Amounts Of Rare Earth Elements Research Articles

Valorisation of acid mine drainage through effective recovery of selected rare earth elements using cationic resins

Acid mine drainage (AMD) presents a challenge to the environment if not well managed, but it also presents an opportunity for the recovery of economically valuable products, including rare earth elements (REEs), which are critical for the development of advanced, and green technologies. REE concentrations in AMD samples from coal and gold mines were determined using inductively coupled plasma optical emission spectroscopy (ICP-OES) and their sorption by different cationic resins (CHT4083, CHP4502 and CHP00712) was evaluated. Optimum conditions for the sorption of the REEs by these resins were determined through batch experiments and desorption of the REEs from the resins using different concentrations of sulphuric acid (H2SO4) solutions. Coal mine drainage (CMD), with a low pH of 2.37, had higher amounts of REEs (ΣREE 226.3732 mg/L) than AMD from the gold mines (ΣREE 4.9705 mg/L), with a pH of 3.21. A REE sorption efficiency of up to 98% was obtained with CHP4502 and CHP00712 resins and further optimisation of CHP00712 revealed that a resin volume of 250 mL and a contact time of 10 min were required to successfully remove REEs from 500 mL AMD. The sorption capacities of the resin for the selected REEs were 3.88 mg/g, 0.88 mg/g, 1.37 mg/g, 3.18 mg/g, 0.67 mg/g, 0.01 mg/g and 0.27mg/g for Pr, Gd, Nd, Ce, Sm, Eu and Y, respectively. Elution of the resin with a 0.5 N solution of sulphuric acid desorbed the REEs. AMD from coal mines could be an alternate source of REEs and cationic resins can be used to recover these REEs from the CMD. Further investigations, including impregnation of resin to improve its sorption capacity, and temperature effects on the sorption process, are recommended.

Sulfuric Acid Leaching Recovery of Rare Earth Elements from Wizów’s Phosphogypsum in Poland

Rare earth elements (REEs) are considered vital raw materials for the economy and are on the European Union’s list of critical raw materials (CRMs). Europe is mainly dependent on REE imports. This dependence could be reduced if locally available primary or secondary resources would be processed. In Poland, there are, for instance, over 5 million metric tons of phosphogypsum (PG), a fine powdery byproduct from the fertilizer industry, available near the former Wizów Chemical Plant near Bolesławiec. This material that is considered a waste in Poland contains significant amounts of REEs that could theoretically be recovered and contribute to Europe’s economy. This work is the first systematic analysis of REE leaching studies with sulfuric acid and PG from Wizów. Process parameters such as temperature, particle size, concentration of the leaching solution, and the addition of oxidant and reductant agents were tested to determine the most efficient process. Ultimately, a leaching efficiency of 99% was obtained. Lanthanum exhibited the highest leaching efficiency at almost 100%, followed by Yttrium, Neodymium, Terbium, and Dysprosium. The results of the laboratory experiments are promising and suggest that larger pilot or commercial experiments can be performed next.

Raman characterization of lunar highlands simulants for in-situ resource utilization in a lunar setting

Lunar regolith simulants from the NU-LHT series were characterized using different configurations for performing Raman spectroscopy measurements, including with different excitation wavelengths and spot sizes. This testing was performed to explore various Raman measurement configurations for analyzing lunar regolith, especially in terms of capturing distinctive fluorescence features that can provide more information about the composition of the regolith. Results obtained utilizing configurations having a 785 nm laser for excitation showed relatively narrow, intense fluorescence signals between 870 and 890 nm, which, to the best of our knowledge, has not been observed before in lunar regolith or lunar simulant samples. These distinctive fluorescence features, attributed to a specific rare earth element (REE) impurity, adds further support that these types of features can be utilized for identification and potentially quantification of the amount of REE or transition metal impurities in lunar regolith. Further, other aspects of these Raman instrument configurations and their advantages were explored, especially those applicable for use in a lunar environment in support of in-situ resource utilization (ISRU).

Preparation of imprinted cryogels of cellulose cross-linked ionic liquids for selective separation of Gd(III) from rare earth leachate

The development of high technology has elevated industry’s dependence on rare earth resources. The hydrometallurgical process is widely used for the separation of rare earth elements (REEs) from rare earth ores, producing acidic leachate with trace amounts of REEs. Recovery of REEs from rare earth leachate not only mitigates the negative impact of leachate on the environment, but also contributes to the realization of sustainable resource utilization. In this study, two novel imprinted cryogel adsorbents, methyltrioctylammonium chloride-derivative carboxymethylated cellulose nanocrystal imprinted cryogel (LR-ICMC) and ethylmethylimidazolium bromide-derivative carboxymethylated cellulose nanocrystal imprinted cryogel (LM-ICMC), were constructed by using carboxymethylated modified cellulose nanocrystals as a backbone structure, and successfully branched ionic liquids (ILs) methyltrioctylammonium chloride-derivative and ethylmethylimidazolium bromide-derivative, respectively, for the separation of gadolinium ions (Gd(III)) from rare earth leachate. Firstly, SEM and TEM results showed that the incorporation of ILs retained part of the pore structure of carboxymethylated cellulose nanocrystals (CMCNCs). BET and TG results illustrated that the incorporation of ILs effectively increased the specific surface area and thermal stability of LR-ICMC and LM-ICMC. FT-IR and XPS results showed that LR-ICMC and LM-ICMC could adsorb Gd(III) by electrostatic and chelating effects. Secondly, adsorption isotherm experiments demonstrated the adsorption capacities of 66.880 mg/g and 75.895 mg/g for LR-ICMC and LM-ICMC, respectively; adsorption kinetic experiments demonstrated the ability of LR-ICMC and LM-ICMC to rapidly adsorb 85.152 % and 87.989 % of the maximum adsorption capacity, respectively, within the initial first 40 min. Finally, cycling experiments demonstrated the advantages of LR-ICMC and LM-ICMC in reuse, maintaining 89.245 % and 90.734 % of the original performance after five adsorption–desorption cycles, respectively. Based on these results, LR-ICMC and LM-ICMC were demonstrated to be highly efficient and reusable adsorbents for selective recovery of Gd(III) from rare earth leachate. This study deepens the application of ILs in solid-phase adsorbents and highlights the great potential of LR-ICMC and LM-ICMC in the field of REEs recovery.

Acute and chronic toxicity of rare earth elements-enriched sediments from a prospective mining area: Effects on life history traits, behavioural and physiological responses of Gammarus fossarum (Crustacea Amphipoda)

Rare earth elements (REE) have an essential role and growing importance in the world's economy. They are attracting interest from society, policymakers, and scientists. The rapidly growing global demand for REE in several strategic industrial and agricultural sectors led many countries to consider the (re)-opening of mining activities for REE extraction. Hence, their increasing use led to the disruption of their biogeochemical cycles with anthropic abnormalities already observed in aquatic ecosystems. Nonetheless, REE remain less studied, and their mechanisms of toxicity actions are not fully understood. As amphipods, Gammarus fossarum represent an important part of the aquatic macroinvertebrate assemblage and are generally used in ecotoxicological studies for their high ecological relevance. However, their use for the study of REE effects has been rather limited so far. The current study aims to assess the potential effects of two naturally REE-enriched sediments (N2 and B4) on G. fossarum. Effects on life history traits, behavioural and physiological responses have been evaluated. Exposing G. fossarum males for 72h to sediments N2 and B4 led to a decrease in haemolymph osmolality and locomotion while an increase in ventilatory activity was observed. Exposing G. fossarum pre-copula pairs with females at the same reproductive stage to the naturally REE-enriched sediments, for one moult cycle duration (∼30 days) showed that sediment B4 led to i) a significant uptake of REE, ii) a significant decrease in the proportion of females with oocytes and iii) a significant reduction in the total number of juveniles. The physicochemical analyses of sediments showed that B4 contains the highest amount of REE with a higher proportion of light REE. The present study gives the first insights into the potential toxicity of REE on G. fossarum as they may have deleterious effects on G. fossarum population's dynamics, which may alter the functioning of aquatic ecosystems.

Experimental metasomatic alteration of titanite in a series of metamorphic fluids at 700 °C and 200 MPa

Seven experiments exploring the reaction of titanite with various hydrothermal solutions have been carried out at 700 °C and 200 MPa for a run duration of 16 days. In experiments involving fluids consisting of NaCl+H2O, KCl+H2O, CaCl2+H2O, 2M NaOH, or 2M KOH, no reaction of the titanite with the fluid was observed other than a slight dissolution of the titanite. Experiments involving NaF+H2O and Ca(OH)2+H2O resulted in visible alteration of the titanite in texture and composition, coupled with the formation of perovskite. In the NaF+H2O experiment, perovskite, enriched with rare earth elements (REE), formed as euhedral to subhedral crystals on the surface of the recrystallized titanite. In the Ca(OH)2+H2O experiment perovskite took in minor amounts of REE, and formed as a reaction rim partially replacing the titanite via a coupled dissolution-reprecipitation reaction. Wollastonite, along with minor calcite, and grossular garnet, formed as an outer rim on the perovskite. In the NaF+H2O experiment major and trace elements were leached from the titanite, whereas in the Ca(OH)2+H2O experiment no leaching of major or trace elements was observed. Nb/Ta, Th/U, and Y/Ho were investigated as potential indicators of hydrothermal processes. While the Nb/Ta ratio was altered in the experimentally metasomatised titanite, the degree of alteration was the same for both fluids. In contrast, only small changes in the Th/U and Y/Ho ratios between the altered and original titanite were seen for either experiment. The formation of perovskite at the expense of titanite in NaF+H2O or Ca(OH)2+H2O fluids demonstrates how titanite reacts with these fluids in simple, low silica activity systems under mid to upper crustal P-T conditions.

Robust r-process Nucleosynthesis beyond Lanthanides in the Common Envelop Jet Supernovae

The common envelop jet supernovae (CEJSNe) r-process scenario has been proposed as an r-process nucleosynthesis site in the past decade. Jets launched by a neutron star that spirals in inside the core of a red supergiant star in a common envelope evolution supply the proper conditions for forming elements heavier than iron through the rapid neutron-capture process. The present work initially unveils the r-process abundance patterns that result from the density profile in the relatively long-lived jets. The results indicate that the expansion profile unique to the CEJSN scenario can produce the largest ratio of the third r-process peak elements to lanthanides among current r-process scenarios and, in addition, can form quite an amount of lanthanides, about 1% of matters above the first peak, in a single event. The comparison of the ratio of the third-peak elements to the lanthanides with several observed r-enhanced metal-poor stars and with other r-process scenarios suggests that a high mass of third-peak elements is anticorrelated with a high fraction of lanthanides, both in observations and theory. The CEJSN-like scenario plays a significant role in this conclusion since it reproduces the observational features of some particular r-enhanced metal-poor stars where other r-process scenarios encounter problems. Due to the formation of extremely heavy elements, the CEJSN also offers a credible estimation of the age of the most actinide-boosted star by cosmochronometry.

Features of Distribution of Rare-Earth Elements in Coals of the Far East

For the first time, the distribution of rare earth elements (REE) has been studied in detail for a number of coal facilities (30 deposits, 650 samples of coal and 210 samples of carbonaceous rocks). The ubiquitous presence of elevated concentrations of REE in coals has been noted. The REE mineral cluster in coals includes the association: ash content of coals – SiO2 – K2O – Al2o3 – TiO2 – Sc – Y – Dy – Ho – Er – Tm – Yb – Lu, and the association La – Ce – Pr – Nd – Sm – Eu – Gd – Tb. The presence of these elements of the mineral part of the coals is preferably in the composition of phosphate minerals – monazite and apatite (according to electron microscopy with microanalysis, the correlation of REE with P2o5). The content of individual REE in humic acids isolated from coals and fractions of coals of different densities has been studied. The specific role of organic matter(s) in the concentration of REE, their presence in the humus component of S and in low-ash coals is shown. Selective accumulation (fractionation) of heavy REE by organic matter has been experimentally established for the first time. Two genetic types of REE mineralization have been identified in coals: mainly terrigenous (hydrogenic) and tufogenic. The increased concentrations of REE in coals are due to the influence of the petrofund. The deposits were ranked according to the degree of prospects for REE based on an assessment of the resource potential of associated REE in the coals of the studied brown coal deposits. REE raw materials (lanthanides in coal ash) differ significantly from traditional types of rare earths ores by an incomparably large relative amount of heavy REE (on average 3–4 times), sometimes reaching 46% of the total REE content. Thus, coal ash is a unique non–traditional source of heavy lanthanides – more rare, valuable and expensive. The coals of the studied deposits should be considered as associated raw materials for rare earths.

Research Progress on the Oxidation Behavior of Ignition-Proof Magnesium Alloy and Its Effect on Flame Retardancy with Multi-Element Rare Earth Additions: A Review.

The phenomenon of high-temperature oxidation in magnesium alloys constitutes a significant obstacle to their application in the aerospace field. However, the incorporation of active elements such as alloys and rare earth elements into magnesium alloys alters the organization and properties of the oxide film, resulting in an enhancement of their antioxidation capabilities. This paper comprehensively reviews the impact of alloying elements, solubility, intermetallic compounds (second phase), and multiple rare earth elements on the antioxidation and flame-retardant effects of magnesium alloys. The research progress of flame-retardant magnesium alloys containing multiple rare earth elements is summarized from two aspects: the oxide film and the matrix structure. Additionally, the existing flame-retardancy models for magnesium alloys and the flame-retardant mechanisms of various flame-retardant elements are discussed. The results indicate that the oxidation of rare earth magnesium alloys is a complex process determined by internal properties such as the structure and properties of the oxide film, the type and amount of rare earth elements added, the proportion of multiple rare earth elements, synergistic element effects, as well as external properties like heat treatment, oxygen concentration, and partial pressure. Finally, some issues in the development of multi-rare earth magnesium alloys are raised and the potential directions for the future development of rare earth flame-retardant magnesium alloys are discussed. This paper aims to promote an understanding of the oxidation behavior of flame-retardant magnesium alloys and provide references for the development of rare earth flame-retardant magnesium alloys with excellent comprehensive performance.

Recovery of rare earth elements from rare earth molten salt electrolytic slag via fluorine fixation by MgCl2 roasting

Rare earth fluoride molten-salt electrolytic slag (REFES) is a precious rare earth element (REE) secondary resource, and considerable amounts of REEs exist in REFES as REF3; they are difficult to dissolve in acid or water and impede efficient REE extraction. In REFES recovery, the REF3 species in REFES are usually transformed into acid-soluble rare earth compounds by NaOH roasting or sulfating roasting and then extracted by acid leaching. Moreover, the fluorides in REFES are released as HF gas in the roasting process or enter the liquid phase during the water washing process; both of these processes cause fluorine pollution. Fixing the fluorine into the solid slag provides a way to avoid fluorine pollution. In this study, a novel method was proposed to extract REEs from REFES via MgCl2 roasting followed by HCl leaching. Thermodynamics calculations and thermogravimetry‒differential thermal analyses (TG-DTA) were conducted to investigate the reactions occurring in the roasting process. First, MgCl2 reacts with the REF3 and RE2O3 to form RECl3 and REOCl, respectively. Second, the RECl3 absorbs water and forms RE(OH)3. Third, MgCl2·6H2O is gradually dehydrated to MgCl2·2H2O and reacts with REF3 and RE(OH)3, and REOCl, MgF2 and MgO are formed. Through HCl leaching, the REOCl in the roasting products is leached by HCl acid, while fluoride remains in the solid slag as MgF2. The optimum experimental conditions are as follows: mass ratio of MgCl2 to REFES of 30%, roasting temperature of 700 °C, roasting time of 2 h, hydrochloride acid concentration of 4 mol/L, leaching time of 2 h, leaching temperature of 90 °C and leaching L/S ratio of 20:1. The efficiencies for total leaching of the REEs, La, Ce, Pr, and Nd are 99.13%, 99.20%, 98.42%, 99.38%, and 99.08%, respectively. Moreover, the concentration of fluoride in the leaching solution is 2.191 × 10−6 mol/L. This method has a short process flow with low reagent costs, and the problem of fluoride pollution from REFES recovery is solved; thus, our study has great industrial application potential.

Laser ablation (in situ) Lu-Hf geochronology of epidote group minerals

Epidote group minerals, including allanite, clinozoisite and epidote are common in a range of metamorphic, igneous and hydrothermal systems, and are stable across a wide range of pressure–temperature (P–T) conditions. These minerals can incorporate substantial amounts of rare earth elements (REEs) during their crystallisation, making them potential candidates for Lu–Hf geochronology to provide age constraints on various geological processes. Here we report on a first exploration into the feasibility of in situ Lu–Hf geochronology for epidote group minerals from various geological settings and compare the results with age constraints from other geochronometers. Magmatic allanite samples from pegmatites and monzogranites in the Greenland anorthosite complex, Coompana Province and Qingling Orogen provided dates consistent with magmatic events spanning from c. 2660 to 1171 Ma. In the Qingling pegmatites, a younger phase of hydrothermal allanite was dated at c. 215 Ma, consistent with the timing of regional REE mineralisation. Allanite from the Yambah Shear Zone, Strangways Metamorphic Complex, yielded Lu–Hf age of c. 430 Ma. It predates the garnet and apatite growth at c. 380 Ma, suggesting the Lu–Hf system can be preserved in allanite during prograde amphibolite-facies metamorphism. Additionally, Lu–Hf dates for hydrothermal clinozoisite and epidote are consistent with the timing of hydrothermal alteration and mineralisation in a range of settings, demonstrating the utility of the technique for mineral exploration. Despite the current lack of matrix-matched reference materials, the successful application of laser ablation Lu–Hf geochronology to epidote group minerals offers valuable geochronological insights into various geological processes that can be difficult to access through other geochronometers.

Afghanistan’s raw materials policy regarding rare earth elements after the Taliban victory [Polityka surowcowa Afganistanu dotycząca metali ziem rzadkich po zwycięstwie Talibów

The Taliban victory in Afghanistan in 2021 has not only raised geopolitical concerns but has also sparked questions about the state’s policies and strategies concerning its rare earth elements reserves. The main objective of the presented article is to indicate how the current political change in Afghanistan may affect the raw material policy regarding the extraction of rare earth elements, taking into account geopolitical factors. Rare earth elements are a group of critical minerals that are of great importance to modern technologies, ranging from electronics and renewable energy to defence systems. Afghanistan is known to possess significant deposits of these valuable resources, which have the potential to play a crucial role in global supply chains, especially in the face of ongoing rivalry between the People’s Republic of China and the United States of America. The research problem of the considerations undertaken in this article is to assess the key challenges and opportunities in harnessing Afghanistan’s rare earth element resources after the Taliban’s return to power. The research conducted shows that despite having a significant amount of rare earth elements, Afghanistan lacks the infrastructure necessary to extract and process these valuable minerals. After the Taliban victory, the newly established government sees the potential benefit in extracting rare earth elements and is willing to align itself with China to exploit them.

Correlation between nutrients, rare earth elements and heavy metals in O. Sativa rice plant organs by instrumentation neutron activation analysis and proton induced x-ray emission techniques

The accumulation of halogens and metals from roots to stems, leaves and grains of Oryza sativa rice plant collected in Northern Senegal (St Louis region) at the same stages of growth but at different salinity soil levels was investigated by measuring their elemental concentration by invasive instrumental techniques of neutron activation analysis and proton induced x-ray emission. The normalized elemental concentration of Na, Cl, K, (Cs, Rb, Sr, Sb, Ba Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Br, Rb, Sb was correlated with one of rare earth elements, La, Ce, Sm, Yb, Nd, Eu, Tb, Tm, and Lu) and the one of the heavy metals Hf, Ta and Th and to assess their subsequent distribution within the Oryza sativa rice plant in a particular salinity environment. The exploration of the experimental data was performed by applying machine learning techniques with Python to find their elemental correlations. This study shows that the accumulation of iron is highly correlated with the amount of rare earth elements and heavy metals investigated. We observe an inverse correlation between Fe and Cl concentrations in the roots and stems of the Oryza sativa rice plant, in which higher levels of Fe in the roots relative to stems correspond to lower levels of Cl. We also remark that there is no accumulation of rare earth elements in the root tissues of the different Oryza sativa rice plants studied. Whereas, in the stem, leaf, and grain organs there is a strong correlation between metal contents and rare earth elements.

RARE-EARTH elements in the topsoils of a Russian industrial city: Sources and human health risk assessment

Research on rare-earth elements (REEs) in urban soils of Russian industrial cities is extremely limited. This study investigates the potential sources and human health risks of REEs contained in the topsoils of the industrial Russian city of Chelyabinsk. The study also takes into account natural sources of REE as the city is located on the border of granites (Urals) and sedimentary rocks (Western Siberia). We analyzed the concentration and distribution of REEs in the soils of four types of locations: residential courtyards, city parks, roadsides, and industrial locations. The total REE concentrations ranged from 44 to 255 mg/kg, with average concentrations of 140, 124, 113 and 89 mg/kg in the courtyards, roadsides, industrial location and city parks, respectively. The REE content in courtyard soils could be influenced by poor cleaning of fallen leaves. The ratios of light REE (LREE) to heavy REE (HREE) ranged from 9.5 to 10.1, revealing an obvious fractionation between them. The fractionation of LREE and HREE, and the REE/ES (European Shale) pattern showed that REE accumulation in Chelyabinsk soils has been disturbed by human activities. It was shown that the dust from industrial emissions was the main anthropogenic source of REE accumulation in urban soil. The largest amounts of REEs are emitted from an electrometallurgical plant and zinc production plant. Fortunately, the estimated daily intakes of REE from soils for children and adults were well below the safety thresholds. At the same time, in order to prevent social tension and reduce the anthropogenic load on the urban area, it is recommended to use phytoremediation technologies, smart landscaping of industrial and residential areas, more thorough cleaning of fallen leaves and road dust. It is also recommended to move the most dangerous production processes outside the urban area.

Electrical Structure between the Main and Eastern Deposits of the Bayan Obo Mine: Results from Time-Domain CSEM Methods

Bayan Obo is a well-known polymetallic deposit containing significant quantities of rare earth elements, niobium, thorium, and iron. However, the epoch in which mineralization occurred and the mineralization process are still debated due to the complex nature of its mineralization and geological evolution. Inadequate geophysical exploration has further contributed to this lack of clarity surrounding critical issues, such as the deep link between the main orebody and the eastern orebody, the form and distribution of the extensive dolomite, and the geologic structures in the area. Therefore, we implemented the time-domain controlled-source electromagnetic method (CSEM) to acquire electrical structures at depths down to 2.5 km between the Main and Eastern mines. According to the inverted resistivity structure, in conjunction with existing geological and drilling data, we classified the main lithologies and faults based on their resistivity characteristics. Overall, the mineralized carbonatite reflects high to moderately high resistivity. The mineralized carbonatite dips overall from north to south, with a maximum extension depth not exceeding 1.5 km, and its range of occurrence is controlled by nearly east–west-striking faults distributed along the bounding line between the roof and floor rocks. The Main and Eastern mines are connected at depth, but the morphology and position of the ore bodies have significantly changed due to multiple phases of tectonic activity. The electrical structure does not reveal any obvious syncline structures, further refuting the traditional view that the Bayan syncline controls ore formation.

Rare‐earth element phytoextraction efficiency in southern Chinese mines under different clipping intensities using a co‐cropping system (Dicranopteris pedata and Pinus massoniana)

AbstractOur understanding of how varying clipping intensities affect the efficiency of phytoextraction remains limited, particularly with co‐cropping systems. This study focuses on assessing the effects of different clipping intensities on phytoextraction efficiency within co‐cropping systems dominated by the key species Dicranopteris pedata and Pinus massoniana in rare‐earth mines of southern China. Our results confirmed the following. Firstly, the compensation index, dry aboveground biomass, and rare‐earth elements (REE) accumulation of clipped D. pedata per unit area were highest under 100% clipping (p < 0.05). Meanwhile, the bioabsorption coefficient, bioconcentration factor, and translocation factor of P. massoniana were less than 1. Secondly, the soil catalase, sucrase, and α‐diversity indices of bacteria and fungi separately indicated no significant variation between the clipping treatments and control. The REE content in tree rings increased, and the total REE contents in thicker tree rings were higher than those in the thinner tree rings of P. massoniana from 1997 to 2016. Additionally, the soil erosion intensity diminished significantly in the growth area of P. massoniana from 1995 to 2019. Thirdly, both D. pedata and P. massoniana, when subjected to 100% clipping, could effectively remove excess REEs from the 0–20 cm soil layer within 18.57–61.19 years. In contrast, P. massoniana alone achieved a removal rate of excess REEs in the 20–60 cm layer, within 923.16–1899.62 years. Thus, D. pedata with 100% clipping can phytoextract the maximum amount of REEs. It is noted that P. massoniana cannot be used for REEs phytoextraction or phytostabilization. Co‐cropping with 100% clipping would have a less negative impact on growth and REEs extraction, and the co‐cropping system can phytoextract excess REEs from the surface soil within decades. However, it is not efficient for the phytoextraction of excess REEs from deep soil layers.

High efficiency simultaneous adsorption of rare earth elements from aqueous solutions using carbon xerogel-chitosan composite

ABSTRACT This study investigated the simultaneous sorption of rare earth elements (REEs) from acidic media using carbon xerogel functionalised with chitosan. The combined carbon xerogel with chitosan that was synthesised has a sphere-like structure and a larger BET surface area (275 m2 g−1) than pure carbon xerogel alone (228 m2 g−1). To determine the optimal conditions, adsorption of REEs was established under different variables, including pH, contact time, initial concentration, adsorbent wt. and temperature, as well as desorption experiments. The adsorption isotherms showed that both the Freundlich and Langmuir models were followed, in addition to a pseudo-second order kinetic model. The adsorption is likely exothermic, which confirms it is favourable at low temperatures, and a dissociative adsorption process is involved, according to analysis of thermodynamic state functions. Langmuir calculations revealed that the maximum amount of REEs that were adsorbed was 164 mg/g. Because of its superior adsorption capacity and simplicity in using a recycled material following several desorption cycles, carbon xerogel-chitosan is being employed as a novel adsorbent material to remove REEs from aqueous solutions.

Heflikite, ideally Ca2(Al2Sc)(Si2O7)(SiO4)O(OH), the first scandium epidote-supergroup mineral from Jordanów Śląski, Lower Silesia, Poland and from Heftetjern, Tørdal, Norway

Abstract Heflikite, the first Sc-dominant epidote-supergroup mineral, was discovered in two occurrences. The holotype was found in a granitic pegmatite associated with rodingite-like calc-silicate rocks and metasomatised granitic bodies exposed in a serpentinite quarry at Jordanów Śląski near Sobótka, Lower Silesia, SW Poland. The cotype comes from the Heftetjern pegmatite, Tørdal region, Norway. The holotype is composed of (in wt.%): 35.69 SiO2, 0.22 TiO2, 21.98 Al2O3, 6.12 Sc2O3, 0.07 V2O3, 1.10 Fe2O3, 0.11 Y2O3, 1.55 La2O3, 4.05 Ce2O3, 0.31 Pr2O3, 1.53 Nd2O3, 0.40 Sm2O3, 0.11 EuO, 0.56 Gd2O3, 0.14 MnO, 3.56 FeO, 0.16 MgO, 19.16 CaO and 1.78 H2O(+)calc.; total 98.60. The cotype contains: 34.92 SiO2, 0.44 TiO2, 0.82 SnO2, 19.13 Al2O3, 4.79 Sc2O3, 1.96 Fe2O3, 2.55 La2O3, 7.39 Ce2O3, 0.48 Pr2O3, 0.67 Nd2O3, 0.12 EuO, 0.61 Gd2O3, 0.13 MnO, 5.97 FeO, 17.66 CaO and 1.73 H2O(+)calc.; total 99.37. The compositions correspond to the following empirical formulae: (Ca1.729Ce0.125La0.048Nd0.046Gd0.016Sm0.012Pr0.010Y0.005Eu2+0.003)Σ1.994[(Al2.182Sc0.449Fe3+0.070V3+0.005)Σ2.706(Fe2+0.251Mg0.020Mn0.010)Σ0.281Ti0.014]Σ3.001(Si3.006O11)O(OH) and (Ca1.644Ce0.235La0.082Nd0.021Gd0.018Pr0.015Eu2+0.004)Σ1.019[(Al1.958Sc0.362Fe3+0.128)Σ2.448(Fe2+0.434Mn0.009)Σ0.443(Ti0.029Sn0.029)Σ0.058]Σ2.949(Si3.033O11)O(OH), respectively, and to the ideal formula Ca2(Al2Sc)(Si2O7)(SiO4)O(OH). The crystal structure of the holotype was refined in the monoclinic system with an R1 index of 8.62%. The crystal-structure refinement indicates exclusively Si occupied T sites, Al occupied M1 and M2 sites, and a Ca occupied A1 site. The M3 site is filled predominantly by trivalent cations, mainly Sc3+, with divalent cations (mainly Fe2+) as minor occupants. The A2 site is filled mostly by Ca with minor amounts of rare earth elements (REE). The holotype heflikite crystallised from metasomatic fluids that infiltrated a contact between the granitic pegmatite and the surrounding rodingite-type calc-silicate rocks and serpentinites. The fluids that introduced Sc into the pegmatite could have been either hydrothermal or related to low-grade regional metamorphism that postdated the formation of the pegmatite. The cotype heflikite formed during the late-stage hydrothermal crystallisation of the Sc-enriched granitic pegmatite.

Rare Earth Element Characteristics of Shales from Wufeng-Longmaxi Formations in Deep-Buried Areas of the Northern Sichuan Basin, Southern China: Implications for Provenance, Depositional Conditions, and Paleoclimate.

To explore the sedimentary environment and the background of the source area of organic-rich shales in the Wufeng-Longmaxi Formations in the northern Sichuan Basin, samples from Well XX1 in the area were subjected to geochemical testing and analysis of organic carbon content, trace elements, and rare earth elements (REEs). The results show that the total content of REE (ΣREE) of the shale in the Wufeng-Longmaxi Formations varied from 183.08 to 234.66 μg/g with an average of 212.59 μg/g, which is significantly higher than the content of the North American shale composite. The fluctuations in the total amount of REEs in the shale of the Wufeng-Longmaxi Formations reflect certain differences in the geochemical conditions of the Upper Ordovician-Lower Silurian shale. The ratios of LREE/HREE, LaN/YbN, LaN/SmN, and GdN/YbN and the distribution of normalized REE patterns indicate that the source supply or sedimentary structural background may have changed during the shale deposition period of the Wufeng Formation, while the shale deposition period of the Longmaxi Formation may be in a relatively stable source supply and sedimentary structural background. There is no significant correlation between δCe and ΣREE, and the obviously negative Eu abnormity and the weak Ce abnormity indicated that the diagenesis had a limited impact on REEs. Geochemical parameters such as values of ∑REE, δEu, δCe, Ceanom, and LaN/YbN indicate that the climate during the Wufeng-Longmaxi Formation shale deposition period was warm and humid, and the shale was deposited mainly in the suboxic-anoxic water environment. The deposition rate was stable and slow, providing good conditions for the production and preservation of organic matter. At the same time, this shows that the water environment of Wufeng Formation is more anoxic and reductive than that of Longmaxi Formation, which is more conducive to the preservation of organic matter. The correlation between ΣREE and the content of Sc, Ti, Cr, Co, Zr, Nb, Th, Hf, Ta, and other elements indicates that the sources of REEs in the shale of Wufeng and Longmaxi Formations in the study area are similar, mainly terrestrial clasts, and some may come from the sea. The REE distribution pattern shows that the shale provenance of the Wufeng-Longmaxi Formations mainly comes from the upper crust. The La/Yb-∑REE diagram shows that the sediment-parent rocks are mainly early sedimentary rocks and these sediment-parent rocks have granite provenance characteristics. Compared to La/Yb, LREE/HREE, LaN/YbN, and other REE characteristic parameters, it is inferred that the tectonic background of the study area is dominated by passive continental margin.

Impact of Rare Earth Elements on CaCO3 Crystallization: Insights into Kinetics, Mechanisms, and Crystal Morphology.

This study investigated the crystallization kinetics and mechanisms of calcium carbonate (CaCO3) in the presence of rare earth elements (REEs) including lanthanum (La), neodymium (Nd), and dysprosium (Dy). Through a comprehensive approach utilizing UV-vis spectrophotometry, powder X-ray diffraction, and high-resolution electron microscopy, we examined the effects of REEs on CaCO3 growth from solution at varying concentrations and combinations of REEs. Our findings highlight that even trace amounts of REEs significantly decelerate the rate of CaCO3 crystallization, also leading to alterations in crystal morphology and mechanisms of growth. The impact of REEs becomes more pronounced at higher concentrations and atomic mass, although the potential formation of poorly ordered REEs carbonate precursor phases can result in a decrease in the REE3+/Ca2+ ratio, influencing the crystallization rate of CaCO3. Vaterite and calcite were identified as the main crystallized polymorphs, with vaterite exhibiting distinct growth defects and calcite developing complex morphologies at higher REEs concentrations and an internal architecture suggesting a nonclassical growth route. We propose that REEs ions selectively adsorb onto different calcite surfaces, impeding growth on specific sites and resulting in intricate morphologies.