Rare Earth Element Variability Research Articles

Spatial Variability of Rare Earth Elements in Groundwater in the Vicinity of a Coal-Fired Power Plant and Associated Health Risk.

This study investigated the occurrence and distribution of rare earth elements (REEs), including 14 lanthanoids, scandium (Sc), and yttrium (Y), in groundwater around a large coal-fired thermal power plant (TPP). The ICP-MS technique was used to analyze 16 REEs in groundwater samples collected from monitoring wells. REE concentrations ranged from 59.9 to 758 ng/L, with an average of 290 ng/L. The most abundant was Sc, followed by La, accounting for 54.2% and 21.4% of the total REE concentration, respectively. Geospatial analysis revealed the REE enrichment at several hotspots near the TPP. The highest REE concentrations were observed near the TPP and ash landfill, decreasing with the distance from the plant and the landfill. REE fractionation ratios and anomalies suggested the Light REE dominance, comprising over 78% of the total REEs. Correlation and principal component analyses indicated similar behavior and sources for most REEs. Health risk assessment found hazard indices (HI) of 1.36 × 10-3 and 1.98 × 10-3 for adults and children, respectively, which are far below the permissible limit (HI = 1). Likewise, incremental lifetime cancer risks (ILCR) were all below 1 × 10-6. Nevertheless, ongoing ash disposal and potential accumulation in the environment could elevate the REE exposure over time.

Rare Earth Element Variability in Italian Extra Virgin Olive Oils from Abruzzo Region.

Extra virgin olive oil is a food product from the Mediterranean area that is particularly and continuously experiencing to increasing instances of fraudulent geographical labeling. Therefore, origin protection must be improved, mainly based on its intrinsic chemical composition. This study aimed to perform a preliminary chemical characterization of Abruzzo extra virgin olive oils (EVOOs) using rare earth elements (REEs). REEs were evaluated in EVOO samples of different varieties produced in different geographical origins within the Abruzzo region (Italy) in three harvest years using ICP-MS chemometric techniques. Principal component, discriminant, and hierarchical cluster analyses were conducted to verify the influence of the variety, origin, and vintage of the REE composition. The results of a three-year study showed a uniform REE pattern and a strong correlation in most EVOOs, in particular for Y, La, Ce, and Nd. However, europium and erbium were also found in some oil samples. Compared with cultivar and origin, only the harvest year slightly influenced the REE composition, highlighting the interactions of the olive system with the climate and soil chemistry that could affect the multielement composition of EVOOs.

Marine sponges as coastal bioindicators of rare earth elements bioaccumulation in the French Mediterranean Sea

In recent years, the widespread use of rare earth elements (REEs) has raised the issue of their harmful effects on the aquatic environment. REEs are now considered as contaminants of emerging concern. Despite the increasing interest of REEs in modern industry, there is still a lack of knowledge on their potential impact on the environment and especially in the marine environment.In this context, the need for monitoring tools to assess REEs pollution status in marine ecosystems is considered as the first step towards their risk assessment. Similar to mussels, filter-feeder sponges have emerged as a key bio-monitor species for marine chemical pollution. Their key position at a low level of the trophic chain makes them suitable model organisms for the study of REEs potential transfer through the aquatic food web. We therefore undertook a comparative study on seven marine sponge species, assessing their capability to bioaccumulate REEs and to potentially transfer these contaminants to higher positions in the trophic chain. A spike experiment under controlled conditions was carried out and the intra- and inter-species variability of REEs was monitored in the sponge bodies by ICP-MS. Concentrations were found to be up to 170 times higher than the corresponding control specimens. The tubular species Aplysina cavernicola showed the highest concentrations among the studied species. This study shows, for the first time, the potential of marine sponges as bio-monitor of REEs as well as their possible application in the bioremediation of polluted sites.

Fractionation Trends and Variability of Rare Earth Elements and Selected Critical Metals in Pelagic Sediment from Abyssal Basin of NE Pacific (Clarion-Clipperton Fracture Zone)

The geochemical and mineralogical characteristics of pelagic sediments collected from the Interoceanmetal Joint Organization (IOM) claim area, located in the eastern part of the Clarion-Clipperton Fracture Zone (CCFZ; eastern tropical Pacific), are described in this paper. The concentrations of rare earth elements (REE), as well as other selected critical elements contained in 135 sediment samples of siliceous clayey silts, are presented. The vertical and spatial variabilities of elements, with particular emphasis on REE as well as metals of the highest economic interest such as Cu, Ni, and Co, are detailed. The applied methods include grain size analysis by laser diffraction, geochemistry examination using ICP-MS, XRF, AAS, and CNS spectrometry, and XRD analysis of mineral composition (Rietveld method). Additionally, statistical methods such as factor analysis (FA) and principal components analysis (PCA) were applied to the results. Finally, a series of maps was prepared by geostatistical methods (universal kriging). Grain size analysis showed poor sorting of the examined fine-grained silts. ICP-MS indicated that total REE contents varied from 200 to 577 ppm, with a mean of 285 ppm, which is generally low. The contents of critical metals such as Cu, Ni, and Co were also low to moderate, apart from some individual sampling stations where total contents were 0.15% or more. Metal composition in sediments was dominated by Cu, Ni, and Zn. A mineral composition analysis revealed the dominance of amorphous biogenic opaline silica (27–58%), which were mostly remnants of diatoms, radiolarians, and sponges associated with clay minerals (23% to 48%), mostly Fe-smectite and illite, with mixed-layered illite/smectite. The high abundance of diagenetic barite crystals found in SEM−EDX observations explains the high content of Ba (up to 2.4%). The sediments showed complex lateral and horizontal fractionation trends for REE and critical metals, caused mostly by clay components, early diagenetic processes, admixtures of allogenic detrital minerals, or scavenging by micronodules.

Temporal variability of rare earth elements in Ultisol soil under citrus plants

The objective of this study was to evaluate temporal variability of rare earth elements (REE) in soils of citrus agroecosystems. Instrumental neutron activation analysis was applied for measuring La, Ce, Nd, Sm, Eu, Tb, Yb, Lu and Sc. Sampling was performed in four citrus farms, with Valencia variety (Citrus sinensis L. Osbeck) grafted onto ‘Rangpur’ lime (Citrus limonia Osbeck), comprising both organic and conventional production systems in the Borborema region, Sao Paulo State, Brazil. There was slight temporal variability of some REE in different farms, however no clear positive or negative trend could be observed along the 3 years.

Statistical evaluation of the geochemical variability in overbank sediments in Spain.

The overall objective of this study is to estimate, detect and specify the main sources of variance which affect the contents of the different elements in overbank sediments across Spain. These sources of variance were assessed and compared by means of a series of analyses of variance (ANOVAs), by regarding two parameters: their significance and their contribution to the total variance. Overbank sediments, sampled in erosion banks, were studied in several locations, in basins which drain different types of geological backgrounds and land uses (urban, mining, agricultural or pristine) across the Iberian Peninsula. Forty-eight elements (mostly in the < 63μm fraction) were analysed by ICP-OES, ICP-MS and INAA. After an isometric log ratio (ilr) transformation of the data, three ANOVA analyses were performed considering three perspectives: (1) local scale, (2) regional scale: within-profile perspective and (3) regional scale: inter-profile perspective. On a local scale, it was observed that the variability of rare earth elements (REE) depends mostly on the grain size and that heavy metals are also influenced by depth. In the analysis carried out on a regional scale, from a within-profile perspective, depth and duplicates do not influence significantly the variability of the element contents. Finally, from an inter-profile perspective, the selected sources of variance were land use and provenance, whose significance is the highest. While grain size and the selection of depth are of crucial importance in the final results, on local studies, land use and provenance are the ones that influence the most the composition of sediments in regional studies.

Fraction-specific rare earth elements enable the reconstruction of primary seawater signatures from iron formations

Rare earth element (REE) abundances in iron formations (IFs) provide key evidence to track the redox evolution of the Precambrian oceans. Deriving information about processes and sources from IFs is complicated by the variable roles of diagenetic dissolution and precipitation that modify primary depositional signals in the rocks. Iron formations are typically mineralogically heterogeneous with varying amounts of carbonate (ankerite + siderite), oxide (predominantly magnetite) and silicate (chert and Fe-silicates). To date, little is known about the respective contributions of these fractions to the bulk-rock REE signal, and which fraction most accurately records primary seawater signals. Here we evaluate an optimized sequential extraction scheme for REE analysis in the ca. 2.46 Ga Asbestos Hills IFs from the Griqualand-West Basin in South Africa. These rocks were deposited immediately before the Great Oxidation Event and are potentially an important archive for large-scale redox changes in the (near) surface environment.To fully evaluate our method, we measured lanthanide elements plus ytrrium (REY) in individual minerals, in bulk rock samples and in three separate fractions using acetate, oxalate and total digestion sequential extractions. The extraction techniques were then verified using a mass balance approach, the first time that this has been comprehensively applied to IFs. Similarities between the carbonate fraction data and modern seawater, coupled with strong measurement reproducibility and systematic stratigraphic variability suggests that carbonate most closely tracks the primary seawater composition. The Asbestos Hills IFs show distinctive REY signatures with strongly variable (Yb/Pr)SN ratios, positive La anomalies, positive and constant Y/Ho, weakly positive Eu anomalies and a lack of Ce anomalies in their carbonate fraction. Stratigraphic variations in these parameters suggest deposition in a stratified fully anoxic ocean, which became shallower over time. The silicate fraction was influenced by various amounts of allochthonous material (detrital and volcanic ash), although some minerals including greenalite, minnesotaite and stilpnomelane may have tracked seawater REE variability. The oxide fraction was found to be the most REY-depleted and therefore susceptible to allochthonous influences as well as diagenetic controls. It shows a systematic MREE enrichment that has not been described in IFs before, but has been seen in sub-oxic, ferrous environments. An increase in the ratio of carbonate to oxide minerals ongoing upwards through the Asbestos Hills IF, from deep to shallow water conditions, most likely reflected an increase in dissimilatory iron reduction close to the margin of the anoxic basin.

Geochemistry and Spatial Variability of Rare Earth Elements in Soils under Different Geological and Climate Patterns of the Brazilian Northeast

ABSTRACT Growth in the agricultural and industrial sectors has increased the demand for rare earth elements (REEs) in the production of technological devices and fertilizers. Thus, the accumulation of these elements in the soil has become an environmental concern. Here, we aim to determine the natural contents of REEs in soils derived from different parent materials and under climatic conditions ranging from humid to semi-arid. We then evaluate the influence of major elements and soil properties on the geochemistry of [...]

Spatial variability and geochemistry of rare earth elements in soils from the largest uranium-phosphate deposit of Brazil.

The Itataia uranium-phosphate deposit is the largest uranium reserve in Brazil. Rare earth elements (REEs) are commonly associated with phosphate deposits; however, there are no studies on the concentrations of REEs in soils of the Itataia deposit region. Thus, the objective of the research was to evaluate the concentration and spatial variability of REEs in topsoils of Itataia phosphate deposit region. In addition, the influence of soil properties on the geochemistry of REEs was investigated. Results showed that relatively high mean concentrations (mgkg-1) of heavy REEs (Gd 6.01; Tb 1.25; Ho 1.15; Er 4.05; Tm 0.64; Yb 4.61; Lu 0.65) were found in surface soils samples. Soil properties showed weak influence on the geochemical behavior of REEs in soils, except for the clay content. On the other hand, parent material characteristics, such as P and U, had strong influence on REEs concentrations. Spatial distribution patterns of REEs in soils are clearly associated with P and U contents. Therefore, geochemical surveys aiming at the delineation of ore-bearing zones in the region can benefit from our data. The results of this work reinforce the perspective for co-mining of P, U and REEs in this important P-U reserve.

Measurements of Natural Carbonate Rare Earth Elements in Femtogram Quantities by Inductive Coupled Plasma Sector Field Mass Spectrometry

A rapid and precise standard-bracketing method has been developed for measuring femtogram quantity rare earth element (REE) levels in natural carbonate samples by inductively coupled plasma sector field mass spectrometry that does not require chemical separation steps. A desolvation nebulization system was used to effectively reduce polyatomic interference and enhance sensitivity. REE/Ca ratios are calculated directly from the intensities of the ion beams of (46)Ca, (139)La, (140)Ce, (141)Pr, (146)Nd, (147)Sm, (153)Eu, (160)Gd, (159)Tb, (163)Dy, (165)Ho, (166)Er, (169)Tm, (172)Yb, and (175)Lu using external matrix-matched synthetic standards to correct for instrumental ratio drifting and mass discrimination. A routine measurement time of 3 min is typical for one sample containing 20-40 ppm Ca. Replicate measurements made on natural coral and foraminiferal samples with REE/Ca ratios of 2-242 nmol/mol show that external precisions of 1.9-6.5% (2 RSD) can be achieved with only 10-1000 fg of REEs in 10-20 μg of carbonate. We show that different sources for monthly resolved coral ultratrace REE variability can be distinguished using this method. For natural slow growth-rate carbonate materials, such as sclerosponges, tufa, and speleothems, the high sample throughput, high precision, and high temporal resolution REE records that can be produced with this procedure have the potential to provide valuable time-series records to advance our understanding of paleoclimatic and paleoenvironmental dynamics on different time scales.

Novel phosphors of Eu 3+, Tb 3+ or Tm 3+ activated LaBGeO 5

Rare earth borogermanates as a group of stable compounds provided various potential properties important for modern sciences. Among the properties of interests, luminescence was manifested due to the variability of rare earth elements and the compounds constituted an important group of potential candidate. In this work, novel phosphors of Eu 3+, Tb 3+ or Tm 3+ doped LaBGeO 5 with the stillwellite type structure were synthesized by the solid state reaction method. Their X-ray and UV excitation luminescent properties showed that LaBGeO 5 was an excellent host lattice for the luminescence of Eu 3+, Tb 3+ and Tm 3+. The LaBGeO 5:Eu 3+, LaBGeO 5:Tb 3+ and LaBGeO 5:Tm 3+ presented bright red, green and blue emission light for both UV and X-ray excitation.

Heterogeneous rare earth element (REE) patterns and concentrations in a fossil bone: Implications for the use of REE in vertebrate taphonomy and fossilization history

Abstract A bone fragment (CGDQ-3) of Falcarius utahensis , a therizinosaur from the Early Cretaceous Cedar Mountain Formation, Utah, contained within a carbonate nodule, was analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in order to investigate REE variability within a thin-walled phalanx. Previous studies have found depth-related REE pattern variations; however, in CGDQ-3 variation occurs along the circumference of the bone. NASC-normalized REE patterns and concentrations vary between two apparent end members. A light-REE enriched (LREE) pattern, similar to solution ICP-MS analysis of this bone, characterizes approximately two-thirds of the bone fragment. Total REE concentrations are high and do not vary significantly from the periosteal surface to the medullar surface. Conversely, the remaining one-third of the bone has REE patterns that are MREE-depleted and low in total REE concentrations. REE concentrations in this part of the bone do not vary significantly from the periosteal to the medullar surface. A positive Ce anomaly is found throughout the entire bone, and is greatest within the LREE-enriched portion of the bone. This, in combination with the LREE-enrichment, suggests that the bone fossilized under reducing conditions. The distance between the LREE-enriched and MREE-depleted regions is less than 1 mm. Isotopic and petrographic analyses of the bone and surrounding carbonate matrix suggest the REE patterns in the bone were the result of partial fossilization/incomplete filling of micro-pore spaces around bone crystallites in an environment with changing redox conditions. The lower, MREE-depleted part of the bone fossilized contemporaneously with a pendant cement that formed on the underside of the bone in the vadose zone. Formation of the pendant cement restricted water flow through the bone, isolating the lower portion, which incorporated a MREE-depleted pattern. The upper part of the bone (LREE-enriched side) fossilized under more reducing conditions than the lower part. This resulted in reductive dissolution of minerals (such as hydrous ferric oxides and manganese-oxides) which were LREE-enriched with positive Ce anomalies. These REE were then incorporated into the upper part of the bone. This likely occurred after the bone entered the saturated zone (below the water table). The thinness of the bone and presence of a pendant cement helped facilitate partial fossilization of the bone, preserving the REE signature of an earlier fluid. As demonstrated by this case study, differences in REE patterns within a fossil may record changes in geochemical conditions during fossilization, particularly, when bones are encased in a material that reduces fluid permeability, such as micritic vadose calcite. Analysis of such bones may offer the opportunity to decipher complex fluid histories that occur during fossilization. LA-ICP-MS should be utilized to confirm solution ICP-MS analysis if it yields high REE variability, prior to an interpretation of reworking or time-averaging.

Genesis of ferromanganese crusts from the TAG hydrothermal field

The rare earth element (REE) geochemistry and Nd isotopic composition of marine ferromanganese crusts allow insight into their environment of deposition. We present REE along with major and trace element data from a suite of samples collected near an active hydrothermal site from the Mid-Atlantic Ridge and demonstrate extreme REE variability over short spatial scales. Both positive and negative Ce anomalies are observed, along with varied fractionation of the REEs. Some of the Fe–Mn crusts are formed directly from low-temperature hydrothermal fluids, channelled over 3 km from any high-temperature vent site. A significant hydrothermal component is observed in one Fe–Mn crust sampled. Other samples, collected from the same area, are predominantly hydrogenous and form at a wide range of accumulation rates depending on the hydrothermal plume input. The identification of extreme heterogeneity in source and depositional environment within one hydrothermal field suggests that (1) this variability can be resolved both spatially and temporally within a fossil hydrothermal deposit and (2) the integrated record provided by bulk analysis should be interpreted with caution.