Rare Earth Element Variations Research Articles

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

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

Assessment of rare earth elements variations in five water systems in Beijing: Distribution, geochemical features, and fractionation patterns

This study investigates the distribution of rare earth elements (REEs) within the Beijing water system, specifically examining the Yongding, Chaobai, Beiyun, Jiyun, and Daqing rivers. Results indicate that the Beiyun River exhibits the highest REE concentrations, ranging from 35.95 to 59.78 μg/mL, while the Daqing River shows the lowest concentrations, ranging from 15.79 to 17.48 μg/mL. LREEs (La to Nd) predominate with a total concentration of 23.501 μg/mL, leading to a notable LREE/HREE ratio of 7.901. Positive Ce anomalies (0.70–1.11) and strong positive Eu anomalies (1.38–2.49) were observed. The study suggests that the Beijing water system's REEs may originate from geological and anthropogenic sources, such as mining and industrial activities in neighboring regions, including Inner Mongolia. These findings underscore the importance of ongoing monitoring and effective water management strategies to address REE-related environmental concerns.

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

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

Petrogenetic and geochemical constraints on ca. 1.89–1.88 Ga Bastanar mafic dyke swarm, Bastar craton, India: Insights into MORB- and OIB-type contributions and interactions with metasomatized subcontinental lithospheric mantle

The Bastar craton of the Indian Shield hosts several generations of mafic dyke swarms of various trends, compositions, and ages, which span from ca. 2.7 Ga to 1.42 Ga. This study focuses on geochemical attributes of the ca. 1.89–1.88 Ga NNW-trending Bastanar swarm, aiming to address a perceived discrepancy between its arc-like geochemistry and the influence of a heterogeneous mantle source. To resolve the intra-swarm geochemical variations, we conducted a comprehensive geochemical characterization and petrogenetic interpretation of the ca. 1.89–1.88 Ga Bastanar swarm. The samples from this swarm are categorized into two distinct groups, primarily based on their geochemical composition. The Group 1 samples exhibit higher TiO2 (1.06–1.86 wt%), (La/Yb)N (7.2–8.6), (Gd/Yb)N (2- 2.27), Nb (14.6–16.6 ppm), Th (1.23–3.03 ppm) and Zr (104–118.72 ppm) concentrations than the Group 2 samples. Furthermore, rare-earth element patterns and variations in high-field strength element contents in the Group 1 samples suggest derivation from a deeper, less depleted mantle source resembling an OIB/less MORB-type. This inference is further supported by higher TiO2/Yb, Zr/Nb, and Nb/Y ratios. In contrast, the Group 2 samples indicate derivation from a shallower, more MORB/less OIB-type depleted mantle source, as evidenced by lower TiO2/Yb, Zr/Nb, and Nb/Y ratios. Variations in Dy/Yb and Gd/Yb ratios confirm the involvement of variable mantle sources, implying the derivation of the Group 1 and 2 samples from garnet-rich and spinel-rich lherzolite mantle sources, respectively. The absence of consistent negative Nb-Ta-Ti anomalies in the Group 1 samples suggests an uncontaminated nature, ruling out any role of crustal contamination. On the other hand, the Group 2 samples display negative Nb-Ta-Ti anomalies with enriched LREE and LILE patterns, indicating the involvement of crustal components in their genesis. A trace-element modelling suggests that the ca. 1.89–1.88 Ga mafic dyke swarm exhibits significant intra-swarm variability, with at least two distinct source components contributing to its genesis – a depleted MORB-type and an enriched OIB-type mantle. Notably, the geochemical characteristics of the Group 2 samples suggest interaction with a metasomatized mantle source, possibly enriched by fluids from an earlier subducted slab. Geochemical evidence presented in this work supports Archean subduction-related processes for the crustal growth of the Bastar craton and highlight the enduring influence of a metasomatized sub-continental lithospheric mantle on subsequent magmatism over millions of years.

Rare earth element enrichment in sedimentary phosphorites formed during the Precambrian–Cambrian transition, Southwest China

Numerous sedimentary phosphorites in Southwest China were formed around the Precambrian–Cambrian transition (PC–C), including the upper Ediacaran Doushantuo Formation and lower Cambrian Gezhongwu Formation. The Gezhongwu phosphorites in Zhijin exhibit marked rare earth element (REE) enrichment (>1000 ppm), and may represent new REE resources. Although the main characteristics of the Gezhongwu phosphorites have been well constrained, the REE enrichment mechanisms remain unclear. We undertook a comparative study of three typical sedimentary phosphorites with variable REE contents formed at the PC–C transition in central Guizhou Province, Southwest China. These include sections A and B of the Doushantuo phosphorites (560 ± 8 Ma) from the Weng’an area (i.e., WA-A and WA-B), and the Gezhongwu phosphorites (527 ± 24 Ma) from the Zhijin area (ZJ). The phosphorites were investigated with state-of-the-art macroscale to nanoscale analytical techniques. In contrast to the extraordinary REE enrichment in the ZJ phosphorites (average ΣREE = 1157 ppm), the phosphorites in WA-A (average ΣREE = 234 ppm) and WA-B (average ΣREE = 114 ppm) are REE-poor. Elemental mapping by laser ablation–inductively coupled plasma–mass spectrometry, along with transmission electron microscopy analyses, showed the REEs in the studied phosphorites are hosted in nanoscale francolites. The 87Sr/86Sr and Y/Ho ratios of the francolite grains indicate that greater terrigenous input may have led to more REE enrichment in the WA-A than WA-B phosphorites, but this cannot explain the extraordinary REE enrichment in the ZJ phosphorites. The F/P2O5 values of the francolite grains in the ZJ phosphorites (∼0.097) are higher than those in the WA-A (∼0.084) and WA-B (∼0.084) phosphorites, and the grain size of the francolite in the ZJ phosphorites (∼89.9 nm) is larger than those in the WA-A (∼56.6 nm) and WA-B (∼57.4 nm) phosphorites, indicative of more intense reworking of the ZJ than WA phosphorites during early diagenesis. A plot of Nd concentration versus Ce/Ce* reveals that lower sedimentation rates characterized the ZJ phosphorites. Therefore, intense sedimentary reworking during early diagenesis resulted in more REEs being sequestered by the marine phosphates from seawater and pore waters at a lower sedimentation rate, which resulted in the extraordinary REE enrichment in the ZJ phosphorites. Our findings highlight the multiple factors that controlled formation of sedimentary phosphorites around the PC–C transition (especially the intense reworking and redox conditions of the overlying seawater), and provide further insights into REE enrichment in sedimentary phosphorites worldwide.

Geochemistry of dissolved rare earth elements in the Lancang River with cascade dams and implications for anthropogenic impacts

Anthropogenic effects like the construction of cascade dams are increasingly affecting the biogeochemical cycles of rare earth elements (REE) in rivers. However, our understanding on the REE compositions of dissolved loads in rivers under the effect of cascade dams remains limited. In this study, forty-four water samples in the Lancang River were analyzed for REE concentrations to assess the impact of cascade dams. The results showed that total dissolved REE concentrations ranged from 4.0 to 65.7 ng/L, with an average value of 21.8 ng/L. The concentrations in the middle (519.6 ng/L) and lower (331.5 ng/L) reaches were higher than those in the upper reaches (108.1 ng/L). All river samples showed (La/Yb)N values < 1, and the PAAS-normalized REE patterns indicated a substantial enrichment of heavy REE, characterized by negative Ce (0.1–0.9) and positive Eu (1.5–32.1) anomalies. The enrichment of heavy REE can be attributed to their preferential release from minerals during the weathering process and their interaction with inorganic complex anions. The negative Ce anomaly observed is likely the result of redox conditions, while the positive Eu anomaly was inherited from the REE characteristics of the source rocks. Moreover, the Ce anomaly decreased to 0.29 in the Huangdeng reservoir and 0.12 in the Dachaoshan reservoir. The value of Ce anomaly displayed a sharp decline in the middle and lower reaches affected by the cascade reservoirs. The effect of the dams played an important role in Ce anomaly by decreasing the DOC concentrations, and rivers with low DOC concentrations are commonly associated with negative Ce anomaly. This study revealed that cascade dams paly an essential role in the variation of REE in dissolved loads and REE anomaly may have the potential to track anthropogenic activities.

Fluid-mineral dynamics at the Rincón de la Vieja volcano—hydrothermal system (Costa Rica) inferred by the study of major, minor and rare earth elements in the hyperacid crater lake

Volcanic lakes are complex natural systems and their chemical composition is related to a myriad of processes. The chemical composition of major, minor, Rare Earth Elements (REE) and physico-chemical parameters at the hyperacid crater lake of Rincón de la Vieja volcano (Costa Rica) are here investigated during February 2013–August 2014. The study of the lake chemical composition allows to identify the main geochemical processes occurring in the lake and to track the changes in the volcanic activity, both important for active volcanoes monitoring. The total REE concentration (∑REE) dissolved in the crater lake varies from 2.7 to 3.6 mg kg−1 during the period of observation. REE in the water lake samples normalized to the average volcanic local rock (REEN-local rock) are depleted in light REE (LREE). On the contrary REEN-local rock in the solids precipitated (mainly gypsum/anhydrite), from lake water samples in laboratory at 22°C, are enriched in LREE. The low variability of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios (0.92–1.07 and 0.66–0.81, respectively) in crater lake waters is consistent with the low phreatic activity (less than 10 phreatic eruptions in 2 years) observed during the period of observation. This period of low activity precedes the unrest started in 2015, thus, it could be considered as a pre-unrest, characterized by infrequent phreatic eruptions. No clear changes in the REE chemistry are associated with the phreatic eruption occurred at mid-2013. The results obtained investigating water-rock interaction processes at the Rincón de la Vieja crater lake show that rock dissolution and mineral precipitation/dissolution are the main processes that control the variability of cations composition over time. In particular, precipitation and dissolution of gypsum and alunite are responsible for the variations of REE in the waters. Despite the low variations of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios, this study allows to suggest that REE can be used, together with major elements, as practical tracers of water-rock interaction processes and mineral precipitation/dissolution at active hyperacid crater lakes over time, also during periods of quiescence and low phreatic activity.

Response of trace and rare earth elements to environmental changes in a stalagmite from southern India for the last deglaciation

Speleothems, particularly stalagmites are extensively used to reconstruct paleoclimatic and paleomonsoon changes by using stable oxygen and carbon isotopes along the growth profile of a stalagmite sample. Trace and rare earth elements (REEs) variations in stalagmites are widely recognized as indicators of past precipitation and local hydrology. The amalgamation of isotopic and trace element proxies in speleothems has been regarded as an important tool to infer past climate and hydro-chemical fluctuations. Current advancements in geochemical techniques have enabled us to generate high-resolution paleo-records of almost all trace and REEs from stalagmites. However, their assessment is dependent on numerous factors that control the formation of a stalagmite.Here we present a geochemical record from a well dated stalagmite (VSPM1) from a cave located in the southern India. The stalagmite grew between 15,610 and 13,160 yr BP as revealed by its StalAge modelled ages from eight U–Th dates. This study demonstrates significant variations in trace and REEs during the last deglacial time interval of 2100 years and suggests variations in drip water chemistry. The relative amount of trace elements in colloidal solutions originating from the soil organics and weathered particles of host dolomitic rock may have altered with climatic changes. It appears that trace and REEs of VSPM1 stalagmite have responded to fluctuations in Indian Summer Monsoon (ISM) intensity during the time interval of this study.

Synchronous formation of the ‘forearc’ Bay of Islands ophiolite and its basal high-temperature metamorphic sole constrained by U–Pb zircon ages

The welded metamorphic sole at the base of the Bay of Islands Ophiolite Complex (BOIC) in the Northern Appalachians of Newfoundland shows a typical inverted pressure-temperature (P-T) metamorphic gradient from HT-MP granulite to LT-LP greenschist facies. It incorporates mafic volcanic/plutonic protoliths mixed with pelagic, hemi-pelagic and coarser epiclastic sedimentary protoliths. New LA-ICP-MS U–Pb concordia ages, trace elements, and Ti-in-zircon geothermometry for ∼250 zircon analyses from three metabasites of the upper HT sole amphibolites with N-MORB-like protoliths are reported. Two samples collected within meters of the ophiolite peridotite-sole contact of the Blow Me Down Mountain and North Arm Mountain massifs yielded the oldest comparable concordia ages of 487.7±2.6 Ma and 489.1±3.1 Ma, respectively, that are both within error of the igneous age of 488.3±1.5 Ma of the directly overlying BOIC ophiolite, which formed at a supra-subduction zone (SSZ) forearc spreading center. A third slightly younger age of 484.2±2.4 Ma was obtained for an upper HT amphibolite sample with similar phase assemblages but collected ∼30 m below the peridotite contact of the Table Mountain massif. Zircon crystals analyzed have similar size and morphologies, subparallel rare earth element (REE) variation patterns, and steep heavy REE-enrichments ((Lu/Gd)cn >20), significant positive Ce anomalies (dominantly >5) and slight positive to dominantly negative Eu anomalies (1.2 – 0.4). Zircon shows Th/U mean values of 0.37 – 0.48 with little to no rim to core variation. Minimum Ti-in-zircon mean crystallization temperatures range from ∼764 – 787 °C. These neocrystallized zircon crystals appear to be derived from thin leucosomes within the three amphibolites. Two other samples also from the upper HT sole show evidence of inherited detrital zircon with core dates spanning the Cambrian Notre Dame Arc through older Laurentian-like basement and rift age ranges.Subcretion of the sole took place below a hot forearc asthenospheric wedge, that is, a consequence of the newly-formed BOIC forearc spreading center extending from the back arc to a triple junction along the westward- (or paleo-northward) verging trench of the Notre Dame arc. The early HT sole formation age at ca. 489–488 Ma is long prior to initiation of obduction at ca. 470 Ma and long after initiation of subduction beneath the paleo-northward verging Notre Dame peri-Laurentian arc at ca. 514 Ma. This indicates Newfoundland sole ages of the BOIC and St. Anthony Complex are correlated with the age of SSZ spreading, but not necessarily subduction initiation because previously existing and self-sustaining subduction was ongoing. Sole ages are then not correlated with the younger age of obduction-related orogenic events (e.g., proposed Taconic I and II) in the Newfoundland Appalachians.

Insight study of rare earth elements in PM2.5 during five years in a Chinese inland city: Composition variations, sources, and exposure assessment

The booming development of rare earth industry and the extensive utilization of its products accompanied by urban development have led to the accelerated accumulation of rare earth elements (REEs) as emerging pollutants in atmospheric environment. In this study, the variation of REEs in PM2.5 with urban (a non-mining city) transformation was investigated through five consecutive years of sample collection. The compositional variability and provenance contribution of REEs in PM2.5 were characterized, and the REEs exposure risks of children and adults via inhalation, ingestion and dermal absorption were also evaluated. The results showed an increase in the total REEs concentration from 46.46 ± 35.16 mg/kg (2017) to 81.22 ± 38.98 mg/kg (2021) over the five-year period, with Ce and La making the largest contribution. The actual increment of industrial and traffic emission source among the three pollution sources was 1.34 ng/m3. Coal combustion source displayed a downward trend. Ingestion was the main exposure pathway for REEs in PM2.5 for both children and adults. Ce contributed the most to the total intake of REEs in PM2.5 among the population, followed by La and Nd. The exposure risks of REEs in PM2.5 in the region were relatively low, but the trend of change was of great concern. It was strongly recommended to strengthen the concern about traffic-related non-exhaust emissions of particulate matter.

Plate tectonics in action in the Mesoarchean: Implication from the Olondo greenstone belt on the Aldan Shield of Siberian Craton

The Archean Olondo greenstone belt (OGB) is located on the Aldan shield, the largest basement of the Siberia craton. With well-preserved abundant mafic-ultramafic rocks, ≥30% in volume, the OGB is unique among other greenstone belts in the world. In this study, we present the most up-to-date geochemical and isotopic data for the ultramafic-mafic rocks of the OGB, in order to better constrain their mantle sources and the plate tectonic process involved in the formation of OGB at ca. 3 Ga. The ultramafic rocks vary from fresh to serpentinized dunites, and are highly refractory as residual mantle phase as indicated by depletion in P-Platinum Group Elements (PGE) relative to I-PGEs for highly siderophile elements (HSE). Fresh dunites show U-shaped rare earth element (REE) patterns, with positive to negative Nb anomalies, indicative of late metasomatism in their mantle source. Rhenium-Osmium isotopic compositions of these dunites yield mantle model age (TMA) of 2960–3020 Ma, comparable to the formation age of the OGB at ca. 3 Ga. Together, the data suggest that, unlike mantle cumulate origin for most of the Archean ultramafic rocks, the OGB dunites were mantle residuals after a high degree of partial melting (>30%), which subsequently interacted with the subduction-related melt/fluid. On the other hand, the OGB mafic rocks including komatiitic and tholeiitic basalts show geochemical characteristics relative to the ultramafic residuals that reinforce a subduction-related regime as their formation setting, despite extra mid-ocean ridge and plume settings. Tholeiitic basalts yield variable REE patterns from depleted, chondritic, to enriched light rare earth elements (LREE) patterns, with variable Nb-Ta anomalies, indicating their similarities with modern N-MORB and boninites, comparable to mafic rocks in typical supra-subduction zone (SSZ) ophiolites. Such mafic rocks with combined lower εNd(t) and negative Nb-Ta anomalies were most likely the result of mixing with subducted components, consistent with the observed Nb depletion in the residual dunites. The Al-depleted komatiitic basalts may have originated from deep mantle source, corresponding to garnet stability field, confirmed by their depletion in HREE and requiring a mantle plume to transport and melt at such a depth. The OGB ultramafic-mafic rocks could be a record to witness plume-induced subduction initiation processes such that mantle plume, sea-floor spreading and subduction were all in operation in the Mesoarchean time.

Trace element evidence for serial processing of the lunar flotation crust and a depleted bulk Moon

Plagioclase in lunar anorthositic crust have rare earth element (REE) patterns and Eu abundances which cannot be directly produced by lunar magma ocean (LMO) solidification. This is surprising as the LMO is invoked to explain the mineralogy of the crust, and other lunar surface and interior properties. We explored geological processes subsequent to LMO solidification that could reconcile anorthositic compositions with an LMO, finding that subsolidus reequilibration after addition of a minor KREEPy component successfully reproduces REE variations in natural samples. Monte-Carlo simulations used to constrain conditions of subsolidus reequilibration suggest the Moon has a light-REE depleted bulk composition. We propose a post-LMO serial processing model to reconcile the petrological, geochronological, and isotopic characteristics of lunar anorthosites and contemporaneous magmatism. If the bulk Earth is chondritic and the Moon accreted from material ejected from a depleted terrestrial reservoir, Earth underwent an early differentiation event prior to the Moon-forming giant impact.

High MREE-HREE solubility in a carbonatite-derived hydrothermal fluid: Evidence from fluorite-hosted fluid inclusions in the Amba Dongar carbonatite complex, India

Recent experimental works suggest that complexation with alkalis, carbonate, and hydroxyl groups enhances rare earth element (REE) transport and HREE/LREE fractionation, seen in carbonatite-hosted REE deposits. The Amba Dongar carbonatite complex in western India hosts fluorite and REE-fluorcarbonate mineralization occurring as vug/vein fillings or as disseminated ores associated with calcite, dolomite, apatite, baryte, and quartz. In this study, we analyzed the major and trace element composition of fluorite-hosted fluid inclusions, and the trace element chemistry of calcite and fluorite, using laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) to characterize the nature of the hydrothermal fluid and the processes of mineral-fluid interaction. Fluorite contains aqueous bi-phase (liquid + vapor) fluid inclusions of variable size that furnish low salinities (0.4–2.2 wt% NaCl equivalent) and liquid-vapor homogenization temperatures (130 °C–155 °C). The fluid inclusions have high concentrations of alkalis (Na, K), Si, Al, Mg, and Mn, and their chemistry resembles orthomagmatic fluid derived from evolved carbonatite melts. They also have elevated MREE and HREE concentrations relative to the LREE, that is significantly higher than in many other hydrothermal settings. Such fluids with fractionated LREE/HREE were likely derived from residual brines post the LREE-mineralization stage, when the HREE still remained in solution. This report of hydrothermal fluids with elevated MREE and HREE solubility from natural carbonatites supports experimental findings that alkali‑carbonate-hydroxyl complexation helps to mobilize REE and fractionate the LREE from MREE and HREE. Magmatic calcite has LREE-enriched REE patterns while those of hydrothermally-altered calcite is nearly flat. The secondary calcite also has elevated concentrations of Na and K, which suggests that the alkali-rich fluids scavenged the REE from magmatic calcite and redistributed them into more insoluble REE-fluorcarbonates. The REE patterns of fluorite mimic those of its fluid inclusions, with the inclusions containing higher and more variable REE concentrations, suggesting that the REE signals of fluorite are coming from the ablation of fluid inclusions, and not from fluorite themselves.

Tracing the effects of fO2, pressure and H2O on the ore-forming magmas: Perspective from zircon REE composition

Efforts have been devoted to explore if there are independent zircon trace element ratios that could be proxy of oxidation state and magmatic water content, and can distinguish between mineralization and barren granites. In this study, I evaluated the difference of the zircon elemental signatures between fertile magmatic suites (which host porphyry Cu-Mo, Mo, Cu-Au, Cu, Cu-Mo-Au, Mo-Cu, and Au deposits) and infertile I-type granites. The “potential” magmatic suites, which means that they are supposed to develop porphyry deposits based on the previously proposed ore-forming criteria (e.g., zircon Eu/Eu* > 0.5) and yet no associated mineralization has been found, were also included in this comparison. Most of the trace elemental signatures cannot differentiate the I-type granite zircons from fertile zircons and “potential” zircons, except for the Eu anomaly (∼0.5 < Eu/Eu* < ∼0.8 for ore-related and “potential” suites; ∼0.2 < Eu/Eu* < ∼0.5 for I-type granites) and middle/heavy rare earth element variation diagrams (MREE and HREE; e.g., Eu/Gd versus Gd/Yb, Lu/Yb versus Gd/Yb, Sm/Ho versus Sm/Lu, and Yb/Lu versus Dy/Lu). The behavior of zircon REE possibly indicate a more MREE-depleted signature for the ore-forming and “potential” suites. Taken together, zircon REE features documented in this study highlight the fractional crystallization of hornblende and garnet, and the delay of plagioclase crystallization, revealing the combined effect of high overlying pressure, high fO2 and high H2O (or H+) concentration on the differentiation of fertile magmas.

Abundance, spatial variation, and sources of rare earth elements in soils around ion-adsorbed rare earth mining areas

Rare earth elements (REEs) concentrated in soils have attracted increasing attention about their impact on soil health as emerging contaminants. However, the sources of REEs enriched in soils are diverse and need to be further investigated. Here, surface soil samples were collected from southern Jiangxi Province, China. REEs contents and soil physicochemical properties were determined, and cerium (Ce) and europium (Eu) anomalies were calculated. Moreover, we established a model to further identify the main sources of REEs accumulation in the studied soils. Results show that the abundance of soil REEs reveals larger spatial variation, suggesting spatially heterogeneous distribution of REEs. The median content of light REEs in soils (154.5 mg kg−1) of the study area was higher than that of heavy REEs and yttrium (35.8 mg kg−1). In addition, most of the soil samples present negative Ce anomalies and all the soil samples present negative Eu anomalies implying the combined effect of weathering and potential exogenous inputs on soil REEs. Positive matrix factorization modeling reveals that soil REEs content is primarily influenced by soil parent materials. Potential anthropogenic sources include mining-related leachate, traffic exhaust, and industrial dust. These results demonstrate that the identification of sources of soil REEs is an important starting point for targeted REEs sources management and regulation of excessive and potentially harmful REEs levels in the soil.

Mineralogy and Mineral Chemistry of the REE-Rich Black Sands in Beaches of the Kavala District, Northern Greece

The coastal area of the Kavala district, Northern Greece, is characterized by minerals enriched in rare earth elements (REE). The present study focuses on the mineralogy of the black sands from six different locations and the comprehensive mineral chemistry of the REE-bearing minerals, allanite-(Ce), epidote, monazite, thorite, zircon and titanite. Allanite-(Ce) is the most important carrier of light REE (LREE) in the studied black sands, reaching up to 23.24 wt % ΣREE. The crystal chemistry of allanite-(Ce) transitions into ferriallanite-(Ce), due to the significant involvement of Fe3+. High resolution backscattered electron (BSE) images were used to identify zoning that corresponds to variations in REE, Th and U. These modifications follow the exchange scheme: (Ca + (Fe3+, Al))−1(LREE, Y, Th, U + (Fe2+, Mg, Mn))+1. Epidotes may also contain up to 0.5 REE3+ apfu. Monazite and thorite are found as inclusions in allanite-(Ce) and are enriched in Ce, La and Nd, together with Th and U. Some zircons are enriched in Hf, while some titanites host Nb and V.

Scavenging and release of REE and HFSE by Na-metasomatism in magmatic-hydrothermal systems

Exploitable or potentially exploitable deposits of critical metals, such as rare-earth (REE) and high-field-strength elements (HFSE), are commonly associated with alkaline or peralkaline igneous rocks. However, the origin, transport and concentration of these metals in peralkaline systems remains poorly understood. This study presents the results of a mineralogical and geochemical investigation of the Na-metasomatism of alkali amphiboles and clinopyroxenes from a barren peralkaline granite pluton in NE China, to assess the remobilization and redistribution of REE and HFSE during magmatic-hydrothermal evolution. Alkali amphiboles and aegirine-augites from the peralkaline granites show evolutionary trends from sodic-calcic to sodic compositions, with increasing REE and HFSE concentrations as a function of increasing Na-index [Na#, defined as molar Na/(Na+Ca) ratios]. The Na-amphiboles (i.e., arfvedsonite) and aegirine-augites can be subsequently altered, or breakdown, to form hydrothermal aegirine during late- or post-magmatic alteration. Representative compositions analyzed by in-situ LA-ICPMS show that the primary aegirine-augites have high and variable REE (2194–3627 ppm) and HFSE (4194–16,862 ppm) contents, suggesting that these critical metals can be scavenged by alkali amphiboles and aegirine-augites. Compared to the primary aegirine-augites, the presentative early replacement aegirine (Aeg-I, Na# = 0.91–0.94) has notably lower REE (1484–1972) and HFSE (4351–5621) contents. In contrast, the late hydrothermal aegirine (Aeg-II, Na# = 0.92–0.96) has significantly lower REE (317–456 ppm) and HFSE (6.44–72.2 ppm) contents. Given that the increasing Na# from aegirine-augites to hydrothermal aegirines likely resulted from Na-metasomatism, a scavenging-release model can explain the remobilization of REE and HFSE in peralkaline granitic systems. The scavenging and release of REE and HFSE by Na-metasomatism provides key insights into the genesis of globally significant REE and HFSE deposits. The high Na-index of the hydrothermal aegirine might be useful as a geochemical indicator in the exploration for these critical-metals.

Diagenesis of Ediacaran − early Cambrian phosphorite: Comparisons with recent phosphate sediments based on LA-ICP-MS and EMPA

“Old phosphorite” deposits (Ediacaran to early Cambrian) located in Central Guizhou, South China, are hosted in carbonate and represent the earliest phosphogenesis. These old phosphorites, as well as Pliocene to Pleistocene and modern phosphate sediments (recent phosphorite) have been extensively studied. However, the possibility of recent phosphorite being the incipient stage of long-time phosphorite remains uncertain. Taking Weng’an (Ediacaran) and Zhijin (early Cambrian) phosphorites as examples, this study conducted in situ geochemical and mineralogical analyses of phosphate minerals (old apatites). Analogies between recent and old apatites were determined by comparing geochemistry based on rare earth elements (REE) and yttrium (REE + Y). Old phosphorite could be divided into authigenic grains and biodetritus, both comprising closely accumulated apatite nanocrystals. REE + Y concentrations (∑REE + Y) were much higher in the outer rim than in the inner core of biodetritus, whereas the authigenic grains showed relatively homogeneous REE + Y distributions. Three REE + Y patterns were observed: (1) “left-inclined” type, with no Ce anomalies; (2) shale-like pattern, with weak MREE enrichment and slightly negative Ce anomalies; (3) “hat-shaped” pattern, with notable MREE enrichment, evident HREE depletion, and remarkable negative Ce anomalies. Positive La, Gd, and Y anomalies, as well as MREE enrichment increased from type (1) to type (3), which can be explained by increasing degrees of oxidation. The REE + Y distributions of old apatites were similar to those of recent apatites, but exhibited MREE enrichment and HREE depletion and old authigenic apatites had no Ce anomalies. Furthermore, old apatite compositions lie in the diagenetic area on Y/Ho vs SmN/YdN plots. These characteristics indicate that old phosphorite could have been subjected to long-term diagenetic modification after burial, during which apatites recrystallized and absorbed REE + Y. Hence, it can be concluded that recent apatites could serve as predecessors of major ancient phosphorite, especially biogenic phosphorites. Globally, typical old phosphorites have quite variable REE + Y compositions, suggesting that the phosphorites experienced different depositional conditions and diagenetic alteration despite their contemporaneous formation. This study provides new data and insight on the diagenesis of old phosphorite and improves our deeper understanding of phosphogenesis in paleo- and modern environments.

Rare Earth Elements Variations in a Hyperacid Crater Lake and Their Relations With Changes in Phreatic Activity, Physico-Chemical Parameters, and Chemical Composition: The Case of Poás Volcano (Costa Rica)

Decades of geochemical monitoring at active crater lakes worldwide have confirmed that variations in major elements and physico-chemical parameters are useful to detect changes in volcanic activity. However, it is still arduous to identify precursors of single phreatic eruptions. During the unrest phase of 2009–2016, at least 679 phreatic eruptions occurred at the hyperacid and hypersaline crater lake Laguna Caliente of Poás volcano (Costa Rica). In this study, we investigate the temporal variations of Rare Earth Elements (REE) dissolved in Laguna Caliente in order to 1) scrutinize if they can be used as a new geochemical tool to monitor changes of phreatic activity at hyperacid crater lakes and 2) identify the geochemical processes responsible for the variations of REE concentrations in the lake. The total concentration of REE varies from 950 to 2,773 μg kg−1. (La/Pr)N-local rock ratios range from 0.93 to 1.35, and Light REE over Heavy REE (LREE/HREE)N-local rock ratios vary from 0.71 to 0.95. These same parameters vary in relation to significant changes in phreatic activity; in particular, the (La/Pr)N-local rock ratio increases as phreatic activity increases, while that of (LREE/HREE)N-local rock decreases when phreatic activity increases. REE concentrations and their ratios were compared with the variations of major elements and physico-chemical parameters of the lake. Calcium versus (La/Pr)N-local rock and versus (LREE/HREE)N-local rock ratios show different trends compared to the other major elements (Na, K, Mg, Al, Fe, SO4, and Cl). Moreover, a higher loss of Ca (up to 2,835 ppm) in lake water was found with respect to the loss of Al, K, and Na. This loss of Ca is argued to be due to gypsum precipitation, a process corroborated by the mass balance calculation simulating the precipitation of gypsum and the contemporaneous removal of REE from the lake water. The observed relations between REE, changes in phreatic activity, and the parameters commonly used for the monitoring of hyperacid volcanic lakes encourage investigating more on the temporal and cause-effect relationship between REE dynamics and changes in phreatic activity at crater lake-bearing volcanoes.

Geochemical behavior and fractionation characteristics of rare earth elements (REEs) in riverine water profiles and sentinel Clam (Corbicula fluminea) across watershed scales: Insights for REEs monitoring

The increasing global demand for rare earth elements (REEs) has led to their recognition as emerging contaminants; however, the effect that biota have on the cycling of these elements at the watershed scale is not currently well understood. In this study, water samples and field freshwater clams Corbicula fluminea were concurrently collected along watershed gradients, and concentration profiles of 14 naturally occurring REEs were measured in operationally defined water fractions and soft tissues of the freshwater clams. Moreover, Post Archean Australian Shale (PAAS) normalized REE patterns, fractionation indices, and anomalous values were determined to further extract characteristic features. As a result, both the water and biological samples had variable REE compositions, with higher concentrations of light REEs (LREEs) than middle REEs (MREEs) and heavy REEs (HREEs), while decreasing concentrations were generally observed as filter pore size decreased, implying that large colloidal and particulate fractions were important carriers of REEs. The spatial distribution patterns of REEs revealed a clear site effect among profiles, with variability more pronounced among watersheds and with peaks in sites from a small watershed near the hotspots of the mining area, and then exhibited a decreasing trend with distance from there. Meanwhile, significant bioaccumulation of REEs was observed potentially reflecting different degrees of contamination gradients among the watersheds. The PAAS-normalized distribution patterns tended to be slightly enriched in MREEs, producing a peculiar “roof-shaped” feature and characteristic fractionation. Remarkably, bio-concentration factors (BCFs) highlighted the importance of large colloidal and particulate phases in assessing biologically available REEs for filter-feeding species. Collectively, our study strongly favored that accumulation patterns and fractionation characteristics of REEs in C. fluminea can serve as a reliable indicator of geochemical behavior, providing a promising biomonitoring tool to quantitatively denote different degrees of REE contamination and assess possible impacts in mining watersheds.