Rare Earth Mixtures Research Articles

Association between Exposure of Rare Earth Elements and Outcomes of In Vitro Fertilization-Embryo Transfer in Beijing

Objective The study aimed to investigate the impact of rare earth elements (REEs) exposure on pregnancy outcomes of in vitro fertilization-embryo transfer (IVF-ET) by analyzing samples from spouses.Methods A total of 141 couples were included. Blood and follicular fluid from the wives and semen plasma from the husbands, were analyzed for REEs using inductively coupled plasma mass spectrometry (ICP-MS). Spearman's correlation coefficients and the Mann–Whitney U test were used to assess correlations and compare REE concentrations among three types of samples, respectively. Logistic models were utilized to estimate the individual REE effect on IVF-ET outcomes, while BKMR and WQS models explored the mixture of REE interaction effects on IVF-ET outcomes.Results Higher La concentration in semen (median 0.089 ng/mL, P = 0.03) was associated with a lower fertilization rate. However, this effect was not observed after artificial selection intervention through intracytoplasmic sperm injection (ICSI) (P = 0.27). In semen, the REEs mixture did not exhibit any significant association with clinical pregnancy.Conclusion Our study revealed a potential association between high La exposure in semen and a decline in fertilization rate, but not clinical pregnancy rate. This is the first to report REEs concentrations in follicular fluid with La, Ce, Pr, and Nd found at significantly lower concentrations than in serum, suggesting that these four REEs may not accumulate in the female reproductive system. However, at the current exposure levels, mixed REEs exposure did not exhibit reproductive toxicity.

Biostimulant Response of Foliar Application of Rare Earth Elements on Physiology, Growth, and Yield of Rice.

Rare earth elements (REEs) have been intentionally used in Chinese agriculture since the 1980s to improve crop yields. Around the world, REEs are also involuntarily applied to soils through phosphate fertilizers. These elements are known to alleviate damage in plants under abiotic stresses, yet there is no information on how these elements act in the physiology of plants. The REE mode of action falls within the scope of the hormesis effect, with low-dose stimulation and high-dose adverse reactions. This study aimed to verify how REEs affect rice plants' physiology to test the threshold dose at which REEs could act as biostimulants in these plants. In experiment 1, 0.411 kg ha-1 (foliar application) of a mixture of REE (containing 41.38% Ce, 23.95% La, 13.58% Pr, and 4.32% Nd) was applied, as well as two products containing 41.38% Ce and 23.95% La separately. The characteristics of chlorophyll a fluorescence, gas exchanges, SPAD index, and biomass (pot conditions) were evaluated. For experiment 2, increasing rates of the REE mix (0, 0.1, 0.225, 0.5, and 1 kg ha-1) (field conditions) were used to study their effect on rice grain yield and nutrient concentration of rice leaves. Adding REEs to plants increased biomass production (23% with Ce, 31% with La, and 63% with REE Mix application) due to improved photosynthetic rate (8% with Ce, 15% with La, and 27% with REE mix), favored by the higher electronic flow (photosynthetic electron transport chain) (increase of 17%) and by the higher Fv/Fm (increase of 14%) and quantum yield of photosystem II (increase of 20% with Ce and La, and 29% with REE Mix), as well as by increased stomatal conductance (increase of 36%) and SPAD index (increase of 10% with Ce, 12% with La, and 15% with REE mix). Moreover, adding REEs potentiated the photosynthetic process by increasing rice leaves' N, Mg, K, and Mn concentrations (24-46%). The dose for the higher rice grain yield (an increase of 113%) was estimated for the REE mix at 0.72 kg ha-1.

Occurrence of rare earth elements in umbilical cord serum and association with thyroid hormones and birth outcomes in newborns

Rare earth elements (REEs) are emerging contaminants that are increasingly used in high technology products. However, limited information is available regarding exposure to REEs and associated health effects in neonates. This study aimed to investigate the association between REE concentrations and thyroid hormone levels, as well as birth outcomes in 109 newborns in Beijing, China. We measured the concentrations of 16 REEs and thyroid hormones in umbilical cord serum. To assess the impact of exposure to individual REEs and REE mixtures on thyroid hormone levels and birth outcomes, we employed univariate linear regression, least absolute shrinkage and selection operator (LASSO), and weighted quantile sum (WQS) models. We detected 14 REEs at high rates (92.6%–100%), with yttrium exhibiting the highest median (interquartile range) concentration [43.94 (0.33–172.55) ng/mL], followed by scandium [3.64 (0.46–11.15) ng/mL]. Univariate analyses showed that per logarithmic (ln)-unit change of neodymium (Nd) and samarium (Sm) was associated with 0.039 [95% confidence interval (CI): 0.001, 0.007] and 0.031 (95% CI: 0.003, 0.060) increases in free thyroxine (FT4) levels, respectively. Moreover, 14 REEs exhibited significant associations with triiodothyronine (T3) levels, resulting in increases ranging from 0.066 to 0.307. Elevated concentrations of terbium (Tb) [per ln-unit change: −0.021 (95% CI: −0.041, −0.01)] and lutetium (Lu) [-0.023 (95% CI: −0.043, −0.002)] were inversely correlated with birth length in newborns. A further multiple exposure analysis employing the LASSO model identified Sm, Nd, Y, Sc, and Lu as critical factors influencing FT4 and T3 levels. Additionally, WQS analyses showed positive associations between exposure to a mixture of 14 REEs and FT4 (P = 0.046), T3 (P < 0.001), and birth length (P = 0.049). These findings suggest that in utero exposure to REEs might disrupt thyroid hormone homeostasis and impact intrauterine growth. Further studies are warranted to validate these findings and elucidate the underlying mechanisms.

Hydrothermal synthesis of zirconia doped with naturally mixed rare earths oxides and their electrochemical properties for possible applications in solid oxide fuel cells

Solid oxide fuel cells (SOFC) are electrochemical conversion devices that produces electricity directly from oxidizing a fuel and their development became of high importance to drastically reduce the greenhouse emission. Rare earth elements (REEs) are widely used as materials and dopants in controlling the ionic conductivity of solid electrolytes for SOFCs. Their criticality and high costs for separation to individual REEs lead to first studies aiming to search possible use of mixed REEs with natural occurrence as extracted from concentrates. This paper focused on obtaining sintered pellets based on zirconia doped with natural mixture of REEs extracted from monazite and study their microstructure, impedance spectra and dielectric properties vs. operating temperatures to assess their potential applications as solid electrolyte. ZrO2 doped powders with 8% natural mixture of REEs (8ZrMZ) were synthesized by hydrothermal process. ZrO2 doped with 4% Y2O3 (4ZrY) and 8%Y2O3 (8ZrY) were also obtained by the same route and used as standard materials already used in commercial SOFCs. All powders were uniaxially pressed and sintered in air, with highest densities obtained for 1400 °C. The Niquist diagrams for 8ZrMZ samples show significantly lower ionic conductivity compared to standards 4ZrY and 8 ZrY. This may be attributed to the presence of detrimental Fe and Si impurities following the mixed REE after Th and U removal from monazite concentrates and the ratio of REEs in the dopant composition affecting the ionic conductivity due to possible association of structural defects. Research works are further needed to improve the receipt for using naturally mixed REEs and asses their possible use as a competitive dopant for solid electrolytes.

Association between prenatal exposure to rare earth elements and the neurodevelopment of children at 24-months of age: A prospective cohort study

The increasing consumption of rare earth elements (REEs) has resulted in a considerable risk of environmental exposure. However, the adverse effects of prenatal REEs exposure on children's neurodevelopment are not yet fully recognized. Therefore, we investigated the individual and joint effects of prenatal exposure to 13 REEs on children's neurocognitive development based on 809 mother-child pairs from a large birth cohort in Wuhan, China. Maternal urinary concentrations of 13 REEs were repeatedly measured by inductively coupled plasma mass spectrometry. Children's neurodevelopment [e.g., mental and psychomotor development index (MDI/PDI)] at 24-months was assessed using Bayley Scales of Infant Development of Chinese Revision. GEE and BKMR models were applied to estimate the individual and joint effects of prenatal REE exposure on child neurodevelopment level. After controlling for typical confounders, we observed that exposure to 9 REEs during the first trimester were significantly associated with decreased MDI scores [βs and 95% confidence intervals (CIs) ranging from −2.24 (−3.86 ∼ −0.63) to −1.44 (−2.26∼ −0.26)], and 7 REEs during third trimester were significantly associated decreased PDI scores [β and 95% CIs ranging from −1.95 (−3.19 ∼ −0.71) to −1.25 (−2.34 ∼ −0.16)]. Higher quantiles of REE mixture in first and third trimester were associated with decreased MDI and PDI score. Thulium, erbium in the first trimester and cerium, lanthanum in the third trimester accounted most importance to joint effects on MDI and PDI, respectively. In conclusion, prenatal exposure to higher concentrations of REEs during the first and third trimester were negative associated with children's neurodevelopment.

Associations of maternal urinary rare earth elements individually and in mixtures with neonatal size at birth

Prenatal rare earth elements (REEs) exposure is linked to unfavorable health consequences. Epidemiologic research on repeated measurements of REEs during gestation correlated with fetal growth is exiguous. Until now, few studies have characterized exposure characteristics of REEs in pregnant women. We aimed to ascertain the characteristics and predictors of REEs exposure over three trimesters among pregnant women and examine the possible effects of prenatal REEs exposure on size at birth. Urinary REEs concentrations exhibited considerable within-subject variation with intraclass correlation coefficients ranging from 0.16 to 0.58. Maternal age, household income, gestational weight gain, passive smoking during pregnancy, parity, and neonatal gender were associated with maternal urinary REEs concentrations. Elevated maternal urinary holmium and thulium concentrations in the 3rd trimester were significantly related to reductions in birth weight. Weighted quantile sum (WQS) regression model identified that urinary REEs mixture in the 3rd trimester were negatively related to birth weight (WQSREEs β = −26.22; 95% confidence interval [CI]: −47.62, −4.82), with holmium (40%) and thulium (24%) receiving the highest weights. Male infants received the most weight (>50%) related to decreased birth weight. This study revealed a significant association between individual and mixture REE exposure in late pregnancy with a reduction in birth weight.

Associations between maternal urinary rare earth elements during pregnancy and birth weight-for-gestational age: Roles of cord blood vitamin D levels

Prenatal exposure to rare earth elements (REEs) may contribute to adverse birth outcomes in previous studies. Cord blood vitamin D has been suggested to modify or mediate the effects of environmental exposures. However, none has investigated these roles of cord blood vitamin D in the associations of prenatal exposure to REEs with fetal growth. Maternal trimester-specific urinary concentrations of 13 REEs, cord blood total 25-hydroxyvitamin D at delivery, and birth weight (BW)-for-gestational age (GA) were determined in 710 mother-newborn pairs from Wuhan, China. Higher maternal average urinary concentrations of europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), erbium (Er), and ytterbium (Yb) across three trimesters, either individually or jointly, were significantly associated with lower BW-for-GA Z-scores and higher odds of small for gestational age (SGA) [β = −0.092; 95 % confidence interval (CI): −0.149, −0.035 for BW-for-GA Z-scores, and odds ratio = 1.60; 95 % CI: 1.14, 2.24 for SGA involved in each unit increase in weighted quantile sum index of REEs mixture]. When stratified by cord blood vitamin D levels, the associations mentioned above persisted in participants with relatively low vitamin D levels (<13.94 μg/L, the first tertile of distribution), but not among those with relatively high levels (≥13.94 μg/L) (all p-values for interaction < 0.05). The mediation analyses taking account of exposure-mediator interaction showed that the relationships between REEs (as individual and mixture) exposure and lower BW-for-GA were partly mediated through decreasing cord blood vitamin D levels. The proportions mediated by cord blood vitamin D levels were 24.48 % for BW-for-GA Z-scores and 29.05 % for SGA corresponding to the REEs mixture exposure. Conclusively, our study revealed that prenatal exposures to Eu, Gd, Dy, Ho, Er, and Yb were related to fetal growth restriction. Cord blood vitamin D might alleviate toxic effects of these REEs and its reduction might partly mediate REE-induced fetal growth restriction.

Fate, subcellular distribution and biological effects of rare earth elements in a freshwater bivalve under complex exposure

Rare earth elements (REE) are emerging contaminants due to their increased use in diverse applications including cutting-edge and green-technologies. Their environmental concerns and contradicting results concerning their biological effects require an extensive understanding of REE ecotoxicology. Thus, we have studied the fate, bioaccumulation and biological effects of three representative REE, neodymium (Nd), gadolinium (Gd) and ytterbium (Yb), individually and in mixture, using the freshwater bivalve Corbicula fluminea. The organisms were exposed for 96 h at 1 mg L−1 REE in the absence and presence of dissolved organic matter (DOM) reproducing an environmental contamination. Combined analysis of the fate, distribution and effects of REE at tissue and subcellular levels allowed a comprehensive understanding of their behaviour, which would help improving their environmental risk assessment. The bivalves accumulated significant concentrations of Nd, Gd and Yb, which were decreased in the presence of DOM likely due to the formation of REE-DOM complexes that reduced REE bioavailability. The accumulation of Nd, Gd and Yb differed between tissues, with gills > digestive gland ≥ rest of soft tissues > hemolymph. In the gills and in the digestive gland, Nd, Gd and Yb were mostly (>90 %) distributed among metal sensitive organelles, cellular debris and detoxified metal-rich granules. Gadolinium, Yb and especially Nd decreased lysosome size in the digestive gland and disturbed osmo- and iono-regulation of C. fluminea by decreasing Na concentrations in the hemolymph and Ca2+ ATPase activity in the gills. Individual and mixed Nd, Gd and Yb exhibited numerous similarities and some differences in terms of fate, accumulation and biological effects, possibly because they have common abiotic and biotic ligands but different affinities for the latter. In most cases, individual and mixed effects of Nd, Gd, Yb were similar suggesting that additivity approach is suitable for the environmental risk assessment of REE mixtures.

Removal of REE and Th from solution by co-precipitation with Pb-phosphates

The supply of technologically important rare earth elements (REE) is a concern in Europe, hence the recovery of REE from alternative sources has recently become widely investigated. One of the problems is the lack of cost-effective technologies for REE recovery from leaching solutions. The present work investigated the potential for recovering REE and Th from leaching solutions by co-precipitation with Pb phosphates. A set of four experiments were conducted using analytical reagent grade chemicals to analyze the effects of Pb and different pH on the efficiency of REE and Th removal from aqueous solutions. After selecting the best conditions, two additional experiments were performed using solutions obtained from leaching REE-rich apatite mine waste.The precipitates resulting from the experiments as well as the solutions before and after precipitation were analyzed. It was found that the formation of a crystalline mixture of REE- and Th- enriched pyromorphite, Pb5(PO4)3Cl, and Pb-phosphates, about which little has been known so far, was responsible for complete (>99%) removal of REE and Th from aqueous solutions at pH 4 and 6. At lower pH, the removal is incomplete except for Sc and Th, which probably form a distinct phases. Besides that, no fractionation of LREE and HREE was observed. The experiments included the study of solutions resulting from the leaching of REE-rich apatite waste, which may contribute to the development of new technologies for REE recovery from wastes.

Rare earth elements in sediments from a representative Chinese mariculture bay: Characterization, DGT-based bioaccessibility, and probabilistic ecological risk

Rare earth elements (REEs) are emerging contaminants due to their worldwide exploitation in the high-technology sector. Aquaculture systems, particularly those located within coastal areas, are fragile ecosystems due to anthropogenic impacts regarding urban and aquaculture activities. However, to date, there are no reports on the combined toxicity of rare earth element (REE) mixtures on aquatic biota in sediments from coastal aquaculture systems. In this study, the combined toxicity of REE mixtures based on probabilistic risk assessment indicated that the surface sediments of Zhelin Bay had a 1.86% probability of toxic effects on aquatic biota. The average value of total REEs (TREEs) was 297.37 μg/g, with light REEs representing the major part. A factor analysis (FA)-geographic information system (GIS)-based approach coupled with correlation analysis (CA) revealed that the REEs are derived from anthropogenic sources through fluvial processes.

Effect of HIP and Mixture of Rare Earth Elements on the Microstructure and Mechanical Performance of Aged Nanostructured Inconel 718.

Effect of HIP and Mixture of Rare Earth Elements on the Microstructure and Mechanical Performance of Aged Nanostructured Inconel 718.

Dissolution of Rare Earth Elements Concentrate from Xenotime Sand with Strong Acids

Rare Earth Elements (REE) concentrate from the processing of xenotime minerals still contains a mixture of REE and its impurities, so it requires a further separation process to purify the content of each element. The first step to separating each element of REE is to dissolve the REE concentrate in strong acid as a feed for the liquid-liquid extraction or ion exchange column process. The REE concentrate was dissolved in 3 variations of strong acids, namely hydrochloric acid, nitric acid, and sulfuric acid. XRF and FTIR analyses were done before and after the dissolution process. The results showed that sulfuric acid is the best dissolution reagent for the total rare earth elements (71.75%) but is less selective for separating light REE, heavy REE, and their impurities. Better selectivity for separating light REE and heavy REE is shown by dissolution with nitric acid with dissolution levels of 37.32% and 81.91%, respectively. Meanwhile, hydrochloric acid showed the lowest dissolution results for the total element of REE (63.14%) but had the best selectivity to prevent the dissolving of radioactive elements. The results of the FTIR analysis showed that REE-chloride, REE-nitrate, and REE-sulfate bonds had been formed in each dissolving filtrate.

Free Energy Calculations and Conformational Analysis of Dibenzo-30-crown-10 with Sm2+, Eu2+, and Three Halide Salts in THF Using the AMOEBA Force Field.

Crown ether complexes have been tailored for use in industrial separations of lanthanides (Ln) as a part of rare earth mining and refining. Dibenzo-30-crown-10 (DB30C10) is one of the most efficient complexants for the separation of rare earth mixtures based on the cation size. To understand the origin of this complexation, molecular dynamics (MD) simulations of DB30C10 have been performed using different combinations of divalent Sm and Eu and three halide salts Cl-, Br-, and I- in tetrahydrofuran (THF) solvent. DB30C10 was parameterized here for the polarizable atomic multipole optimized energetics for biomolecular simulation (AMOEBA) force field, and the existing parameters of THF, Sm2+, and Eu2+ were employed from our previous efforts. The large conformational fluctuations present in the DB30C10 systems were found to be dependent both on the identity of the lanthanide and halide complexes. For Cl- and Br- systems, there were no observed conformational changes at 200 ns, while in I- systems, there were two conformational changes with Sm2+ and one with Eu2+ within that same timeframe. In SmI2-DB30C10, there were three stages of conformational changes. In the first stage, the molecule is unfolded, in the second stage, the molecule is partly folded, and finally, in the third stage, the molecule is completely folded. Lastly, the Gibbs binding free energies of DB30C10 with SmBr2 and EuBr2 have been computed, which resulted in nearly identical ΔGcomp values for each lanthanide with Sm2+ being slightly more favorable. Considering the folding mechanism of the SmI2 system with DB30C10, the Gibbs binding free energies of DB30C10 and dicyclohexano-18-crown-6 (DCH18C6) with SmI2 were calculated separately and compared to probe their complexation affinities, in which the former was found to be more favorable.

Chromatographic Separation of Rare Earth Elements as MGDA Complexes on Anion Exchange Resins

Chromatographic separation of rare earth elements (REE) as anionic complexes with chelating aminopolycarboxylate ligand methylglycine N,N-diacetate (MGDA) was studied experimentally. A synthetic mixture of La, Nd, and Eu were used to model a REE mixture obtained from processed secondary sources such as phosphogypsum (PG). In the REE extraction from PG, the REEs can be recovered with MGDA to obtain the REE–MGDA mixture. Three strong base anion exchange resins (Dowex 1X8, IRA-402, and IRA-410) were used as the separation materials. Successful separation of the REEs by elution with dilute HNO3 and HCl was attributed to differences in the stabilities of the REE–MGDA complexes. The pKa values of the complexes were determined by titration to be 3.81, 3.25, and 2.96 for La, Nd, and Eu, respectively. Fractionation of the ternary La-Nd-Eu mixture (with a 1:1:1 mole ratio) were studied. La was recovered at approximately 80% purity and 80% yield, but strong trade-offs between the yield and the purity of Nd and Eu must be made. Chromatographic separation was found to be an efficient process option, considering its simplicity and the recovery of several product fractions. The initial process design offers a promising starting point for investigating more advanced process configurations for the efficient recovery of pure REE from phosphogypsum.

Influence of Synergistic Tributyl Phosphate and Di-(2-ethylhexyl)phosphoric Acid for Separation of Gadolinium and Samarium by Emulsion Liquid Membrane

Gadolinium is one of the rare earth elements, which plays an essential role in modern industry. Its separation from mixtures of other rare earth elements is challenging due to similar physical and chemical properties. The extraction method using an emulsion liquid membrane is an effective and simple method for separating low concentration gadolinium from other rare earth elements mixtures. It is more eco-friendly than the liquid-liquid extraction process and also has various advantages. This study aims to determine the effectiveness, permeability and optimum formulation conditions for the separation of gadolinium and samarium using synergistic ligands tributyl phosphate and di-(2-ethylhexyl)phosphoric acid. The results showed a quantitative extraction (87.40%) of gadolinium ion at the optimum conditions of 0.025 M tributyl phosphate + 0.075 M di-(2-ethylhexyl phosphate), 4% span 80 as surfactant, 9000 rpm emulsification stirring speed and 0.5 M nitric acid as stripping phase, for a feed containing 1.5 mg/L gadolinium ion and 3 mg/L samarium ion at 5 M HNO3.

Association between rare earth element exposure during pregnancy and newborn telomere length.

Telomere length (TL) is considered a marker of biological aging and lifetime health, and some epidemiological studies report that the environmental exposures may influence TL at birth. We aimed to investigate the associations between prenatal rare earth elements (REE) exposure and newborn TL. A total of 587 mother-newborn pairs were recruited during 2013 to 2015 in Wuhan, China. Maternal urinary concentrations of REE collected during three trimesters were measured by inductively coupled plasma mass spectrometry. Quantitative real-time polymerase chain reaction was used to measure relative cord blood TL. The trimester-specific associations between prenatal REE exposure and cord blood TL were evaluated using multiple informant models. Weighted quantile sum regression was used to estimate the mixture effect of urinary REE on cord blood TL. After adjustment for potential confounders, per doubling of urinary REE (Dy, Yb, Pr, Nd, and Tm) concentrations (μg/g creatinine) during the second trimester was respectively associated with 1.94% (95% CI 0.19%, 3.72%), 2.10% (95% CI 0.31%, 3.92%), 2.11% (95% CI 0.35%, 3.89%), 2.08% (95% CI 0.01%, 4.20%), and 1.38% (95% CI 0.09%, 2.70%) increase in cord blood TL. Furthermore, exposure to the mixture of REE during the second trimester was also significantly associated with increased cord blood TL (percent change 1.20%, 95% CI 0.30%, 2.11%). However, these associations were not statistically significant in the first and third trimesters. This study provides new evidence on the potential effect of prenatal REE exposure on the initial (newborn) setting of offspring's telomere biology. Further epidemiological studies are warranted to confirm our findings.

Biosorption and biomagnetic recovery of La3+ by Magnetospirillum magneticum AMB-1 biomass

Biosorption is a simple, efficient, and eco-friendly method for aqueous waste stream treatment. However, the main drawback is the need for biomass removal after adsorption, which can be expensive and energy intensive. In the present study, biomass from the magnetotactic bacterium Magnetospirillum magneticum AMB-1 is evaluated for trivalent lanthanum (La3+) removal and recovery from an aqueous solution, as this naturally magnetic biomass can be easily separated from solution after adsorption using an external magnet. This is the first report of this common magnetotactic strain utilized for biosorption of a rare earth element. The adsorption capacity is 6.0 ± 0.15 mg La3+/g wet biomass (37.2 ± 1.2 mg La3+/g dry biomass) using 10 g/L AMB-1 wet biomass (1.6 g/L dry basis) in a 100 mg/L La3+ solution at pH 6.0, which is greater than that reported for some other bacterial species. Only a minor decrease in biosorption is observed when the salinity is increased to 1.5 M NaCl, and temperature variations up to 50 °C have little to no impact, suggestive of potential applications for biosorption from saline waste streams. The equilibrium biosorption data best fits the Langmuir isotherm model, and thermodynamic analysis indicates thermodynamically favorable lanthanum binding to AMB-1. Binding of La3+ to the AMB-1 biomass occurs through carboxyl, phosphate, and amide functional groups naturally present in the biomass. AMB-1 biomass can be used for at least five rounds of La3+ adsorption and desorption, as well as the separation and concentration of a mixture of rare earth elements. Rapid adsorption and desorption times of 8 min, as well as a simple magnetic separation, make M. magneticum AMB-1 biomass a promising biosorbent for rare earth metals in aqueous waste streams.

Substituted diamides of dipicolinic acid as extractants and ionophores for rare earth metals

The variety of newly synthesized diamides of dipicolinic acid (DPA) bearing methyl- and oxymethyl substituents in various positions of phenyl ring was investigated as potential ligands for liquid–liquid extraction of rare earth metal ions and as membrane active compounds in plasticized polymeric membranes of potentiometric sensors. It is found that scandium is extracted with 2,6-pyridinedicarboxylic acid diamides similarly to heavy lanthanides, while yttrium is extracted together with light group lanthanides. DPA shows high selectivity for the separation of cadmium/zinc, lead/nickel or copper/nickel pairs. The four out of six studied ligands demonstrate significant potentiometric sensitivity towards scandium, yttrium and lanthanides in 10−7–10−3 mol/L concentration range in nitric acid solutions. The trends in sensitivity values vary depending on a ligand structure and the highest values are observed for Sc3+ and heavy lanthanides. According to the evaluated selectivity Sm3+ is the most preferred ion, while La3+ is the most discriminated. The differences in sensor behavior in rare earth metal solutions assume that such devices can be applied in sensor arrays for potentiometric analysis of lanthanide mixtures.

Application of diffusive gradients in thin films to determine rare earth elements in surface sediments of Daya Bay, China: Occurrence, distribution and ecotoxicological risks

Known as burgeoning contaminants, the bioavailability of rare earth elements (REEs) can be determined using diffusive gradients in thin films (DGT). As Daya Bay (South China) has been under serious anthropogenic influences, the present study examined the distribution of REEs in surface sediments and their possible ecological risks in the bay. The range of DGT-labile concentrations of REEs (∑REEs) was from 5.67 μg/L to 8.41 μg/L, with an average of 7.34 μg/L. Results of assessment of single REE toxicity revealed that the risk quotient (RQ) values of Y, Ce and Yb were >1, indicating that their potential negative impacts on the nearby environment. However, analysis of the integral toxicity of REE mixtures through assessment of probabilistic ecotoxicological risks showed that there was a negligibly low probability of toxicity of PRE surface sediments to aquatic organisms in the study area.

Assessment of the toxicity of a mixture of five rare earth elements found in aquatic ecosystems in Hydra vulgaris

Rare earth elements (REEs) are considered critical elements for technology and their extraction through mining activities is expected to increase in the future. Due to their chemical similarities, they often co-occur in minerals and thus their ecotoxicity should be assessed as a group/family. However, the available ecotoxicological studies focused mainly on the evaluation of the potential toxicological impacts of individual REEs rather than their mixtures. The aim of this study was therefore to evaluate the toxicity of a representative mixture of five REEs (La, Ce, Pr, Nd and Sm) spanning environmentally relevant concentrations ranging from 0.05X (29 µg REEs L−1) to 5X (2926 µg REEs L−1) to the test organism, Hydra vulgaris, at the morphological, reproductive and regenerative levels. The data showed that lethality occurred at concentrations near (2.5 fold) to those inducing sublethal effects after chronic exposure of 7 days. The mixture affected reproduction and head regeneration and even lethality at concentrations even below those reported at environmental concentration (0.5X = 293 µg REEs L−1) in lakes. This suggests that REEs concentrations found in lakes near mining activities could disrupt regeneration and impair embryonic development. Our data also revealed that combining the 5 REEs results in an antagonistic effect, suggesting that those elements share the same receptor and that low molecular weight and high radius elements (approaching iron) were less toxic. Taken together, hydra could be used as a sensitive model organism for the assessment of aquatic ecotoxicological risks of REE mixtures but further analyses of biochemical and gene expressions should improve our understanding of the long-term effects of REEs mixtures.