Soluble Rare Earth Elements Research Articles

Mixtures of rare earth elements show antagonistic interactions in Chlamydomonas reinhardtii

In order to better understand the environmental risks of the rare earth elements (REEs), it is necessary to determine their fate and biological effects under environmentally relevant conditions (e.g. at low concentrations, REE mixtures). Here, the unicellular freshwater microalga, Chlamydomonas reinhardtii, was exposed for 2h to one of three soluble REEs (Ce, Tm, Y) salts at 0.5μM or to an equimolar mixture of these REEs. RNA sequencing revealed common biological effects among the REEs. Known functions of the differentially expressed genes support effects of REEs on protein processing in the endoplasmic reticulum, phosphate transport and the homeostasis of Fe and Ca. The only stress response detected was related to protein misfolding in the endoplasmic reticulum. When the REEs were applied as a mixture, antagonistic effects were overwhelmingly observed with transcriptomic results suggesting that the REEs were initially competing with each other for bio-uptake. Metal biouptake results were consistent with this interpretation. These results suggest that the approach of government agencies to regulate the REEs using biological effects data from single metal exposures may be a largely conservative approach.

Application of Eh-pH Diagrams on Acid Leaching Systems for the Recovery of REEs from Bastnaesite, Monazite and Xenotime

Bastnaesite, monazite and xenotime are rare earth minerals (REMs) that are typical sources for rare earth elements (REEs). To advance the understanding of their leaching and precipitation behavior in different hydrometallurgical processes, Eh-pH diagrams were constructed and modified using the HSC 9.9 software. The aqueous stability of rare earth elements in H2O and acid leaching systems, i.e., the REE-Ligands-H2O systems, were depicted and studied based on the Eh-pH diagrams. This study considers the most relevant lixiviants, their resulting equilibrium states and the importance in the hydrometallurgical recovery of rare earth elements (REMs). A literature review was performed summarizing relevant Eh-pH diagrams and associated thermodynamic data. Shifting stability regions for REEs were discovered with additions of acid ligands and a narrow stability region for soluble REE-(SO4/Cl/NO3) complexes under highly acidic conditions. As such, the recovery of REEs can be enhanced by adjusting pH and Eh values. In addition, the Eh-pH diagrams of the major contaminants (i.e., Fe, Ca and Al) in leaching systems were studied. The resulting Eh-pH diagrams provide possible insights into potential passivation on the particle surfaces due to the formation of an insoluble product layer.

Ion-adsorption rare earth ores of China

Geology and geochemistry of China’s ion-adsorption rare earth ores are discussed. The structure and material constitution of Lognan, Huashan, Guposhan and Heling deposits are compared. The weathered layer structure, as well as the distribution, differentiation and occurrence forms of rare earth elements (REE) in the weathered layer are described. The prospecting indicators and criteria of readily dissociated adsorbed REE ore are identified to find this type ores in the territory of Russia. The weathered layer enclosing ion-adsorption rare earth ore features specific differentiation of REE. General composition of such ores is governed by the composition of the primary rare earth mineralization in mother granites. If granites contain much yttrium and heavy lanthanides, then ion-adsorption rare earth ore contain also much yttrium and heavy lanthanides. Regarding differentiation of REE, yttrium and heavy lanthanides mainly concentrate in the middle, most clayey part of the weathered layer, while cerium accumulates in subsurface lateritic soil. The prime feature of ion-adsorption rare earth ore is the prevalence of readily dissociated REE, which can reach a quantity of 80% and more but not less than a half. The rest REE concentrate in relict rock-forming minerals and accessories. The quantitative estimation of adsorption form of REE is necessary for the geological and economic appraisal of a deposit. It is assumed that the quantity of readily soluble REE should be not less than 0.05–50% of the total content. Russia has many regions with such geotectonic environment. It is required to explore ion-adsorption rare earth ore occurrences in these regions.

Rare Earth Elements (REEs) Rich-Phosphate Fertilizers Used in Brazil are More Effective in Increasing Legume Crops Yield Than Their REEs-Poor Counterparts

Rare earths elements (REEs) can affect plant growth positively. Besides their intentional agricultural use, REEs have also been involuntarily applied to soils through phosphate (P) fertilizers. This study aimed to evaluate the effects of REEs contained in P fertilizers on increasing legume crops yield in Brazilian agroecosystems. Field experiments were conducted with Phaseolus vulgaris L. and Glycine max (L.) Merrill with four sources of P (a pure ammonium phosphate with no REEs and three single superphosphates—SSP—with varying REEs contents) applied to the soil at four P rates (0, 17.5, 35, 70 kg ha−1). Irrespectively of the rate, the SSP—Catalao (richest in total and soluble REEs among the sources tested) consistently increased the yield of common bean (~ 30%) in relation to the control (ammonium phosphate). Single superphosphate Araxa (intermediate REEs content) also increased common bean yield. For soybean, the SSP-Catalao, at the 70 kg P ha−1 rate, was superior to the control (at the same level of P) and to the treatment without P addition. Our results showed that the REEs, present as impurities in phosphate fertilizers, increase their effectiveness on legume crops yield. These findings are relevant, as producers could enhance yield with REEs-rich P-fertilizers, especially in tropical agroecosystems, where high application rates are required.

Rare earth elements recovery from secondary wastes by solid-state chlorination and selective organic leaching

Processing of end-of-life products (EoL) containing rare earth elements (REE) has gained increasing importance in recent years with the aim of avoiding supply risks. In addition, circular economy renders complete recirculation of technology metals mandatory. Fluorescent lamp wastes are an important source for REE recovery since they contain significant amounts, up to 55 wt%, of Y and Eu in red phosphors. For these purposes, solid-state chlorination (SSC) is an economically attractive alternative to wet acid leaching treatment, which profits from a considerable reduction of chemicals consumption and process costs. Chlorination takes place with dry HCl(g) produced from thermal decomposition of NH4Cl(s), not only converting the REE content of the Hg-free phosphor waste into water soluble REE metal chlorides, but also avoiding the implications of aqueous complex chemistry of REE. To establish an industrial process viable on a commercial scale, the SSC process has been optimized by (i) using a design of experiment (DOE) varying temperature, residence time, and gNH4Cl/gsolid ratio and (ii) improved leaching of the chlorinated metals with an organic mixture selective for REE. As a result, 95.7% of the Y and 92.2% of the Eu were selectively recovered at 295.9 °C, 67 min and a ratio of 1.27 gNH4Cl/gsolid, followed by quantitative selective leaching of the REE. Owed to its low chemicals consumption and operation costs, the current process allows for valorizing lamp waste even when raw material prices are low.

Syntrophic effect of indigenous and inoculated microorganisms in the leaching of rare earth elements from Western Australian monazite

The unique physiochemical properties exhibited by rare earth elements (REEs) and their increasing application in high-tech industries has created a demand for secure supply lines with established recovery procedures that create minimal environmental damage. Bioleaching experiments conducted on a non-sterile monazite concentrate with a known phosphate solubilising microorganism (PSM) resulted in greater mobilisation of REEs into solution in comparison to experiments conducted on sterile monazite. By combining the native consortia with an introduced PSM, a syntrophic effect between the populations effectively leached a greater amount of REEs than either a single PSM or the indigenous population alone. With sterile monazite, Penicillium sp.CF1 inoculated experiments released a total REE concentration of 12.32 mg L−1 after incubation for 8 days, whereas on non-sterile ore, double the soluble REE concentration was recorded (23.7 mg L−1). Comparable effects were recorded with Enterobacter aerogenes, Pantoea agglomerans and Pseudomonas putida. Alterations in the microbial populations during bioleaching of the monazite ore were determined by diversity profiling and demonstrated noticeable changes in community inhabitants over 14 days. The presence of native Firmicutes on the monazite appears to greatly contribute to the increased leaching recorded when using non-sterile monazite for REE recovery.

Toxicity of Nine (Doped) Rare Earth Metal Oxides and Respective Individual Metals to Aquatic Microorganisms Vibrio fischeri and Tetrahymena thermophila.

Despite the increasing use of rare earth elements (REEs) and oxides (REOs) in various technologies, the information on their ecotoxicological hazard is scarce. Here, the effects of La3+, Ce3+, Pr3+, Nd3+, Gd3+, CeO2, and eight doped REOs to marine bacteria Vibrio fischeri and freshwater protozoa Tetrahymena thermophila were studied in parallel with REO dopant metals (Co2+, Fe3+, Mn2+, Ni2+, Sr2+). The highest concentrations of REOs tested were 100 mg/L with protozoa in deionized water and 500 mg/L with bacteria in 2% NaCl. Although (i) most REOs produced reactive oxygen species; (ii) all studied soluble REEs were toxic to bacteria (half-effective concentration, EC50 3.5–21 mg metal/L; minimal bactericidal concentration, MBC 6.3–63 mg/L) and to protozoa (EC50 28–42 mg/L); and (iii) also some dopant metals (Ni2+, Fe3+) proved toxic (EC50 ≤ 3 mg/L), no toxicity of REOs to protozoa (EC50 > 100 mg/L) and bacteria (EC50 > 500 mg/L; MBC > 500 mg/L) was observed except for La2NiO4 (MBC 25 mg/L). According to kinetics of V. fischeri bioluminescence, the toxicity of REEs was triggered by disturbing cellular membrane integrity. Fortunately, as REEs and REOs are currently produced in moderate amounts and form in the environment insoluble salts and/or oxides, they apparently present no harm to aquatic bacteria and protozoa.

Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand

Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce4+ as CeO2 and transported REE3+ downward to the lower part of the profile. The transported REE3+ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.

Light Rare Earth Elements enrichment in an acidic mine lake (Lusatia, Germany)

The distribution of Rare Earth Elements (REE) was investigated in the acidic waters (lake and groundwater) of a lignite mining district (Germany). The Fe- and SO4-rich lake water (pH 2.7) displays high REE contents (e.g. La∼70 μg/l, Ce∼160 μg/l) and an enrichment of light REE (LREE) in the NASC normalised pattern. Considering the hydrodynamic model and geochemical data, the lake water composition may be calculated as a mixture of inflowing Quaternary and mining dump groundwaters. The groundwater of the dump aquifer is LREE enriched. Nevertheless, the leachates of dump sediments generally have low REE contents and display flat NASC normalised patterns. However, geochemical differences and REE pattern in undisturbed lignite (LREE enriched pattern and low water soluble REE contents) and the weathered lignite of the dumps (flat REE pattern and high water soluble REE contents) suggest that lignite is probably the main REE source rock for the lake water.

Effects of spraying rare earths on contents of rare Earth elements and effective components in tea.

Rare earth (RE) fertilizer is widely applied in China to increase the yield and the quality of crops including tea. However, the effects of spraying RE fertilizer on the contents of rare earth elements (REE) and effective components in tea are unknown. The results from basin and field experiments show that the values of the REE concentrations in new shoots of tea plants and the concentration of REE in the soil (REE/REEs) either from control basins or from treatment basins were smaller than those in other parts of tea plant and similar between control and treatment. The longer the interval between spraying RE fertilizer and picking the shoots of tea plants, the less the effects from spraying. About 80% summation operator REE (the sum of the concentrations of 15 REE) in tea, whether it came from spraying or not, was insoluble in the infusion. About 10% the soluble REE of summation operator REE in tea infusion was bound to polysaccharide, and the amount of REE bound polysaccharide decreased over time. At least a 25 day safety interval is needed between spraying and picking if the microelement fertilizer is used, in order to enhance tea output and to ensure tea safety.

Rare earth elements in naturally grown fern Dicranopteris linearis in relation to their variation in soils in South-Jiangxi region (Southern China)

Ferns (Dicranopteris linearis) and soils, sampled from four rare earth mining areas and one non-mining area locating in South-Jiangxi region, were chosen for analysis of 15 rare earth elements (REEs) by inductively coupled plasma–mass spectrometry (ICP–MS). The fern samples were divided into 4 parts: root, stem, petiole, and lamina. The soils of the same sites were also sampled, and 4 soil layers were observed at the profile: A (0–20 cm depth), B (20–150 cm depth), C (150–400 cm depth), and D (rock). The distribution patterns and transportation characteristics of REEs of different soil layers and of different parts of D. linearis were studied. The results showed that in the soil layers, the ΣREE (the sum of the concentrations of 15 REEs) of A layer, as well as B layer were lower than that of C layer, but Ce was relatively concentrated in A layer. The ΣREE of different parts of D. linearis were lamina, root>stem>petiole. The REE distribution patterns of D. linearis root were similar to the total REE distribution patterns of the A layer of their host soils, especially to the soluble REE distribution patterns of the A layer of their host soils. The REEs were fractionated in their transportation in D. linearis. The abundances of heavy rare earth elements (HREEs, Gd to Lu and Y) in the stem, petiole, lamina are lower than those in the root.

Concentrations and flux of rare earth elements in a semifield plot as influenced by their agricultural application.

The concentrations of rare earth elements (REs) in atmospheric particles, soil, soil water, surface runoff, and different parts of corn in an experimental plot in the suburb of Beijing, China were measured and the flux of REs was estimated. The concentration of REs in air particles with diameter less than 10 microm is 36 ng/m3 and, by ratio analysis, the origin of REs in the atmosphere was likely local soil. The concentration of soluble REs is 0.69 microg/L in rainwater, 5-7 microg/L in surface runoff, as well as 1-4 microg/L in soil water and the application of RE mixture has no observed influences on their concentrations. The concentration of soluble REs in surface runoff and soil water was dominated by aqueous-solid-phase partitioning. By estimation of the flux, most of the REs applied will remain in the soil phase and continued application of REs will cause an accumulation of REs in agricultural soil.

Rare earth element supply to the Ocean

More insight on rare earth element pathways from land to ocean comes from analyses of suspended matter in four major world rivers (Amazon, Congo, Ganges, Mekong), while their geochemical behavior at the river-ocean boundary has been studied in the Gironde estuary (France). The Gironde data indicate that soluble rare earth elements are removed from solution in the estuarine zone; this observation invalidates any rare earth element balance to the ocean which would not take into account the river-ocean boundary processes. Data on rare earth element concentrations in soluble and detrital river loads show that solid discharge represents the major part of rare earth elements supplied by rivers to the ocean. A rare earth material balance to the ocean is discussed on the basis of the results presented in this paper.