Efficient Recovery of Rare Earth Elements from Acidic Wastewater by a Green ß-CDs-Functionalized Nanosponge.

The recovery of rare earth elements (REEs) from acidic wastewater is crucial to sustainable development, industrial processes, and human health. In this research, ß-cyclodextrin-based nanosponges (ß-CD/PVA-SA NSs) have been proposed as potential adsorbents for europium (Eu), dysprosium (Dy), and gadolinium (Gd) recovery. The nanosponges are synthesized by cross-linking ß-cyclodextrin (ß-CD) functionalized polyvinyl alcohol (PVA) and sodium alginate (SA). Experimental results indicate that ß-CD/PVA-SA NSs exhibit favorable selectivity for Eu, Dy, and Gd, with the maximum adsorption capacity of 222, 217, and 204 mg/g, respectively, in addition to stability and cyclicity. ß-CD/PVA-SA NSs maintain selective adsorption effects towards RE ions that are present in acidic mine drainage (AMD), thereby highlighting their potential for practical applications. Furthermore, density functional theory (DFT) simulations have unveiled the fundamental interactions between the functional groups anchored in ß-CD/PVA-SA NSs and the REEs, providing vital insights into their adsorption mechanism. Hence, the utilization of ß-CD/PVA-SA NSs has the potential to advance initiatives in remediating acidic water pollution and facilitating the sustainable recycling of RE resources.

Hydrothermal alteration processes in monzogranite: a case study from the Eastern Desert of Egypt: implications from remote sensing, geochemistry and mineralogy.

The South Eastern Desert (SED) of Egypt is one of the most promising areas in Egypt; it is widely explored for exploring the rare earth elements (REEs) and uranium-bearing ores. It is a main part of the Arabian-Nubian Shield (ANS). Therefore, the present study concerns with Sikait-Nugrus area as one of the most prolific sites in this region. The study provides a detailed geological, structural, and mineralogical investigation of the monzogranites to describe and characterize the various alteration types and sequence. For this purpose, remote sensing, geochemical and petrographical techniques were applied. The remote sensing technique helped in constructing a detailed geologic map of the study area to follow up strictly the alteration zone of the Sikait-Nugrus area. Petrographically, the granites predominates in the study area, they are described as slightly and highly altered monzogranites. The slightly altered one is composed mainly of quartz (~ 20-35%), alkali feldspar (~ 25-30%), plagioclase (~ 25-30%), and mica (~ 5-15%), while accessory minerals are represented by zircon and monazite. On the other hand, the portion of this granite close to the shearing zone is intensively altered and characterized by sericitization as the main alteration processes. This sheared portion is characterized by accessory minerals as, uranothorite, allanite, fluorite and Nb-minerals (ishikawaite). Minerlogically, the altered monzogranites are predominated by the following mineral groups: (1) radioactive minerals as uranyl silicates (soddyite, uranophane and kasolite), and thorium minerals (thorite and uranothorite), (2) Nb-Ta minerals (betafite, plumbobetafite, columbite, fergusonite, and aeschynite), (3) REE minerals (monazite, cheralite and xenotime), and (4) zircon and fluorite as accessory minerals. Geochemically, the recorded pattern of the REEs tetrad effect (M-type) for the highly altered samples indicate that these granites are highly evolved and affected by late stage of hydrothermal alteration and the effective water-rich alteration processes that connected to intensive physico-chemical changes. The total REE concentrations equal 241.8 and 249.75 ppm for the highly and slightly altered samples. A significant mass change (MC) was analyzed by the isocon technique (22.95 & 11.11) and volume change (VC) (1.8 &-7.99) for the highly and slightly altered samples, respectively. The mass balance calculations and the isocon diagrams revealed that some major oxides were removed from the slightly altered monzogranites and transformed later into highly altered monzogranites with increasing the alteration intensity due to the impacts of hydrothermal alteration processes. The studied area is virgin, where no detailed studies have been applied to this region. It is extendable to other parts of the Arabian-Nubian Shield in around the Red Sea in Egypt, Sudan, Saudi Arabia and Yemen. The applied technical workflow is also extendible to other surface analogues everywhere.

ZIF-8 Used for the Selective Recovery of Heavy Rare Earth Elements from Mining Wastewater.

In this study, a sample of 2-methylimidazole zinc salt (ZIF-8) demonstrated high selectivity for the recovery of heavy rare earth elements (REEs) from real rare earth mining wastewater. Results show that the distribution coefficient values of Y3+ (4.02 × 104 mL·g-1), Gd3+ (7.8 × 104 mL·g-1), and Dy3+ (6.8 × 104 mL·g-1) are orders of magnitude higher than those of K+ (359.51 mL·g-1), Mn2+ (266.67 mL·g-1), Ca2+ (396.42 mL·g-1), and Mg2+ (239.48 mL·g-1). Moreover, the desorption efficiency of heavy REEs exceeded 40%. Advanced characterizations and density functional theory (DFT) calculations were utilized to elucidate that the heavy REEs were more likely to bind to the nitrogen atoms of imidazole groups on ZIF-8 compared to non-REEs. Furthermore, the adsorption and desorption of heavy REEs primarily depend on the chemical interaction confirmed by adsorption kinetics, isotherm model, and thermodynamic analysis, which involves the dissociation of water and the formation of REE-O bonds. Finally, the ZIF-8 exhibits a remarkable recovery efficiency of over 40% for heavy REEs in column tests conducted over 7h. The findings reported here provide new insights into the selective recovery of heavy REEs from real mining wastewater.

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.

Selectively recovering rare earth elements with carboxyl immobilized metal-organic framework from ammonium-rich wastewater.

The material with high adsorption capacity and selectivity is essential for recovering rare earth elements (REES) from ammonium (NH4+-N)-rich wastewater. Although the emerging metal-organic framework (MOF) has gained intensive attention in REES recovery, there are scientific difficulties unsolved regarding restricted adsorption capacity and selectivity, hindering its extensive engineering applications. In this work, a diethylenetriamine pentaacetic (DTPA)-modified MOF material (MIL-101(Cr)-NH-DTPA) was prepared through an amidation reaction. The MIL-101(Cr)-NH-DTPA showed enhanced adsorption capacity for La(III) (69.78 mg g-1), Eu(III) (103.01 mg g-1) and Er(III) (83.41 mg g-1). The adsorption isotherm and physical chemistry of materials indicated that the adsorption of REEs with MIL-101(Cr)-NH-DTPA was achieved via complexation instead of electrostatic adsorption. Such complexation reaction was principally governed by -COOH instead of -NH2 or -NO2. Meanwhile, the resulting material remained in its superior activity even after five cycles. Such a constructed adsorbent also exhibited excellent selective adsorption activity for La(III), Eu(III), and Er(III), with removal efficiency reaching 70% in NH4+-N concentrations ranging from 100 to 1500 mg L-1. This work offers underlying guidelines for exploitation an adsorbent for REEs recovery from wastewater.

Hyperaccumulator extracts promoting the phytoremediation of rare earth elements (REEs) by Phytolacca americana: Role of active microbial community in rhizosphere hotspots.

The increased usage of rare earth elements (REEs) leads to the extensive exploitation of rare earth mines, and the REEs pollution in soil caused by the legacy mine tailings has brought great harm to environment and human health. Although Phytolacca americana can remove REEs from contaminated soil to some extent, there is still an urgent problem to improve its efficiency. Hyperaccumulator extract is a new organic material with potential in metal phytoextraction, but its role in REEs phytoremediation and the related underlying processes remain unclear. In this study, hyperaccumulator extracts from P. americana root (PR), stem (PS), leaf (PL) and EDTA were used to improve the phytoremediation efficiency of REEs with P. americana. Soil zymography was applied to assess the enzyme hotspots' spatial distribution in the rhizosphere, and the hotspots' microbial communities were also identified. The results indicated that the application of hyperaccumulator extracts improved the biomass and REEs uptake of P. americana, and the highest REEs content in plant was observed in the treatment of PS, which increased 299% compared to that of the control. Hotspots area of ß-glucosidase, leucine aminopeptidase and acid phosphatase were concentrated in the pant rhizosphere along the roots and increased 2.2, 5.3 and 2.2 times after PS application compared to unamended soils. The PS application increased the relative abundance of Proteobacteria, Cyanobacteria, Bacteroidota and Firmicutes phyla in rhizosphere. Soil fungi have a higher contribution on promoting REEs activation than that of bacteria. Available P and extractable REEs were leading predictors for the plant biomass and REEs concentrations. The co-occurrence network showed that the application of PS creates a more efficient and stable microbial network compared to other treatments. In conclusion, stem-derived hyperaccumulator extract is excellent in stimulating REEs phytoremediation with P. americana by improving hotspots microbial activities and form a healthy rhizosphere microenvironment.

Study on the role of microbial metabolites in in-situ noncontact bioleaching of ion-adsorption rare earth ore.

Ion adsorption rare earth ore nearly satisfy global market demand for heavy rare earth elements (HREEs). Bio-leaching has important potential for the clean and efficient extraction of ion-adsorption rare earth ore. However, the complexities of in-situ mining restrict the use of contact/direct bio-leaching, and non-contact/indirect bio-leaching would be the best choice. This study explore the potential of fermentation broths prepared by Yarrowia lipolytica (ATCC 30162) for the bio-leaching of ion-adsorption rare earth ore, and three typical metabolites (potassium citrate (K3Cit), sodium citrate (Na3Cit) and ammonium citrate ((NH4)3Cit) of Yarrowia lipolytica were further evaluated in simulated bioleaching (non-contact bioleaching) of ion-adsorption rare earth ore, including leaching behavior, seepage rule and rare earth elements (REEs) morphological transformation. The column leaching experiments shown that direct leaching of REEs using fermentation broths results in incomplete leaching of REEs due to the influence of impurities. Using the purified and prepared metabolites as lixiviant, REEs can be effectively extracted (leaching efficiency >90%) at cation concentration was only 10 % of the commonly used ammonium sulfate concentration (45 mM). Cation type had less effect on leaching efficiency. During the ion-adsorption rare earth ore leaching process, rare earth ions form a variety of complex chelates with citrate, thus transferring rare earth elements from the mineral surface to the leachate. Experimental results showed that pH and concentration together determined the type and form of rare earth chelates, which in turn affect the leaching behavior of REEs and solution seepage rule. This study helps to provide a theoretical basis for the regulation and enhancement of ion-adsorption rare earth ore non-contact bioleaching process.

Sedimentary characteristics of ion-adsorption rare earth elements and assessment of their resource reuse potential due to soil and water erosion in western Fujian.

With severe soil and water erosion, the crucial ion-adsorption rare earth elements (REEs) have attracted much global attention. REEs play a vital role in tracing material sources and exploring sedimentary characteristics due to their unique and stable geochemistry properties. In the present work, three representational possible redeposition areas in western Fujian were selected as the study areas. The geochemical characteristics of REEs in the sediments of the study areas were evaluated to elucidate that REEs are the products of soil and water erosion and to assess their redeposition characteristics. In the research results, the properties of the parent rocks shown in the samples, together with the negative correlation between the content of REEs in the samples and altitude as well as the relief degree on the land surface (RDLS), fully indicate that the sediments in the study areas are the products of migration caused by soil erosion and redeposition in the downstream areas. At the same time, according to the widely applicable standard of rare earth resources exploitation, that is the boundary grade of ion-adsorption rare earth ore in southern China (∑REE = 500 mg·kg-1), we found that the content of REEs in the study areas was close to or exceeded this standard, and the maximum ∑REE of Guozhai Reservoir (869.11 mg·kg-1) was much larger than this standard. Therefore, the redeposited rare earth in Changting Country has high reuse potential under the current scarce resources.

Transport and distribution of residual nitrogen in ion-adsorption rare earth tailings.

A large amount of nitrogen remains in ion-absorption rare earth tailings with in-situ leaching technology, and it continually ends up in groundwater sources. However, the distribution and transport of ammonium nitrogen (NH4+-N) and nitrate nitrogen (NO3--N) across tailings with both depth and hill slopes is still unknown. In this study, the amount of NH4+-N and nitrate nitrogen (NO3--N) was determined in tailings, and a soil column leaching experiment, served to assess the transport and distribution following mine closure. Firstly, a high concentration of NH4+-N in the leachate at the initial leaching stage was detected, up to 2000 mg L-1, and the concentration of NH4+-N clearly diminished as time passed. Meanwhile, the NH4+-N contents remained relatively high in soil. Secondly, both the content of NH4+-N and NO3--N varied greatly according to vertical distribution after leaching lasting several years. The amounts of NH4+-N and NO3--N in surface soil were much smaller than those in deep soil, with 3-4 orders of magnitude variation with depth. Thirdly, when disturbed by NH4+-N, the pH not only diminished but also changed irregularly as depth increased. Fourthly, although the amount of NO3--N was smaller than that of NH4+-N, both their distribution trend was similar with depth. In fact, NH4+-N and NO3--N were significantly correlated but this declined from the knap to the piedmont. Based on these results, it is suggested that mining activity could cause nitrogen to be dominated by NH4+-N and acidification in a tailing even if leaching occurs over several years. NO3--N derived from NH4+-N transports easily and it becomes the main nitrogen pollutant with the potential to be a long-lasting threat to the environment around a mine.

Toxicokinetics of praseodymium and cerium administered as chloride salts in Sprague-Dawley rats: impacts of the dose and of co-exposure with additional rare earth elements.

We conducted a rat exposure study to assess the impacts of dose and co-exposure with other rare earth elements (REEs) on the toxicokinetics of praseodymium (Pr) and cerium (Ce). We first determined the kinetic profiles of elemental Pr and Ce in blood, urine and feces along with tissue levels at sacrifice on the seventh day following intravenous injection of PrCl3 or CeCl3 at 0.3 or 1 mg/kg bw (of the chloride salts) in adult male Sprague-Dawley rats (n = 5 per group). In blood, Pr and Ce half-lives for the initial phase (t1/2α) increased with increasing doses, while their half-lives for the terminal phase (t1/2ß) were similar at both doses. In urine, a minor excretion route, no significant effect of the dose on the cumulative excretion was apparent. In feces, a major excretion route, the fraction of the Pr dose recovered was significantly lower at the 1 mg/kg bw dose compared to the 0.3 mg/kg bw dose, while no significant dose effect was apparent for Ce. In the liver and spleen, which are the main sites of REEs accumulation, there was a significant effect of the dose only for Ce retention in the spleen (i.e., increased retention of Ce in spleen at higher dose). Results were compared with those of a previous toxicokinetic study with a similar design but an exposure to a quaternary mixture of CeCl3, PrCl3, NdCl3 and YCl3, each administered at 0.3 mg/kg bw or 1 mg/kg bw. A mixture effect was apparent for the initial elimination phase (t1/2α) of Pr and Ce from blood and for the fecal excretion of Ce at the 1 mg/kg bw. In urine and liver, there was no evident overall mixture effect; in the spleen, there was a higher retention of Pr and Ce in rats exposed to the mixture at the 0.3 mg/kg bw, but not at the 1 mg/kg bw dose. Overall, this study showed that the dose and mixture exposure are two important factors to consider as determinants of the toxicokinetics of REEs.

Toxic effects of lanthanum(III) on photosynthetic performance of rice seedlings: Combined chlorophyll fluorescence, chloroplast structure and thylakoid membrane protein assessment.

Rare earth elements (REEs) are emerging as an anticipated pollution in the environment due to their active use in many areas. However, the effects of REEs on the photosynthesis of rice have not been thoroughly explored. Therefore, this study emphasizes how high levels of La(III) affect the thylakoid membrane of rice seedlings, thereby inhibiting photosynthesis and growth. Here, we reported that rice plants treated with La(III) exhibited an increase in La accumulation in the leaves, accompanied by a decrease in chlorophyll content and photosynthetic capacity. La(III) exposure decreased Mg content in leaves, but possibly increased other nutrients including Cu, Mn, and Zn through systemic endocytosis. K-band and L-band appeared in the fluorescence OJIP transients, indicating La(III) stress destroyed the donor and receptor sides of photosystem II (PSII). Numerous reaction centers (RC/CSm) were inactivated by La(III) treatment, which resulted in a reduction in electron transport capacity (decreased ETo/RC and ETo/CSm) and an increase in the dissipation of the excess excitation energy by heat (increased DIo/RC and DIo/CSm). The BN-PAGE analysis of thylakoid membrane protein complexes showed that La(III) induced the degradation of supercomplexes, PSII core, LHCII, PSI core, LHCI, and F1-ATPase binding Cyt b6f complex. Collectively, this study revealed that La(III) causes significant degradation of thylakoid membrane proteins, thereby promoting the decomposition of photosynthetic complexes, ultimately destroying the chloroplast structure and reducing the photosynthetic performance of rice seedlings.

A pilot scale study on the treatment of rare earth tailings (REEs) wastewater with low C/N ratio using microalgae photobioreactor.

Microalgae appear to be a promising and ecologically safe way for nutrients removal from rare earth tailings (REEs) wastewater with CO2 fixation and added benefits of resource recovery and recycling. In this study, a pilot scale (50 L) co-flocculating microalgae photobioreactor (Ma-PBR) as constructed and operated for 140 days to treat REEs wastewater with low C/N ratio of 0.51-0.56. The removal rate of ammonia nitrogen (NH4+-N) reached 88.04% and the effluent residual concentration was as low as 9.91 mg/L that have met the Emission Standards of Pollutants from Rare Earths Industry (GB 26451-2011). Timely supplementation of trace elements was necessary to maintain the activity of microalgae and then prolonged the operation time. The dominant phyla in co-flocculating microalgae was Chlorophyta, the relative abundance of which was higher than 80%. Tetradesmus belonging to Chlorophyceae was the dominant genus with relative abundance of 80.35%. The results provided a practical support for the scaling-up of Ma-PBR to treat REEs wastewater.

Geochemistry and 14C dating of guano deposits in the Karaftu Cave, Kurdistan, Iran: implication for paleoenvironment.

Karaftu Cave in the northwest of Divandareh includes four floors plus an underground area. The bat hall and its underground area are covered with guano deposits. 14C dating indicates the onset of guano deposition is about 14,260±50 BP years, and its average accumulation rate is about 4.1 mm/yr for depths of 360 to 205 cm. Bacterial and fungal metabolisms decay guano, release acids, and disperse large amounts of microorganisms inside the cave. Interactions between acids and guano caused leaching, dissolution, change in the distribution, and abundance of elements, which leads to the formation of secondary minerals in guano. These variations in minerals and elements also depend on the local climatic conditions. Distribution of elements in the Ce/Ce* versus Pr/Pr* diagram and the correlation coefficient between Ce and Mn display three different paleoclimate conditions (dry, wet, and dry) during the accumulation of the guano. Also, dolomite, phosphate, and iron oxide minerals have been formed during the passage of water through bedrock beneath the guano. This water is unsuitable for drinking and harmful to the organisms in the region. Effect of these acids on the substrate also leads to the collapse of the cave floor, generation of a new underground, fall in the groundwater level, change in the groundwater drainage system, drying of springs around the cave, loss of green cover, and a negative impact on the ecosystem in the region. To keep the cave environment clean and remove these problems, it is better to harvest guano and use it as fertilizer.

Lack of Environmental Sensitivity of a Naturally Occurring Fluorescent Analog of Cholesterol.

Dehydroergosterol (DHE, Δ5,7,9(11),22-ergostatetraen-3ß-ol) is a naturally occurring fluorescent analog of cholesterol found in yeast. Since DHE has been shown to faithfully mimic cholesterol in a large number of biophysical, biochemical, and cell biological studies, it is widely used to explore cholesterol organization, dynamics and trafficking in model and biological membranes. In this work, we show that DHE, in spite of its localization at the membrane interface, does not exhibit red edge excitation shift (REES) in model membranes, irrespective of the membrane phase. These results are reinforced by semi-empirical quantum chemical calculations of dipole moment changes of DHE in ground and excited states, which show a very small change in the dipole moment of DHE upon excitation. We conclude that DHE fluorescence exhibits lack of environmental sensitivity, despite its usefulness in monitoring cholesterol organization, dynamics and traffic in model and biological membranes.

Effect of Copolymer Structure on Rare-Earth-Element Chelation Thermodynamics.

Rare-earth elements (REEs) are crucial to modern technology, leading to a high demand for materials capable of REE extraction and purification. Metal-chelating polymers (e.g., polycarboxylic acids, polyamines, and others) are particularly useful in these applications due to their synthetic accessibility and high selectivity. Copolymers with varied mole fractions of acrylic acid and methyl acrylate are synthesized and isothermal titration calorimetry (ITC) to measure the thermodynamics of REE binding for each material is used. Across a series of copolymer compositions, entropically driven binding thermodynamics (∆G, ∆H, and ∆S) that appear to be independent of χAcrylic Acid  are found. ITC stoichiometry data reveal that each copolymer requires between four and five repeat units to bind each REE. These data suggest that alterations in the copolymer structure do not affect the overall binding thermodynamics of REEs to these copolymers.

Adsorption of REEs from Aqueous Solution by EDTA-Chitosan Modified with Zeolite Imidazole Framework (ZIF-8).

Chitosan (CS) modified with ethylenediamine tetraacetic acid (EDTA) was further modified with the zeolite imidazole framework (ZIF-8) by in situ growth method and was employed as adsorbent for the removal of rare-earth elements (REEs). The material (EDTA-CS@ZIF-8) and ZIF-8 and CS were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), and nitrogen adsorption/desorption experiments (N2- Brunauer-Emmet-Teller (BET)). The effects of adsorbent dosage, temperature, the pH of the aqueous solution, contact time on the adsorption of REEs (La(III), Eu(III), and Yb(III)) by EDTA-CS@ZIF-8 were studied. Typical adsorption isotherms (Langmuir, Freundlich, and Dubinin-Radushkevich (D-R)) were determined for the adsorption process, and the maximal adsorption capacity was estimated as 256.4 mg g-1 for La(III), 270.3 mg g-1 for Eu(III), and 294.1 mg g-1 for Yb(III). The adsorption kinetics results were consistent with the pseudo-second-order equation, indicating that the adsorption process was mainly chemical adsorption. The influence of competing ions on REE adsorption was also investigated. After multiple cycles of adsorption/desorption behavior, EDTA-CS@ZIF-8 still maintained high adsorption capacity for REEs. As a result, EDTA-CS@ZIF-8 possessed good adsorption properties such as stability and reusability, which have potential application in wastewater treatment.

Environment-Sensitive Fluorescence of 7-Nitrobenz-2-oxa-1,3-diazol-4-yl (NBD)-Labeled Ligands for Serotonin Receptors.

Serotonin is a neurotransmitter that plays a crucial role in the regulation of several behavioral and cognitive functions by binding to a number of different serotonin receptors present on the cell surface. We report here the synthesis and characterization of several novel fluorescent analogs of serotonin in which the fluorescent NBD (7-nitrobenz-2-oxa-1,3-diazol-4-yl) group is covalently attached to serotonin. The fluorescent ligands compete with the serotonin1A receptor specific radiolabeled agonist for binding to the receptor. Interestingly, these fluorescent ligands display a high environmental sensitivity of their fluorescence. Importantly, the human serotonin1A receptor stably expressed in CHO-K1 cells could be specifically labeled with one of the fluorescent ligands with minimal nonspecific labeling. Interestingly, we show by spectral imaging that the NBD-labeled ligand exhibits a red edge excitation shift (REES) of 29 nm when bound to the receptor, implying that it is localized in a restricted microenvironment. Taken together, our results show that NBD-labeled serotonin analogs offer an attractive fluorescent approach for elucidating the molecular environment of the serotonin binding site in serotonin receptors. In view of the multiple roles played by the serotonergic systems in the central and peripheral nervous systems, these fluorescent ligands would be useful in future studies involving serotonin receptors.

Prospect on Rare Earth Elements and Metals Fingerprint for the Geographical Discrimination of Commercial Spanish Wines.

This paper presents a novel tool for Spanish commercial wine discrimination according to their designation of origin (PDO). A total of 65 commercial wines from different Spanish designation of origin (Alicante, Bullas, Campo de Borja, Jumilla, Castilla la Mancha, Ribeiro, Ribera de Duero, Rioja, Rueda, Utiel-Requena, Valdepeñas and Valencia) were characterized. The rare earth elements (REEs) content was determined by a high-temperature torch integrated sample introduction system (hTISIS) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The REE content was used to draw characteristic PDOs radar charts. Results indicated that the REEs fingerprint provides a good prospect to discriminate the different Spanish PDOs, except for Alicante, Castilla la Mancha, Jumilla, Utiel-Requena and Valdepeñas. Finally, for those PDOs that were not properly distinguished, a second fingerprint obtained from Ba, Co, Cr, Mn, Ni, Pb and V content was used for discrimination purposes.

Compositions and mobility of major, δD, δ18O, trace, and REEs patterns in water sources at Benue River Basin-Cameroon: implications for recharge mechanisms, geo-environmental controls, and public health.

Hydro-geochemical data are required for understanding of water quality, provenance, and chemical composition for the 2,117,700 km2 Niger River Basin. This study presents hydro-geochemical analysis of the Benue River Basin, a major tributary of the Niger River. The distribution of major ions, Si, δD, and δ18O, trace and rare-earth elements (TE and REEs, respectively) composition in 86 random water samples, revealed mixing of groundwater with surface water to recharge shallow aquifers by July and September rains. Equilibration of groundwater with kaolinite and montmorillonites, by incongruent dissolution, imprints hydro-chemical signatures that vary from Ca + Mg - NO3 in shallow wells to Na + K - HCO3 in boreholes and surface waters, with undesirable concentrations of fluoride identified as major source of fluorosis in the local population. Our results further indicate non-isochemical dissolution of local rocks by water, with springs, wells and borehole waters exhibiting surface water-gaining, weakest water-rock interaction, and strongest water-rock interaction processes, respectively. Poorly mobile elements (Al, Th and Fe) are preferentially retained in the solid residue of incongruent dissolution, while alkalis, alkaline earth and oxo-anion-forming elements (U, Mo, Na, K, Rb, Ca, Li, Sr, Ba, Zn, Pb) are more mobile and enriched in the aqueous phase, whereas transition metals display an intermediate behavior. Trace elements vary in the order of Ba > Sr > Zn > Li > V > Cu > Ni > Co > As > Cr > Sc > Ti > Be > Pb > Cd, with potentially harmful elements such as Cd, As, and Pb mobilized in acidic media attaining near-undesirable levels in populated localities. With the exception of Y, REEs distribution in groundwater in the order of Eu > Sm > Ce > Nd > La > Gd > Pr > Dy > Er > Yb > Ho > Tb > Tm differs slightly with surface water composition. Post-Archean Average Australian Shale-normalized REEs patterns ranging from 1.08 to 199 point to the dissolution of silicates as key sources of trace elements to groundwater, coupled to deposition by eolian dust.

Investigation of the relationship between rare earth elements, trace elements, and major oxides in soil geochemistry.

Investigation on the behavior of elements in the soil is important both in exploration and environmental geochemistry studies. Rare earth elements (REEs) are the most useful among all trace elements. REE studies have shown that they have important applications in igneous, sedimentary, and metamorphic petrology. This work aims to investigate the relationship of these elements with one another and the behavior of the major oxides and trace elements with REEs. Soil samples were obtained from the alteration site possibly related to mineralization and were analyzed for major oxides, trace elements, and REEs. The relationships between the major oxide-trace element/heavy metal and REE were investigated by statistical methods, such as descriptive statistics, correlation coefficient, and principle component analysis. According to the correlation coefficient matrix, light REEs (LREEs) showed weak to moderate negative correlation with MgO and MnO and moderately positive correlation with SiO2 and K2O. No association was detected between the heavy REEs (HREEs) and the main oxides, but a strong positive correlation with LREEs was observed. For the trace elements, LREE showed a weak positive correlation with Ba and Sn and moderate to strong positive correlation with As, Hf, Nb, Rb, Ta, Th, U, W, and Zr. They also displayed weak to moderate correlation with Sc, Co, Zn, Ni, and V. HREE showed weak to moderate positive correlation with Ni, Cs, Ga, Hf, Th, Zr, As, and LREE. Although REEs exhibited no direct correlation with Au and Ag, they showed a good correlation with some trace elements that are related to hydrothermally altered products. This study showed that REEs can also be used in exploration and environmental geochemistry studies by exploiting the relationship between REEs and other trace/heavy metal elements.