast, middle REE enrichment may be attributed to local fractionation below the sediment-water interface. Nd/La and REE/P2O5 ratios indicate local sedimentation rate and residence time in contact with seawater. Elevated La/Yb ratios indicate shallowing and submarine reworking events. Most of the REE patterns in the studied coprolites were acquired in the early stages of diagenetic phosphatization and crystallization of the apatite, and minor modifications took place later. The REE behavior in phosphate coprolites proved useful indicators of marine sedimentary environments in the present reconnaissance study and encourage further work on phosphate coprolite samples from other world deposits.

The potential for REEs in igneous-related apatite deposits in Europe

Abstract Phosphate rocks and rare earth elements (REEs) as potential by-products are listed as Critical Raw Materials (CRMs) by the European Commission. In Europe, igneous-related phosphate deposits are associated with carbonatites, alkaline complexes, (ultra)mafic intrusions, iron oxide–apatite (IOA) and iron oxide–copper–gold (IOCG) mineralization, and granites or are formed in a metasomatic/hydrothermal context. To provide an overview of these deposits and assess their potential in CRMs, a database gathering in situ analyses of apatite was compiled. The data emphasize the significant REE enrichment of apatite related to alkaline complexes and carbonatites. They also guide the use of apatite in mineral exploration, based on distinct geochemical characteristics. Among the latter are the Sr, Mn, total REE and Y contents of apatite, the degree of light and middle REE enrichment, the Eu anomaly, and the tetrad effect. Additional bulk-rock analyses combined with estimates of reserves/resources of the deposits indicate a sub-economic potential of REEs to be exploited as by-products of phosphate mining at Kodal, Bjerkreim–Sokndal and in the northern Norrbotten district (Sweden). This study helps to identify new deposits/areas of interest for CRM exploration in Europe that could contribute to decreasing the supply risk for these raw materials through domestic production.

Gadolinium-dominant monazite and xenotime: Selective hydrothermal enrichment of middle REE during low-temperature alteration of uraninite, brannerite, and fluorapatite (the Zimná Voda REE-U-Au quartz vein, Western Carpathians, Slovakia)

AbstractA hydrothermal quartz vein with REE-U-Au mineralization in the Zimná Voda (Gemeric Unit, Western Carpathians, Slovakia) is associated with contact metamorphism between Permian granites and host phyllites and metaquartzites. It contains unique REE minerals of the monazite and xenotime groups. Monazite-(Ce), monazite-(Nd), monazite-(Sm), and Gd-dominant monazite [“monazite-(Gd)”], along with xenotime-(Y) to Gd-dominant xenotime [“xenotime-(Gd)”] and Gd-rich hingganite-(Y) show heterogeneous compositions and reflect a strong fractionation trend toward the enrichment of MREE (Sm to Dy), particularly Gd. Here, the gadolinium abundance reported in “monazite-(Gd)” (≤23.4 wt% Gd2O3) and Gd-rich xenotime-(Y) to “xenotime-(Gd)” (≤28.7 wt% Gd2O3) and accompanied by Gd-rich hingganite-(Y) (≤15.8 wt% Gd2O3), is among the highest Gd concentrations ever reported in natural minerals. The Gd-richest compositions show the following formulas: (Gd0.31Sm0.24 Nd0.15Ce0.10La0.05Dy0.03Y0.03…)0.98PO4 [“monazite-(Gd)”], (Gd0.36Y0.32Dy0.13Sm0.08Tb0.05…)0.98 (P0.96As0.04)1.00O4 [“xenotime-(Gd)”] and (Y0.71Gd0.43Dy0.23Sm0.22Tb0.06Er0.04Nd0.06…Ca0.06)1.96 (☐0.87Fe0.132+)1.00(Be1.82B0.18)2.00(Si1.90As0.10)2.00O8(OH1.70O0.30)2.00 [hingganite-(Y)]. The MREE-rich monazites, xenotimes, and hingganite-(Y) precipitated in response to the alteration of primary uraninite, brannerite, and fluorapatite by low-temperature hydrothermal fluids of heterogeneous compositions on a microscale. These are responsible for the strong enrichment of individual MREE, especially Gd in the secondary minerals. This is accompanied by the advancing development of the W-type tetrad effect on REE through monazite species. The substantial incorporation of Gd into both REE-selective monazite and xenotime structures that are accompanied by LREE vs. HREE segregation indicates the possibility of differently sized REE3+ miscibility in REEPO4 solid solutions, as well as the stabilization of the Gd-rich orthophosphate structure by substitution of the remaining A-site cations with smaller HREE+Y in the xenotime-type, and/or larger LREE in the monazite-type structure.

Effects of in situ leaching on the origin and migration of rare earth elements in aqueous systems of South China: Insights based on REE patterns, and Ce and Eu anomalies

In situ leaching of ion-adsorption rare earth element (REE) deposits has released large amounts of REE-containing wastewater. However, the origin, speciation, distribution and migration of REEs in aqueous systems of the mining catchment are poorly understood. Groundwater, surface water, in situ leachates and weathered granite soil samples were collected from a catchment affected by mining activities in South China. The REE concentrations in groundwater (6.18 × 10–3–0.49 μmol L–1) and surface water (2.54–44.05 μmol L–1) decreased from upstream to downstream. REEs in groundwater were detected in organic matter associated (FA-REE) colloids, while the REE3+ and REE(SO4)+ were converted to REE(CO3)+ and FA-REE colloids from leachates and upstream surface water to downstream. The REE patterns of leachates and upstream groundwater (light and middle REE enrichment) resembled those of soil, but showed heavy REE enrichment due to FA-REE colloids in the downstream. REE in surface water were derived from middle REE enriched leachate. The Ce and Eu anomalies in the water samples indicated the REE origin (i.e., mining activities) and the hydrological variations (e.g., oxidation environment and water-rock interaction). Our results reveal the origin and fate of REE in aqueous systems of ion-adsorption REE mining catchments.

Enrichment and Fractionation of Rare Earth Elements in an Estuarine Marsh Soil Receiving Acid Discharges from Legacy Sulfide Mine Wastes

This paper provides new insights into the geochemical cycling of rare earth elements (REEs) in acid sulfate soils developed on salt marsh sediments of the Huelva estuary (Spain) as a result of sulfide mineral oxidation in abandoned ore stockpiles. The study was aimed at determining the REE abundance, fractionation pattern and mineralogical control of the dispersal and retention of REEs in the soil system. Forty-one samples were collected at 13 core sampling sites along two transects extending across the degraded marshland, and they were subjected to XRD, ESEM-EDS and ICP-MS analyses. Measurements revealed that the soil receiving acid discharges has relatively high concentrations of ΣREEs (174.77 ± 19.77 mg kg−1) compared to local baseline concentrations. Shale-normalized REE patterns are generally flat, but a slight middle REE (MREE) enrichment is consistently apparent in all soil samples, involving relatively low LaN/GdN ratios (0.83 ± 0.08) and GdN/LuN ratios up to 1.42. The convex-upward REE pattern supports the possibility that iron oxy-hydroxide minerals play an important role in MREE retention through adsorption and co-precipitation mechanisms. Efflorescent sulfate salts left on the topsoil by the evaporation of acid waters show a strong depletion of light REEs (LaN/GdN = 0.16 ± 0.10) and act as a temporary reservoir of labile MREEs and heavy REEs during dry periods.