Rare Earth Extraction from Phosphogypsum by Aspergillus niger Culture Broth.

The extraction of rare earth elements (REEs) from phosphogypsum (PG) is of great significance for the effective utilization of rare earth resources and enhancing the resource value of PG waste residues. This study used Aspergillus niger (A. niger) fungal culture filtrate as a leaching agent to investigate the behavior of extracting REEs from PG through direct and indirect contact methods. According to the ICP-MS results, direct leaching at a temperature of 30 °C, shaking speed of 150 rpm, and a solid-liquid ratio of 2:1, achieved an extraction rate of 74% for REEs, with the main elements being yttrium (Y), lanthanum (La), cerium (Ce), and neodymium (Nd). Under the same conditions, the extraction rate of REEs from phosphogypsum using an A. niger culture filtrate was 63.3% higher than that using the simulated organic acid-mixed solution prepared with the main organic acid components in the A. niger leachate. Moreover, the morphological changes observed in A. niger before and after leaching further suggest the direct involvement of A. niger's metabolic process in the extraction of REEs. When compared to using organic acids, A. niger culture filtrate exhibits higher leaching efficiency for extracting REEs from PG. Additionally, using A. niger culture filtrate is a more environmentally friendly method with the potential for industrial-scale applications than using inorganic acids for the leaching of REEs from PG.

Immobilization of rare-earth doped aluminate nanoparticles encapsulated with silica into polylactic acid-based color-tunable smart plastic window.

An inorganic/organic nanocomposite was used to develop an afterglow and color-tunable smart window. A combination of polylactic acid (PLA) plastic waste as an environmentally-friendly hosting agent, and lanthanide-activated strontium aluminum oxide nanoparticles (SAON) encapsulated with silica nanoparticles (SAON@Silica) as a photoluminescent efficient agent resulted in a smart organic/inorganic nanocomposite. In order to prepare SAON-encapsulated silica nanoparticles (SAON@Silica), the SAON nanoparticles were coated with silica using the heterogeneous precipitation method. By using transmission electron microscopy (TEM), SAON showed a diameter range of 5-12 nm, while the SAON@Silica nanoparticles showed a diameter range of 50-100 nm. In order to ensure the development of a colorless plastic film, a homogeneous dispersion of the phosphorescent Phosphor@Silica nanoparticles throughout the plastic bulk was confirmed. CIE Lab coordinates and luminescence spectra were used to study the color shift characteristics. Under visible light conditions, the plastic films were transparent. The photoluminescent films emitted green light at 525 nm when excited at 375 nm. The hydrophobicity and ultraviolet protection were enhanced without altering the fundamental physico-mechanical performance of the plastic sheet. The current color-tunable plastic can be used in many potential applications, such as warning signs, anti-counterfeiting barcodes, smart windows, and protective apparel.

Trophic Transfer and Toxic Potency of Rare Earth Elements along a Terrestrial Plant-Herbivore Food Chain.

Extensive rare earth element (REE) mining activities have caused REE contamination of ambient agricultural soils, posing threats to associated food webs. Here, a simulated lettuce-snail food chain was conducted to evaluate the trophic transfer characteristics and the consequent effects of REEs on consumers. After 50-day exposure to soil, lettuce roots dose-dependently accumulated 9.4-76 mg kg-1 REEs and translocated 3.7-20 mg kg-1 REEs to shoots. Snails feeding on REE-contaminated shoots accumulated 3.0-6.7 mg kg-1 REEs with trophic transfer factors of 0.20-0.98, indicating trophic dilution in the lettuce-snail system. REE profiles in lettuce and snails indicated light REE (LREE) enrichment only in snails and the varied REE profiles along the food chain. This was corroborated by toxicokinetics. Estimated uptake (Ku) and elimination (Ke) parameters were 0.010-2.9 kgshoot kgsnail-1 day-1 and 0.010-1.8 day-1, respectively, with higher Ku values for LREE and HREE. The relatively high Ke, compared to Ku, indicating a fast REE elimination, supports the trophic dilution. Dietary exposure to REEs dose-dependently affected gut microbiota and metabolites in snails. These effects are mainly related to oxidative damage and energy expenditure, which are further substantiated by targeted analysis. Our study provides essential information about REE bioaccumulation characteristics and its associated risks to terrestrial food chains near REE mining areas.

Enhancing La(III) biosorption and biomineralization with Micromonospora saelicesensis: Involvement of phosphorus and formation of monazite nano-minerals.

The release of rare earth elements (REEs) from mining wastes and their applications has significant environmental implications, necessitating the development of effective prevention and reclamation strategies. The mobility of REEs in groundwater due to microorganisms has garnered considerable attention. In this study, a La(III) resistant actinobacterium, Micromonospora saelicesensis KLBMP 9669, was isolated from REE enrichment soil in GuiZhou, China, and evaluated for its ability to adsorb and biomineralize La(III). The findings demonstrated that M. saelicesensis KLBMP 9669 immobilized La(III) through the physical and chemical interactions, with immobilization being influenced by the initial La(III) concentration, biomass, and pH. The adsorption kinetics followed a pseudo-second-order rate model, and the adsorption isotherm conformed to the Langmuir model. La(III) adsorption capacity of this strain was 90 mg/g, and removal rate was 94 %. Scanning electron microscope (SEM) coupled with energy dispersive X-ray spectrometer (EDS) analysis revealed the coexistence of La(III) with C, N, O, and P. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) investigations further indicated that carboxyl, amino, carbonyl, and phosphate groups on the mycelial surface may participate in lanthanum adsorption. Transmission electron microscopy (TEM) revealed that La(III) accumulation throughout the M. saelicesensis KLBMP 9669, with some granular deposits on the mycelial surface. Selected area electron diffraction (SAED) confirmed the presence of LaPO4 crystals on the M. saelicesensis KLBMP 9669 biomass after a prolonged period of La(III) accumulation. This post-sorption nano-crystallization on the M. saelicesensis KLBMP 9669 mycelial surface is expected to play a crucial role in limiting the bioimmobilization of REEs in geological repositories.

Adsorption of rare earth elements on a magnetic geopolymer derived from rice husk: studies in batch, column, and application in real phosphogypsum leachate sample.

There is a growing need to develop new strategies for rare earth element (REE) recovery from secondary resources. Herein, a novel approach to utilize biogenic silica (from rice husk) and metakaolin was employed to fabricate magnetic geopolymer (MGP) by incorporating metallic iron. The fabricated MGP adsorbent material was used to uptake Ce3+, La3+, and Nd3+ from synthetic solutions and real phosphogypsum leachate in batch and column modes. The MGP offers a negatively charged surface at pH above 2.7, and the uptake of REEs rises from pH 3 to 6. The kinetic study validated that the kinetics was much faster for Nd3+, followed by La3+ and Ce3+. A thermodynamic investigation validated the exothermic nature of the adsorption process for all selected REEs. The desorption experiment using 2 mol L-1 H2SO4 as the eluent demonstrated approximately 100% desorption of REEs from the adsorbent. After six adsorption-desorption cycles, the MGP maintained a high adsorption performance up to cycle five before suffering a significant decrease in performance in cycle six. The effectiveness of MGP was also assessed for its applicability in recovering numerous REEs (La3+, Ce3+, Pr3+, Sm3+, and Nd3+) from real leachate from phosphogypsum wastes, and the highest recovery was achieved for Nd3+ (95.03%) followed by Ce3+ (86.33%). The operation was also feasible in the column presenting suitable values of the length of the mass transfer zone. The findings of this investigation indicate that MGP adsorbent prepared via a simple route has the potential for the recovery of REEs from synthetic and real samples in both batch and continuous operations modes.

The rare-earth yttrium induces cell apoptosis and autophagy in the male reproductive system through ROS-Ca2+-CamkII/Ampk axis.

China has the world's largest reserves of rare earth elements (REEs), but widespread mining and application of REEs has led to an increased risk of potential pollution. Yttrium (Y), the first heavy REEs to be discovered, poses a substantial threat to human health. Unfortunately, little attention has been given to the impact of Y on human reproductive health. In this study, we investigated the toxic effects of YCl3 on mouse testes and four types of testicular cells, including Sertoli, Leydig, spermatogonial and spermatocyte cells. The results showed that YCl3 exposure causes substantial damage to mouse testes and induces apoptosis and autophagy, but not pyroptosis or necrosis, in testicular cells. Genome-wide gene expression analysis revealed that YCl3 induced significant changes in gene expression, with Ca2+ and mitochondria-related genes being the most significantly altered. Mechanistically, YCl3 exposure induced mitochondrial dysfunction in testicular cells, triggering the overproduction of reactive oxygen species (ROS) by impairing the Nrf2 pathway, regulating downstream Ho-1 target protein expression, and increasing Ca2+ levels to activate the CamkII/Ampk signaling pathway. Blocking ROS production or Ca2+ signaling significantly attenuates apoptosis and autophagy, while supplementation with Ca2+ reverses the suppression of apoptosis and autophagy by ROS blockade in testicular cells. Notably, apoptosis and autophagy induced by YCl3 treatment are independent of each other. Thus, our study suggests that YCl3 may impair the antioxidant stress signaling pathway and activate the calcium pathway through the ROS-Ca2+ axis, which promotes testicular cell apoptosis and autophagy independently, thus inducing testicular damage and impairing male reproductive function.

Rare earth elements in tea garden soils and their bioavailability to tea buds in Taiwan.

Tea (Camellia sinensis) is a widespread beverage plant that prefers aluminum-enriched acidic soils. However, rare earth elements (REEs) might be highly phyto-available in these soils. With the increasing demands for REEs in high-technology industries, understanding the dynamics of REEs in the environment is essential. Thus, this study identified the total concentration of REEs in the root-zone soils and corresponding tea buds (n = 35) collected from tea gardens in Taiwan. Additionally, the labile REEs in the soils were extracted with 1 M KCl, 0.1 M HCl, and 0.05 M ethylenediaminetetraacetic acid (EDTA) to elucidate the fractionation tendency of REEs in the soil-plant system and the relationships between REEs and Al in the tea buds. The concentration of light REEs (LREEs) was higher than those of medium REEs (MREEs) and heavy REEs (HREEs) in all soil and tea bud samples. According to the upper continental crust (UCC) normalization, MREEs and HREEs were more abundant than LREEs in the tea buds. Furthermore, REEs remarkably increased with increasing Al in the tea buds, whereas the linear correlations between Al and MREEs and HREEs were stronger than between LREEs. Compared with LREEs, the extractabilities of MREEs and HREEs by all single extractants in the soils were higher, coinciding with their higher UCC-normalization-based enrichments in the tea buds. Moreover, the 0.1 M HCl- and 0.05 M EDTA-extractable REEs were affected by soil properties and significantly correlated with the total REEs in the tea buds. The concentration of REEs in the tea buds was successfully predicted by empirical equations of extractable REEs with 0.1 M HCl and 0.05 M EDTA, as well as general soil properties including pH, organic carbon, dithionite-citrate-bicarbonate-extractable iron, aluminum, and phosphorus. However, this prediction should be further verified using many soil and tea types in the future.

Critical metal geochemistry in groundwaters influenced by dredged material.

This study investigated critical metal (CM) geochemistry including rare earth elements (REEs), Co, Ni, and Mn in groundwaters below and surrounding two dredged material placement facilities (DMPFs). Metal concentrations are elevated at both sites, spanning several orders of magnitude. The highest CM concentrations measured exceed many environments considered as aqueous resources (Co and Ni > 1 mg L-1, REEs > 3 mg L-1). Correlations between sulfur and iron, major cations, and CMs indicate that oxidation of sulfides present in the DM releases metals both directly from sulfide minerals and indirectly through acid dissolution of and/or desorption from additional minerals. REE fractionation patterns indicate that their mobility in the groundwaters may be influenced by interactions with silicate, carbonate, and phosphate minerals. Significant positive Gd and Eu anomalies were observed, which may be attributed to increased mobility of Eu2+ and anthropogenic Gd. Nanogeochemical analysis of filtered samples revealed several REE-bearing nanoparticulate (diameter < 100 nm) species, some of which co-occurred with aluminum, suggesting an (oxy)hydroxide or a clay mineral component. Further characterization of soluble and nano scale geochemical speciation is needed to fully assess the viability of CM recovery from DM-associated groundwater. CM recovery from DM-associated waters can provide a beneficial use, both offsetting costs associated with disposal, and supplementing domestic CM resources.

[The role of Keap1/Nrf2/HO-1 signal pathway in liver injury induced by rare earth neodymium oxide in mice].

Objective: To investigate the role of Keap1/Nrf2/HO-1 signaling pathway in liver injury induced by neodymium oxide (Nd(2)O(3)) in mice. Methods: In March 2021, forty-eight SPF grade healthy male C57BL/6J mice were randomly divided into control group (0.9% NaCl), low dose group (62.5 mg/ml Nd(2)O(3)), medium dose group (125.0 mg/ml Nd(2)O(3)), and high dose group (250.0 mg/ml Nd(2)O(3)), each group consisted of 12 animals. The infected groups were treated with Nd(2)O(3) suspension by non-exposed tracheal drip and were killed 35 days after dust exposure. The liver weight of each group was weighed and the organ coefficient was calculated. The content of Nd(3+) in liver tissue was detected by inductively coupled plasma mass spectrometry (ICP-MS). HE staining and immunofluorescence was used to observe the changes of inflammation and nuclear entry. The mRNA expression levels of Keap1, Nrf2 and HO-1 in mice liver tissue were detected by qRT-PCR. Western blotting was used to detect the protein expression levels of Keap1 and HO-1. The contents of catalase (CAT), glutathione peroxidase (GSH-Px) and total superoxide dismutase (T-SOD) were detected by colorimetric method. The contents of interleukin 1ß (IL-1ß), interleukin 6 (IL-6) and tumor necrosis factor α (TNF-α) were determined by ELISA. The data was expressed in Mean±SD. Two-independent sample t-test was used for inter-group comparison, and one-way analysis of variance was used for multi-group comparison. Results: Compared with the control group, the liver organ coefficient of mice in medium and high dose groups were increased, and the Nd(3+) accumulation in liver of mice in all dose groups were significantly increased (P<0.05). Pathology showed that the structure of liver lobules in the high dose group was slightly disordered, the liver cells showed balloon-like lesions, the arrangement of liver cell cords was disordered, and the inflammatory exudation was obvious. Compared with the control group, the levels of IL-1ß and IL-6 in liver tissue of mice in all dose groups were increased, and the levels of TNF-α in liver tissue of mice in high dose group were increased (P<0.05). Compared with the control group, the mRNA and protein expression levels of Keap1 in high dose group were significantly decreased, while the mRNA expression level of Nrf2, the mRNA and protein expression levels of HO-1 were significantly increased (P<0.05), and Nrf2 was successfully activated into the nucleus. Compared with the control group, the activities of CAT, GSH-Px and T-SOD in high dose group were significantly decreased (P<0.05) . Conclusion: A large amount of Nd(2)O(3) accumulates in the liver of male mice, which may lead to oxidative stress and inflammatory response through activation of Keap1/Nrf2/HO-1 signal pathway. It is suggested that Keap1/Nrf2/HO-1 signal pathway may be one of the mechanisms of Nd(2)O(3) expose-induced liver injury in mice.

Production regions discrimination of Huangguanyin oolong tea by using the content of chemical components and rare earth elements.

Oolong tea is one of the most popular tea beverages in China. Tea cultivars, processing technology and origin of production affect the quality and price of oolong teas. To investigate the differences in Huangguanyin oolong tea from different production regions, the chemical components, mineral elements and rare earth elements of Huangguanyin oolong tea produced in Yunxiao (YX) and Wuyishan (WY) were analyzed by using spectrophotometry methods, targeted metabolomics and inductive plasma coupled mass spectrometry (ICP-MS). The results of spectrophotometry methods revealed that there were significant differences in thearubigin, tea polyphenols and water extract between Huangguanyin oolong teas from different production regions. Targeted metabolomics identified a total of 31 chemical components in Huangguanyin oolong teas from the two production regions, of which 14 chemical components were significantly different and contributed to the regional differentiation of Huangguanyin oolong tea. Yunxiao Huangguanyin had relatively higher contents of (-)-Epigallocatechin-3-O-(3-O-methylgallate) (EGCG3″Me), ornithine (Orn) and histidine (His), while Wuyishan Huangguanyin had relatively higher contents of glutamic acid (Glu), γ-aminobutyric acid (GABA), ß-aminobutyric acid (ß-ABA) and other components. Moreover, ICP-MS identified a total of 15 mineral elements and 15 rare earth elements in Huangguanyin oolong tea from the two production regions, of which 15 elements were significantly different between YX and WY, and contributed to the regional differentiation of Huangguanyin oolong tea. K had a relatively higher content in Yunxiao Huangguanyin, while rare earth elements had relatively higher contents in Wuyishan Huangguanyin. The classification results by the production region showed that the discrimination rate of the support vector machine (SVM) model based on the 14 different chemical components reached 88.89%, while the SVM model based on the 15 elements reached 100%. Therefore, we used targeted metabolomics and ICP-MS techniques to screen and explore the chemical components, mineral elements and rare earth elements differences among two production regions, which indicated the feasibility of Huangguanyin oolong tea classification by production regions in the study. The results will provide some reference for the distinction between the two production regions of Huangguanyin oolong tea.

Recovery of rare earth elements from waste phosphors via alkali fusion roasting and controlled potential reduction leaching.

Waste phosphors, which contain the quantity of rare earth and toxic metals, need to be recycled for both environmental protection and the sustainable development of rare earth resources. Due to the magnesium-aluminum spinel structure, it is difficult to extract cerium and terbium from waste phosphors. In this study, a facile process for recovering rare earth elements from waste phosphors was developed. First, the waste phosphors were alkali roasted to destroy the aluminum-magnesium spinel structure in the blue and green powders. NaOH was found to be a more suitable additive than Na2CO3, NaHCO3, and K2CO3 for alkali roasting. Then, the roasted slag was washed with water to remove the aluminum and controlled potential reduction leaching was conducted. FeCl2 was used as the reductant (dosage of 0.04) in the 3 mol·L-1 HCl solution at a leaching temperature of 50 °C for 60 min. The leaching efficiencies of Y, Eu, Ce, and Tb were up to 99.1 %, 99.4 %, 98.6 %, and 98.8 %, respectively. The reduction leaching process obeys the shrinking core model and depends on the diffusion. This process can effectively improve the leaching efficiency of rare earth elements from waste phosphors and provides theoretical and technical support for the recycling of waste phosphors.

Rare earth elements detoxification mechanism in the hyperaccumulator Dicranopteris linearis: [silicon-pectin] matrix fixation.

Dicranopteris linearis is the best-known hyperaccumulator species of rare earth elements (REEs) and silicon (Si), capable of dealing with toxic level of REEs. Hence, this study aimed to clarify how D. linearis leaves cope with excessive REE stress, and whether Si plays a role in REE detoxification. The results show that lanthanum (La - as a representative of the REEs) stress led to decreased biomass and an increase of metabolism related to leaf cell wall synthesis and modification. However, the La stress-induced responses, especially the increase of pectin-related gene expression level, pectin polysaccharides concentration, and methylesterase activity, could be mitigated by Si supply. Approximately 70% of the Si in D. linearis leaves interacted with the cell walls to form organosilicon Si-O-C linkages. The Si-modified cell walls contained more hydroxyl groups, leading to a more efficient REE retention compared to the Si-free ones. Moreover, this [Si-cell wall] matrix increased the pectin-La accumulation capacity by 64%, with no effect on hemicellulose-La and cellulose-La accumulation capacity. These results suggest that [Si-pectin] matrix fixation is key in REE detoxification in D. linearis, laying the foundation for the development of phytotechnological applications (e.g., REE phytomining) using this species in REE-contaminated sites.

Accumulation and distribution characteristics of rare earth elements (REEs) in the naturally grown marigold (Tagetes erecta L.) from the soil.

Rare earth elements (REEs) are considered environmental pollutants that have received extensive attention recently. The accumulation of REEs in plants is important because REEs can eventually enter the human body via the food chain. Marigolds are widely utilized as medicinal and commercial plants in medicine, feed, and therapeutics. Due to the extremely high demand for marigold in global, it is urgent to investigate the accumulation and distribution of REEs in marigold plants to reduce human and animal health risks. Marigold leaves tended to bioaccumulate the highest amounts of REEs from soil compared with other tissues. The distribution patterns of REEs in marigold were similar to those in the rhizosphere soil, which was enriched in light rare earth elements. Cerium accumulated most in marigold and soil, accounting for nearly 50% of ΣREEs, followed by lanthanum, neodymium, and yttrium. Roots were the most susceptible tissue affected by soil REE concentration, and a significant positive correlation was observed for REEs in the roots of marigold and soils (R = 0.87), while no significant correlation was observed for REEs in soils and other tissues. REEs were poorly transferred from soil to marigold, with bioaccumulation factor values for all tissues of marigold less than one. Additionally, REEs exhibited a positive correlation with Al and Fe in the roots, stems, leaves, and flowers of marigold. The present research revealed the biological interactions between marigold and soil and the distribution of REEs in various parts of marigold. It provides a reference for large-scale commercial cultivation and potential environmental risk in the future.

Application of Pb Isotopes and REY Patterns in Tracing Heavy Metals in Farmland Soils from the Upper-Middle Area of Yangtze River.

Farmland heavy metal pollution-caused by both human activity and natural processes-is a major global issue. In the current study, principal component analysis (PCA), cluster analysis (CA), rare earth elements and yttrium (REY) analysis, and isotope fingerprinting were combined to identify sources of heavy metal pollution in soil from different farmland types in the upper-middle area of the Yangtze River. The concentrations of Zn and Cu were found to be higher in the vegetable base and tea plantation soil compared with their concentrations in the orangery soil. On the other hand, greater accumulation of Cd and Pb was observed in the orangery soil versus the vegetable base and tea plantation soils. Influenced by the type of bedrock, REY was significantly enriched in the orangery soil and depleted in the vegetable base soil, as compared with the tea plantation soil. The Pb isotopic compositions of the tea plantation (1.173-1.193 for 206Pb/207Pb and 2.070-2.110 for 208Pb/206Pb) and vegetable base (1.181-1.217 for 206Pb/207Pb and 2.052-2.116 for 208Pb/206Pb) soils were comparable to those of coal combustion soil. The compositions of 206Pb/207Pb (1.149-1.170) and 208Pb/206Pb (2.121-2.143) in the orangery soil fell between those observed in soils obtained from coal combustion and ore smelting sites. Using the IsoSource model, the atmospheric Pb contributions of the vegetable base, tea plantation, and orangery soils were calculated to be 66.6%, 90.1%, and 82.0%, respectively, and the bedrock contributions of Pb were calculated to be 33.3%, 9.90%, and 18.1%, respectively. Based on the PCA, CA, and REY results, as well as the Pb isotope model, it appears that heavy metals in the orangery soil may be derived from atmospheric deposition and bedrock weathering, while heavy metals in the vegetable base and tea plantation soils may be derived from mining and the use of fertilizer.

Selective recovery of rare earth elements and value-added chemicals from the Dicranopteris linearis bio-ore produced by agromining using green fractionation.

The increasing demand for Rare Earth Elements (REEs) and the depletion of mineral resources motivate sustainable strategies for REE recovery from alternative unconventional sources, such as REE hyperaccumulator. The greatest impediment to REE agromining is the difficulty in the separation of REEs and other elements from the harvested biomass (bio-ore). Here, we develop a sulfuric acid assisted ethanol fractionation method for processing D. linearis bio-ore to produce the pure REE compounds and value-added chemicals. The results show that 94.5% of REEs and 87.4% of Ca remained in the solid phase, and most of the impurities (Al, Fe, Mg, and Mn) transferred to the liquid phase. Density functional theory calculations show that the water-cation bonds of REEs and Ca cations were broken more easily than the bonds of the cations of key impurities, causing lower solubility of REEs and Ca compounds. Subsequent separation and purification led to a REE-oxide (REO) product with a purity of 97.1% and a final recovery of 88.9%. In addition, lignin and phenols were obtained during organosolv fractionation coupled with a fast pyrolysis process. This new approach opens up the possibility for simultaneous selective recovery of REEs and to produce value-added chemicals from REE bio-ore refining.

The role of Keap1/Nrf2/HO-1 signal pathway in liver injury induced by rare earth neodymium oxide in mice / 中华劳动卫生职业病杂志

Objective: To investigate the role of Keap1/Nrf2/HO-1 signaling pathway in liver injury induced by neodymium oxide (Nd(2)O(3)) in mice. Methods: In March 2021, forty-eight SPF grade healthy male C57BL/6J mice were randomly divided into control group (0.9% NaCl), low dose group (62.5 mg/ml Nd(2)O(3)), medium dose group (125.0 mg/ml Nd(2)O(3)), and high dose group (250.0 mg/ml Nd(2)O(3)), each group consisted of 12 animals. The infected groups were treated with Nd(2)O(3) suspension by non-exposed tracheal drip and were killed 35 days after dust exposure. The liver weight of each group was weighed and the organ coefficient was calculated. The content of Nd(3+) in liver tissue was detected by inductively coupled plasma mass spectrometry (ICP-MS). HE staining and immunofluorescence was used to observe the changes of inflammation and nuclear entry. The mRNA expression levels of Keap1, Nrf2 and HO-1 in mice liver tissue were detected by qRT-PCR. Western blotting was used to detect the protein expression levels of Keap1 and HO-1. The contents of catalase (CAT), glutathione peroxidase (GSH-Px) and total superoxide dismutase (T-SOD) were detected by colorimetric method. The contents of interleukin 1β (IL-1β), interleukin 6 (IL-6) and tumor necrosis factor α (TNF-α) were determined by ELISA. The data was expressed in Mean±SD. Two-independent sample t-test was used for inter-group comparison, and one-way analysis of variance was used for multi-group comparison. Results: Compared with the control group, the liver organ coefficient of mice in medium and high dose groups were increased, and the Nd(3+) accumulation in liver of mice in all dose groups were significantly increased (P<0.05). Pathology showed that the structure of liver lobules in the high dose group was slightly disordered, the liver cells showed balloon-like lesions, the arrangement of liver cell cords was disordered, and the inflammatory exudation was obvious. Compared with the control group, the levels of IL-1β and IL-6 in liver tissue of mice in all dose groups were increased, and the levels of TNF-α in liver tissue of mice in high dose group were increased (P<0.05). Compared with the control group, the mRNA and protein expression levels of Keap1 in high dose group were significantly decreased, while the mRNA expression level of Nrf2, the mRNA and protein expression levels of HO-1 were significantly increased (P<0.05), and Nrf2 was successfully activated into the nucleus. Compared with the control group, the activities of CAT, GSH-Px and T-SOD in high dose group were significantly decreased (P<0.05) . Conclusion: A large amount of Nd(2)O(3) accumulates in the liver of male mice, which may lead to oxidative stress and inflammatory response through activation of Keap1/Nrf2/HO-1 signal pathway. It is suggested that Keap1/Nrf2/HO-1 signal pathway may be one of the mechanisms of Nd(2)O(3) expose-induced liver injury in mice.

A review of the application of cerium and lanthanum in phosphorus removal during wastewater treatment: Characteristics, mechanism, and recovery.

Owing to their strong bond with anions, rare earth elements (REEs) are prime contenders in wastewater treatment to meet the stringent phosphorus (P) effluent quality requirements. REEs outcompete traditional metals to abate phosphorus. The application of lanthanides in wastewater treatment is mainly through adsorption, where REEs are incorporated into a carrier matrix to improve the adsorption capacity. As coagulants, information on the performance of lanthanides is lacking. In this review, the performance of major water coagulants (iron and aluminum) is discussed and compared to two lanthanides: cerium and lanthanum. The use of lanthanides as adsorbents and as coagulants is elucidated during P treatment. The recovery of P and REEs is also discussed. Where details were lacking in the literature, experiments were conducted to fill these research gaps. Using REEs as adsorbents limits their P precipitation potential; as coagulants, REE capacity is 520.79 mg P/g La3+ and 469.96 mg P/g Ce3+. In addition, as coagulants, they are not affected by pH (3.0 < pH < 10.0); however, carbonates and sulfate are the major species that can reduce the performance of REEs during P treatment. REE-P precipitation is orchestrated through the formation of an REE-PO4 bond. Unfortunately, this strong bond between lanthanides and phosphate makes phosphate recovery almost impractical. If the goal is to recover REEs and reuse P in other applications like fertilizers, REEs are not the best candidates. We recommend additional research dedicated to understanding lanthanide coagulants in typical wastewater treatment facilities and their release from phosphate precipitates under different environmental conditions.

The mobility of thorium, uranium and rare earth elements from Mid Ordovician black shales to acid waters and its removal by goethite and schwertmannite.

Previous studies have addressed the occurrence of Acid Rock Drainage (ARD) affecting La Silva stream due to the generation of large dumps of Middle Ordovician black shales during the construction of a highway close to El Bierzo (León, Spain). This ARD was characterized by sulphated acid waters with high concentration of heavy metals and anomalies in dissolved thorium (Th) and uranium (U). In the present study, we analyse in depth black shales and water, streambed sediments and precipitates of La Silva stream and its tributaries using different petrographic, mineralogical and geochemical approaches. Black shales, with average Th and U contents of 20 and 3 µg/g respectively contain disseminated detritic micro-grains of high weathering-resistant minerals, such as monazite and xenotime, that present smaller amounts of yttrium and rare earth elements (REY) and other elements as Ca, U, Th, Si and F. Results of the affected waters by ARD show an enrichment in dissolved Th, U and REY of several orders of magnitude with respect to natural waters. Sampled precipitates were mainly schwertmannite (Fe8O8(OH)8-2x (SO4)xO16•nH2O) and goethite (α-Fe3+O(OH)) that showed an enrichment of Th (up to 798 µg/g) and REY, due to the presence of dissolved anionic species (e.g. [Formula: see text] , [Formula: see text] ) that enables their adsorption. Furthermore, these black shales show a clear enrichment in REE (Rare Earth Elements) with respect to NASC (North American Shales Composite) normalized REE patterns. Likewise, normalized REE patterns of stream waters and precipitates clearly show convex curvatures in middle-REE (MREE) with respect to light- and something less than heavy-REE, indicating the trend towards MREE enrichment. These findings are essential to evaluate the impact of ARD of Mid Ordovician shales in the surrounding environment, and to start considering these site as potential source of REE and critical raw materials, activating a Circular Economy.

Effects of composite materials and revegetation on soil nutrients, chemical and microbial properties in rare earth tailings.

The mining of ionic rare earth elements in Ganzhou left large area of barren tailings with severe vegetation destruction in pressing needs of remediation. However, the remediating effects of soil additives combined with revegetation on the preservation of nutrients in the tailings and microbial communities were rarely studied. For this purpose, pilot experiments were implemented in a field, with the control group (CK) only cultivating plants without adding materials, and three treatments including peanut straw biochar composite (T1), phosphorus­magnesium composite (T2) and modified zeolite composite (T3) along with the cultivation of Medicago sativa L., Paspalum vaginatum Sw. and Lolium perenne L. Soil pH and organic matter in CK significantly decreased from 4.90 to 4.17 and from 6.62 g/kg to 3.87 g/kg after six months, respectively (p ≤ 0.05), while all the treatments could effectively buffer soil acidification (over 5.74) and delay the loss of soil organic matter. Soil cation exchange capacity was still below the detection limit in all the groups except T2. The results of rainfall runoff monitoring indicated that compared with CK, only T2 could significantly reduce the runoff loss of soil NO3- and SO42- by 45.61 %-75.78 % and 64.03 %-76.12 %, respectively (p ≤ 0.05). Compared with CK, the bacterial diversity in T2 and T3 significantly increased 21.18 % and 28.15 %, respectively (p ≤ 0.05), while T1 didn't change the bacterial or fungal diversity (p > 0.05). Co-occurrence network analysis showed that compared with CK, the whole microbial communities interacted more closely in the three treatments. Functional prediction of the microbial communities revealed all the treatments were dominated by carbon transforming bacteria and saprotrophic fungi except T2. This study demonstrated that the composite materials combined with revegetation couldn't retain soil nitrogen compounds and sulfate in rare earth tailings in the long term.

Mechanisms and influencing factors of yttrium sorption on paddy soil: Experiments and modeling.

High-technology rare earth elements (REEs) as emerging contaminants have potentially hazardous risks for human health and the environment. Investigating the sorption of REEs on soils is crucial for understanding their migration and transformation. This study evaluated the sorption mechanisms and influencing factors of the rare earth element yttrium (Y) on paddy soil via integrated batch sorption experiments and theoretical modeling analysis. Site energy distribution theory (SEDT) combined with kinetics, thermodynamics, and isotherm sorption models were applied to illustrate the sorption mechanism. In addition, the effects of phosphorus (P), solution pH, particle size of soil microaggregates, and initial Y content on the sorption processes were evaluated by self-organizing map (SOM) and Boruta algorithm. The sorption kinetic behavior of Y on paddy soil was more consistent with the pseudo-second-order model. Thermodynamic results showed that the Y sorption was a spontaneous endothermic reaction. The generalized Langmuir model well described the isotherm data of Y sorption on heterogeneous paddy soil and soil microaggregates surface. The maximum sorption capacity of Y decreased with increasing soil particle size, which may be related to the number of sorption sites for Y on paddy soil and soil microaggregates, as confirmed by SEDT. The heterogeneity of sorption site energy for Y was the highest in the original paddy soil compared with the separated soil microaggregates. The SOM technique and Boruta algorithm highlighted that the initial concentration of Y and coexisting phosphorus played essential roles in the sorption process of Y, indicating that the addition of phosphate fertilizer may be an effective way to reduce the Y bioavailability in paddy soil in practice. These results can provide a scientific basis for the sustainable management of soil REEs and a theoretical foundation for the remediation of REEs-contaminated soils.