Amounts Of Rare Earth Elements Research Articles

Recovery of Rare Earth Elements Present in Mobile Phone Magnets with the Use of Organic Acids

Currently, the recovery of materials from secondary sources is increasingly necessary because of the scarcity of materials. Significant amounts of rare earth elements (REE) are found in permanent neodymium-iron-boron (NdFeB) magnets, used in various electrical and electronic equipments, such as mobile phones. However, the estimated recycling rate for REEs is only 1%. Hydrometallurgical routes are the most commonly used for REE recovery from secondary sources. This route usually uses inorganic acids, which are expensive and toxic. Thus, in this work the leaching efficiency of organic acids (acetic and citric) in leaching the REE (neodymium and praseodymium) present in magnets of obsolete or defective mobile phones was evaluated. Different concentrations of acids, solid/liquid relations, times and leaching techniques (microwave, ultrasound and conventional) are also evaluated. The results indicate that acetic and citric acids have the potential to leach Nd and Pr. Microwave leaching was the most effective method, compared to ultrasound and conventional methods. In microwaves, citric acid at 0.5 M (ratio s/l 1/100) leached 57% of Nd and 58% of Pr. Acetic acid at 0.5 M (s/l ratio—1/100) leached 48% of Nd and 65% of Pr, in 15 min. Furthermore, both citric acid and acetic acid also leached high percentages of iron (51% and 72%, respectively).

Future material requirements for global sustainable offshore wind energy development

Offshore wind energy (OWE) is a cornerstone of future clean energy development. Yet, research into global OWE material demand has generally been limited to few materials and/or low technological resolution. In this study, we assess the primary raw material demand and secondary material supply of global OWE. It includes a wide assortment of materials, including bulk materials, rare earth elements, key metals, and other materials for manufacturing offshore wind turbines and foundations. Our OWE development scenarios consider important drivers such as growing wind turbine size, introducing new technologies, moving further to deep waters, and wind turbine lifetime extension. We show that the exploitation of OWE will require large quantities of raw materials from 2020 to 2040: 129–235 million tonnes (Mt) of steel, 8.2–14.6 Mt of iron, 3.8–25.9 Mt of concrete, 0.5–1.0 Mt of copper and 0.3–0.5 Mt of aluminium. Substantial amounts of rare earth elements will be required towards 2040, with up to 16, 13, 31 and 20 fold expansions in the current Neodymium (Nd), Dysprosium (Dy), Praseodymium (Pr) and Terbium (Tb) demand, respectively. Closed-loop recycling of end-of-life wind turbines could supply a maximum 3% and 12% of total material demand for OWE from 2020 to 2030, and 2030 to 2040, respectively. Moreover, a potential lifetime extension of wind turbines from 20 to 25 years would help to reduce material requirements by 7–10%. This study provides a basis for better understanding future OWE material requirements and, therefore, for optimizing future OWE developments in the ongoing energy transition.

Mineralogy and distribution of rare earth elements in the Waterberg coalfield high ash coals

Conventional deposits of rare earth elements (REEs) cannot meet the high demand for REEs globally. Therefore, the prospecting of REEs from alternative sources like high ash coal is vital. In this study, coal discard and “Run of Mine” (ROM) coal were studied to evaluate the abundance and association of REEs in these materials. The TESCAN Integrated Mineral Analyzer (TIMA) and X-ray diffractometer (XRD) techniques were employed to determine the mineralogy of the coal samples. TIMA was further utilized to investigate the REE associations and distributions, whilst the inductively coupled plasma-mass spectrometry (ICP-MS) was used to quantify the amount of REEs in the coal samples. Quantitative analysis results revealed that the total REE content in the coal discard and ROM coal was above 225 ppm. Furthermore, the results show that the dominant REE-bearing minerals in the discard and ROM coal samples were kaolinite, pyrite, and hematite. In addition, the heavy REEs (HREEs) displayed a strong affinity for the organic macerals and were enriched in the ROM coal. The encouraging results of significantly light REEs (LREEs) relative to HREEs in both coals suggest they are viable prospects for REE extraction. Hydrometallurgical leaching is therefore recommended to assess the potential for REE recovery from these sources.

Global environmental cost of using rare earth elements in green energy technologies

Decarbonization of economy is intended to reduce the consumption of non-renewable energy sources and emissions from them. One of the major components of decarbonization are “green energy” technologies, e.g. wind turbines and electric vehicles. However, they themselves create new sustainability challenges, e.g. use of green energy contributes to the reduction of consumption of fossil fuels, on one hand, but at the same time it increases demand for permanent magnets containing considerable amounts of rare earth elements (REEs). This article provides the first global analysis of environmental impact of using rare earth elements in green energy technologies. The analysis was performed applying system dynamics modelling methodology integrated with life cycle assessment and geometallurgical approach. We provide evidence that an increase by 1% of green energy production causes a depletion of REEs reserves by 0.18% and increases GHG emissions in the exploitation phase by 0.90%. Our results demonstrate that between 2010 and 2020, the use of permanent magnets has resulted cumulatively in 32 billion tonnes CO2-equivalent of GHG emissions globally. It shows that new approaches to decarbonization are still needed, in order to ensure sustainability of the process. The finding highlights a need to design and implement various measures intended to increase REEs reuse, recycling (currently below 1%), limit their dematerialization, increase substitution and develop new elimination technologies. Such measures would support the development of appropriate strategies for decarbonization and environmentally sustainable development of green energy technologies.

Quantitative analysis of rare earth elements in Mg–Zn–RE(Ce, Y, Gd)–Zr alloy

The solid solution amount of rare earth elements and the mass fraction of compounds were measured by low-temperature phase separation technology, the existing forms of rare earth elements in ZK-RE(Ce, Y, Gd) alloy were quantitatively studied, and the difference of solid solution ability of rare earth elements and the factors affecting the number of rare earth compounds were analyzed. The experimental results show that the solid solution amount of rare earth elements mainly depends on their addition amount, Zn and RE inhibit each other’s solid solution amount, and the order of solid solution amount (wt%) of rare earth elements with the same addition amount is GD > Y > Ce. Rare earth elements are mostly distributed in Mg–Zn–RE compounds, and the increase of rare earth content is helpful to form more Mg–Zn–RE compounds. With the same content of elements, the order of mass fraction of Mg–Zn–RE compounds is ZK-Ce system > ZK-Y system > ZK-Gd system. The order of solid solution ability of rare earth elements is Gd > Y > Ce, and the amount of solid solution directly affects the initial element content of compound precipitation in the remaining melt. The influence of Zn/Ce ratio in the residual melt of ZK-Ce alloy is shown in the number of rare earth compounds, while the Zn/Y(Gd) ratio in the residual melt of ZK-RE(Y, Gd) alloy determines the type and number of rare earth compounds.

Separation of lanthanum and neodymium in a hollow fiber supported liquid membrane: CFD modelling and experimental validation

Nickel metal hydride batteries find extensive use in many electronic devices. They contain a small amount of rare earth elements, such as, lanthanum and neodymium, which can be recovered from waste batteries, and reused. Hollow fiber supported liquid membranes (HFSLM) have been used for separation of different metal ions. In this work, a CFD model has been developed for a HFSLM to study the separation of lanthanum ion (La+3) and neodymium ion (Nd+3) from an aqueous solution. The model considers the effect of pH on distribution coefficient DM, which is a function of hydrogen ion (H+) concentration, and has a significant effect on extraction efficiency. The model was validated with the experimental data. An empirical model was fitted with the simulation data, and the parameters were optimized for the effective separation of La+3 and Nd+3. The maximum extraction of Nd+3 was predicted to be 44.97%, whereas extraction of La+3 was estimated to be 3.39%, at the optimized conditions of flow rate: 118.96 ml/min, feed pH: 3.41, and [PC88A]: 41.63 mol/m3, in once-through mode. The proposed CFD model could be helpful in design as well as, scale-up of HFSLM for separation of metal ions, by changing the design and process parameters.

Effect of substrate properties and phosphorus supply on facilitating the uptake of rare earth elements (REE) in mixed culture cropping systems of Hordeum vulgare, Lupinus albus and Lupinus angustifolius

This study presents how phosphate (P) availability and intercropping may influence the migration of rare earth elements (REEs) in legume–grass associations. In a replacement model, Hordeum vulgare was intercropped with 11% Lupinus albus and 11% Lupinus angustifolius. They were cultivated on two substrates, A (pH = 7.8) and B (pH = 6.6), and treated with 1.5 g P m−2 or 3 g P m−2. Simultaneously, a greenhouse experiment was conducted to quantify carboxylate release. There, one group of L. albus and L. angustifolius was supplied with either 200 µmol L-1 P or 20 µmol L-1 P. L. albus released higher amounts of carboxylates at low P supply than L. angustifolius, while L. angustifolius showed the opposite response. Plants cultivated on substrate B accumulated substantially higher amounts of nutrients and REE, compared to substrate A. Higher P supply did not influence the leaf and stem P concentrations of H. vulgare. Addition of P decreased REE accumulation in barley monocultures on alkaline soil A. However, when H. vulgare was cultivated in mixed culture with L. angustifolius on alkaline substrate A with high P supply, the accumulation of REE in H. vulgare significantly increased. Conversely, on acidic substrate B, intercropping with L. albus decreased REE accumulation in H. vulgare. Our findings suggest a predominant effect of soil properties on the soil–plant transfer of REEs. However, in plant communities and within a certain soil environment, interspecific root interactions determined by species-specific strategies related to P acquisition in concert with the plant’s nutrient supply impact REE fluxes between neighbouring plants.

Fluid Properties and Genesis of Dolomites in the Devonian Guanwushan Formation of Upper Yangtze Platform, SW China

The Guanwushan Formation (GWSF) of Devonian dolomite are extensively developed in the northwest of Sichuan Basin in the Upper Yangtze region, but the properties of dolomitization fluid and the geneses are still unclear. Three types of dolomites can be divided by petrological characteristics: the fine-microcrystalline dolomites (FMD), the fine crystalline dolomites (FCD) and the medium crystalline dolomites (MCD). The order degree of these three types of dolomites increased in turn, and they all showed dark cathodoluminescence (CL) luminescence. The total amount of Rare Earth Elements (∑REE) of the dolomite was low, while the dolomite enriched with light REE and lacking heavy REE presented a distribution pattern consistent with that of limestone. The weak negative anomalies of the Ce and Eu indicated that the dolomites were formed in a weak redox environment with relatively low temperature. The dolomitization fluids were inherited from the original seawater. The respective δ13CPDB values of the three types of dolomites varied a little, indicating that they were not affected by the biological effects. Specifically, the δ18OPDB values of the FMD and FCD dolomites were higher than that of the limestone, indicating that the dolomitization fluid was influenced by evaporation at the penecontemporaneous stage. The interpretations were also supported by the 87Sr/86Sr ratios, as the 87Sr/86Sr ratios of FMD comparable to the Middle Devonian seawater. The δ18OPDB value of the MCD dolomite was lower than that of the limestone. It also showed poor automorphic extent, which clarified that the dolomite experienced more intense dolomitization in greater burial depth and at higher temperatures.

210Po characteristic in selected thermal water sources in Northern Vietnam

There are eight famous thermal water sources, with medium temperature, neutral pH, high ranges of TDS values located in different carbonate formations in Northern Vietnam. The chemical composition results showed the major elements present were Na, K, Mg, Ca, Sr, while trace amounts of rare earth elements (REE), Ag, As, Pb, Th, U were observed. The 210Po activity concentration and the annual committed effective doses for adults, children, and infants in all study areas were far less than 100 mBq L−1 and 0.1 mSv y−1, respectively. Some significant correlations between 210Po and other chemical components have been observed.

Extraction of Lanthanum Oxide from Different Spent Fluid Catalytic Cracking Catalysts by Nitric Acid Leaching and Cyanex 923 Solvent Extraction Methods

A laboratory-scale procedure was developed to obtain lanthanum oxide from spent fluid catalytic cracking catalyst, commonly used in the heavy crude oil cracking process. Two different solids, consisting mainly of silica, alumina, and a certain amount of rare earth elements, were leached under several conditions to recover the rare earths. Nitric acid leaching lead to the highest recovery of lanthanum, reaching a recovery percentage greater than 95% when a 1.5 M concentration was used. Subsequently, liquid phases were subjected to a liquid–liquid extraction process using Cyanex 923 diluted in Solvesso 100, and the lanthanum was quantitatively extracted. Lanthanum was also quantitatively stripped using oxalic acid to obtain the corresponding lanthanum oxalates, as revealed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and Fourier transform infrared (FTIR) techniques. After thermal treatment at 1200 °C for 2 h, these solids yielded lanthanum oxide.

Characteristics of trace elements in crude oil in the east section of the south slope of Dongying Sag and their application in crude oil classification

The east section of the south slope of the Dongying Sag is rich in oil and gas resources, with diverse reservoir types and complex physical properties of crude oil. It has typical characteristics of multi-source and multi-stage accumulation. The classification of crude oil types is the basis of petroleum geology research. By analyzing the content and distribution characteristics of trace elements in typical crude oil samples, combined with mathematical statistics, the effective classification of crude oil types in the study area is realized. The content of alkali metals, alkaline earth metals and transition metal elements in crude oil is significantly higher than that of rare earth elements, and the content of light rare earth elements is higher than that of heavy rare earth elements. There is a good correlation between the total amount of trace elements and the bulk composition of crude oil, while the correlation between the total amount of rare earth elements and the bulk composition of crude oil is relatively poor. The cluster analysis of multiple trace element-related parameters can classify the crude oil into three types, and the biomarker parameters of different type crude oils show obvious differences, indicating that the use of trace elements to classify crude oil types is effective and feasible in the study area. This study shows that the content, distribution characteristics and related parameters of trace elements in crude oil can be used as effective oil source correlation tools, reasonable selection of correlation parameters, and comprehensive analysis of cluster analysis methods can accurately classify the types of crude oil.

U‐Pb Geochronology and Geochemistry of Stratiform Garnet from the Aqishan Pb‐Zn Deposit, Eastern Tianshan, Xinjiang, NW China: Constraints on Genesis of the Deposit

AbstractThe Aqishan lead‐zinc deposit, located in the Jueluotag metallogenic belt of eastern Tianshan, Xinjiang, Northwest China, has a stratiform occurrence in the marine volcanic tuff of the Yamansu Formation. The ore body has a typical double‐layer structure, having a stratified, stratoid, lenticular upper part and a veined, stockwork‐like lower part. The occurrence of the upper orebody is consistent with that of the volcanic tuff wall rock. The ore minerals are mainly chalcopyrite, pyrite, sphalerite, galena and magnetite, the altered minerals mainly being silicified, such as sericite, chlorite, epidote, garnet. The garnetized skarn, being stratiform and stratoid, is closely related to the upper part of the orebody. Geological observations show that the limestone in the ore‐bearing Yamansu Formation is not marbleized and skarnized. Spatially, it is associated with the ferromanganese deposits in the marine volcanic rocks of the Yamansu Formation. These geological features reflect the likelihood that the Aqishan lead‐zinc deposit is a hydrothermal exhalation sedimentary deposit. The results from the EPMA show that the garnet is mainly composed of grossular–andradite series, contents being in a range of 34.791–37.8% SiO2, 32.493–34.274% CaO, 8.454–27.275% FeO, 0.012–15.293% Al2O3, 0.351–1.413% MnO, and lower values of 0.013–1.057% TiO2. The content of SiO2 vs. CaO and FeO vs. Al2O3 has a significant positive correlation. The results of ICP‐MS analysis for the garnet show that the REE pattern is oblique to right in general. The total amount of rare earth elements is relatively low, ΣREE = 71.045–826.52 ppm, which is relatively enriched for LREE and depleted for HREE. LREE/HREE = 8.66–4157.75, LaN/YbN = 23.51–984.34, with obvious positive Eu and Ce anomalies (δEu = 2.27–76.15, δCe = 0.94–1.85). This result is similar to the REE characteristics of ore‐bearing rhyolite volcanic rocks, showing that the garnet was formed in an oxidizing environment and affected by clear hydrothermal activity. The U‐Pb isotopic dating of garnet by fs‐LA‐HR‐ICP‐MS gives an age of 316.3 ± 4.4 Ma (MSWD = 1.4), which is consistent with the formation time of the Yamansu Formation. According to the study of deposit characteristics and geochemical characteristics, this study concludes that the Aqishan lead‐zinc deposit is a hydrothermal exhalation sedimentary deposit, the garnet being caused by hydrothermal exhalative sedimentation.

Comparative evaluation of methods for determination of the rare earth elements content in phosphate raw materials

The increase in the rate of extraction and use of rare earth elements (REE) necessitates the study of their environmental and industrial safety. Despite the relatively low content of REEs in phosphate ores (less than 1.5% (wt.)), significant volumes of production of phosphoric acid and mineral fertilizers based on it require environmental monitoring of REEs both in the soil located in the immediate vicinity of phosphogypsum dumps and in the phosphate fertilizers themselves, which are the main source of REEs in it, paying special attention to the irreplaceable soils of greenhouse farms. Inductively coupled plasma mass spectrometry (ICP – MS) occupies the leading position today among the variety of direct methods for the quantitative determination of REEs. However, for a number of domestic producers of phosphate fertilizers, the ICP – MS method is still too complicated and expensive. As an affordable alternative, we can mention the spectrophotometric method (SPM), based on the formation of a colored complex of rare-earth elements with the analytical reagent Arsenazo III. On the example of a sample of phosphorite from the Polpinsky deposit, a comparative assessment of the possibility of quantitative determination of REEs in phosphate raw materials by the ICP – MS method is presented as the most promising, as well as the SPM as the most accessible. It is shown that the sensitivity of the spectrophotometric method is sufficient for the reliable determination of the amount of REEs in the phosphate raw material. The reasons for significant errors in determination of the amount of REEs in phosphate raw materials by the photometric method and possible ways to reduce them to values comparable with the error of the method are considered.

Selective Scandium (Sc) Extraction from Bauxite Residue (Red Mud) Obtained by Alkali Fusion-Leaching Method.

Bauxite residue, known as “red mud,” is a potential raw material for extracting rare-earth elements (REEs). The main REEs (Sc, Y, La, Ce, Nd, Nb, and Sm) from the raw bauxite are concentrated in RM after the Bayer leaching process. The earlier worldwide studies were focused on the scandium (Sc) extraction from RM by concentrated acids to enhance the extraction degree. This leads to the dissolution of major oxides (Fe2O3 and Al2O3) from RM. This article studies the possibility of selective Sc extraction from alkali fusion red mud (RMF) by diluted nitric acid (HNO3) leaching at pH ≥ 2 to prevent co-dissolution of Fe2O3. RMF samples were analyzed by X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), electron probe microanalysis (EPMA), and inductively coupled plasma mass spectrometry (ICP-MS). It was revealed that Sc concentration in RMF can reach up to 140–150 mg kg−1. Sc extraction was 71.2% at RMF leaching by HNO3 at pH 2 and 80 °C during 90 min. The leaching solution contained 8 mg L−1 Sc and a high amount of other REEs in the presence of relatively low concentrations of impurity elements such as Fe, Al, Ti, Ca, etc. The kinetic analysis of experimental data by the shrinking core model showed that Sc leaching process is limited by the interfacial diffusion and the diffusion through the product layer. The apparent activation energy (Ea) was 19.5 kJ/mol. The linear dependence of Sc extraction on magnesium (Mg) extraction was revealed. According to EPMA of RMF, Sc is associated with iron minerals rather than Mg. This allows us to conclude that Mg acts as a leaching agent for the extraction of Sc presented in the RMF in an ion-exchangeable phase.

Characterisation of rare earth elements and toxic heavy metals in coal and coal fly ash.

Due to increasing demand for rare earth elements (REE), growing concerns over their sustainability, and domination of their supply by China, coal fly ash has recently emerged as a viable target for REE recovery. With billions of tonnes in repositories and still more being generated across the globe, it is necessary to develop environmentally friendly and economical extraction technologies for the recovery of the REEs from coal fly ash, and to consider the environmental implications of such a recovery process. This study reports characterisation of Nigerian simulant coal fly ash, and investigates the distribution and leaching of the REEs and U, Th, As, Cr, Cd and Pb from these materials using ethanoic acid. Significant amounts (14% to 31%) of the REEs were recovered in the acid-soluble fraction of a sequential extraction procedure using ethanoic acid. While the greatest amounts of U (53% to 62%) and Th (89% to 96%) were recovered in the stable residual fraction, significant amounts (3% to 13%) of U were recovered in the acid-soluble fraction. As was the most enriched element in the mobile acid-soluble fraction (46% to 60%), followed by Cd (15% to 34%). These results demonstrate that REEs contained within coal fly ash – especially those sourced from coal-fired power plants burning coal at temperatures between 700 °C and 1100 °C – can be recovered through an environmentally friendly procedure using the cost-effective heap leaching method, with ethanoic acid or the more cheaply-available vinegar as lixiviant. These results are also valuable for cost evaluation of rare earths recovery from coal fly ash generated by fluidised bed combustion coal fired power plants, and the development of methodologies for coal fly ash management.

Strengthening of low-cost rare earth magnesium alloy Mg-7Gd-2Y–1Zn-0.5Zr through multi-directional forging

Conventional rare-earth magnesium alloys have high strength but are not accepted by some fields because of their relatively high price. Magnesium alloys with the addition of small amounts of rare earth elements can improve the mechanical properties by severe plastic deformation while saving cost. In this paper, the effects of multidirectional forging (MDF) process on the microstructure and mechanical properties of low-cost rare earth magnesium alloy Mg-7Gd-2Y–1Zn-0.5Zr were investigated, and the plastic deformation mechanism, dynamic recrystallization mechanism and property strengthening mechanism during the MDF process were analyzed. The results showed that the yield strength, ultimate tensile strength and elongation of Mg-7Gd-2Y–1Zn-0.5Zr alloy were 395.2 MPa, 435.3 MPa and 17.6% after extrusion, MDF at reduced temperature conditions and T5 treatment. The increase in alloy strength is related to solid solution strengthening and is more attributed to the combined effect of grain refinement and aging precipitation. The dynamic recrystallization mechanism leading to grain refinement converts from discontinuous dynamic recrystallization to continuous dynamic recrystallization during MDF at reduced temperatures. And the decrease in deformation temperature leads to difficulties in prismatic and pyramidal slipping, where grain boundary sliding from fine grains and twinning in a few relatively coarse grains play a role in coordinating deformation.

Rare-Earth-Modified Titania Nanoparticles: Molecular Insight into Synthesis and Photochemical Properties.

A molecular precursor approach to titania (anatase) nanopowders modified with different amounts of rare-earth elements (REEs: Eu, Sm, and Y) was developed using the interaction of REE nitrates with titanium alkoxides by a two-step solvothermal–combustion method. The nature of an emerging intermetallic intermediate was revealed unexpectedly for the applied conditions via a single-crystal study of the isolated bimetallic isopropoxide nitrate complex [Ti2Y(iPrO)9(NO3)2], a nonoxo-substituted compound. Powders of the final reaction products were characterized by powder X-ray diffraction, scanning electron microscopy–energy-dispersive spectroscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, Raman spectroscopy, and photoluminescence (PL). The addition of REEs stabilized the anatase phase up to ca. 700 °C before phase transformation into rutile became evident. The photocatalytic activity of titania modified with Eu3+ and Sm3+ was compared with that of Degussa P25 titania as the control. PL studies indicated the incorporation of Eu and Sm cations into titania (anatase) at lower annealing temperatures (500 °C), but an exclusion to the surface occurred when the annealing temperature was increased to 700 °C. The efficiency of the modified titania was inferior to the control titania while illuminated within narrow wavelength intervals (445–465 and 510–530 nm), but when subjected to a wide range of visible radiation, the Eu3+- and Sm3+-modified titania outperformed the control, which was attributed both to doping of the band structure of TiO2 with additional energy levels and to the surface chemistry of the REE-modified titania.

Rare earth elements (REEs): geochemical patterns and contamination aspects in Brazilian benchmark soils

Rare earth elements have been increasingly used in modern societies and soils are likely to be the final destination of several REE-containing (by)products. This study reports REE contents for topsoils (0–20 cm) of 175 locations in reference (n = 68) and cultivated (n = 107) areas in Brazil. Benchmark soil samples were selected accomplishing a variety of environmental conditions, aiming to: i) establishing natural background and anthropogenic concentrations for REE in soils; ii) assessing potential contamination of soils - via application of phosphate fertilizers - with REE; and, iii) predicting soil-REE contents using biomes, soil type, parent material, land use, sand content, and biomes-land use interaction as forecaster variables through generalized least squares multiple regression. Our hypotheses were that the variability of soil-REE contents is influenced by parent material, pedogenic processes, land use, and biomes, as well as that cultivated soils may have been potentially contaminated with REE via input of phosphate fertilizers. The semi-total concentrations of REE were assessed by inductively coupled plasma mass spectrometry (ICP-MS) succeeding a microwave-assisted aqua regia digestion. Analytical procedures followed a rigorous QA/QC protocol. Soil physicochemical composition and total oxides were also determined. Natural background and anthropogenic concentrations for REE were established statistically from the dataset by the median plus two median absolute deviations method. Contamination aspects were assessed by REE-normalized patterns, REE fractionation indices, and Ce and Eu anomalies ratios, as well as enrichment factors. The results indicate that differences in the amounts of REE in cultivated soils can be attributed to land use and agricultural sources (e.g., phosphate-fertilizer inputs), while those in reference soils can be attributed to parent materials, biomes, and pedogenic processes. The biomes, land use, and sand content helped to predict concentrations of light REE in Brazilian soils, with parent material being also of special relevance to predict heavy REE contents in particular.

Differences in the behaviour of trace and rare-earth elements in oxidizing and reducing soil environments: Case study of Terra Rossa soils and Cretaceous palaeosols from the Istrian peninsula, Croatia

This study compares the differences between the distribution of trace elements and rare-earth elements (REEs) formed under reducing and oxidizing soil conditions during pedogenesis on carbonate bedrock. Terra rossa (TR) soils, representing pedogenesis under oxic conditions, and Cretaceous palaeosols (CP), representing pedogenesis under reducing conditions, were sampled on the Istrian peninsula. They were studied by ICP-MS, ICP-OES, XRF, XRD, sequential extraction and statistical analyses. The differences in trace-element behaviour between the TR and CP stem from different redox conditions, but the most remarkable difference was observed in the behaviour of the REEs. Statistical analyses revealed that in TR soils all the REEs showed a very positive correlation, while in CPs the light REEs and heavy REEs showed an internal, very positive correlation. TR soils have almost twice as much REEs as CPs. This difference is pedogenetic, as both materials have a very similar amount of REEs in the residual fraction. While TR soils have the same amount of REEs in fractions other than the residual fraction, CPs have almost no REEs in these fractions. Different REE patterns obtained from sequential extraction, such as a middle-REE enrichment and a positive Ce anomaly in TR soils and light-REE depletion, heavy-REE enrichment, positive Ce and Eu anomalies in CPs, contributed to an understanding of the redox and pedogenetic processes. This study successfully emphasized the influence of different redox conditions on the behaviour of trace and rare-earth elements during pedogenesis on a carbonate bedrock and the ability of the REEs to track pedogenetic processes.

Synthesis of a New Phosphonate-Based Sorbent and Characterization of Its Interactions with Lanthanum (III) and Terbium (III).

High-tech applications require increasing amounts of rare earth elements (REE). Their recovery from low-grade minerals and their recycling from secondary sources (as waste materials) are of critical importance. There is increasing attention paid to the development of new sorbents for REE recovery from dilute solutions. A new generation of composite sorbents based on brown algal biomass (alginate) and polyethylenimine (PEI) was recently developed (ALPEI hydrogel beads). The phosphorylation of the beads strongly improves the affinity of the sorbents for REEs (such as La and Tb): by 4.5 to 6.9 times compared with raw beads. The synthesis procedure (epicholorhydrin-activation, phosphorylation and de-esterification) is investigated by XPS and FTIR for characterizing the grafting route but also for interpreting the binding mechanism (contribution of N-bearing from PEI, O-bearing from alginate and P-bearing groups). Metal ions can be readily eluted using an acidic calcium chloride solution, which regenerates the sorbent: the FTIR spectra are hardly changed after five successive cycles of sorption and desorption. The materials are also characterized by elemental, textural and thermogravimetric analyses. The phosphorylation of ALPEI beads by this new method opens promising perspectives for the recovery of these strategic metals from mild acid solutions (i.e., pH ~ 4).