A Critical Review of the Enhanced Recovery of Rare Earth Elements from Phosphogypsum.

The increasing demand for rare earth elements (REEs), especially from new and innovative technology, has strained their supply, which makes the exploration of new REE sources necessary, for example, the recovery of REEs from phsophogypsum (PG). PG is a byproduct during the wet production of phosphoric acid, which is an attractive secondary resource for REEs due to a large amount of REEs locked in them. In most cases, REEs contained in PG are mainly encapsulated in the gypsum crystal, leading to a low leaching efficiency. Therefore, it is particularly important to use various methods to enhance the leaching of REEs from PG. In this review, we summarized and classified various enhanced leaching methods for the recovery of REEs from PG, and the advantages and disadvantages of different methods were compared. A joint method of recrystallization and RIL may be a promising enhanced leaching approach for the recovery of REEs from PG. Recrystallization could achieve both the complete REE release and simultaneous preparation of industrial materials with high value added, such as high-strength α-hemihydrate gypsum by phase transformation of PG, and the RIL technology could adsorb the releasing REEs and realize their efficient extraction. Such a combination appears to show significant advantages because of high REE recovery, as well as high value-added product preparation at low cost.

Genome-wide investigation of the ZF-HD gene family in two varieties of alfalfa (Medicago sativa L.) and its expression pattern under alkaline stress.

BACKGROUND: Zinc finger homeodomain (ZHD) protein is a plant-specific transcription factor and a potential regulator of phosphoenolpyruvate carboxylase (PEPCase)-coding genes, and it also participates in plant growth regulation and abiotic stress responses. To study the function of MsZF-HD genes in the alkaline stress response, this paper assessed biological information and performed transcriptome analysis of the MsZF-HD gene family by using the genomes of two different varieties of alfalfa (XinJiangDa Ye and Zhongmu No. 1). RESULTS: In total, 49 and 11 MsZF-HD genes were identified in the two different varieties respectively, including the alleles of XinJiangDa Ye. According to their phylogenetic relationships, the 60 MsZF-HD genes were divided into 5 ZHD subfamilies and 1 MIF subfamily. A total of 88.3% of MsZF-HD genes do not contain introns and are unevenly distributed among the 6 chromosomes of alfalfa. A collinearity analysis indicated that 26 genes of XinJiangDa Ye have no orthologous genes in Zhongmu No. 1, although these genes (such as ZHD-X1-2, ZHD-X3-2 and ZHD-X4-2) have homologous genes in Arabidopsis thaliana, Medicago truncatula and Glycine max. Through RNA-seq and qRT-PCR verification, it was found that MsZF-HD genes are downregulated to participate in the alkaline stress response. CONCLUSION: The results of this study may lay the foundation for the cloning and functional study of MsZF-HD genes and provide a theoretical basis for revealing the difference between XinJiangDa Ye and Zhongmu No. 1 at the genome level.

Symbiotic System Establishment between Piriformospora indica and Glycine max and Its Effects on the Antioxidant Activity and Ion-Transporter-Related Gene Expression in Soybean under Salt Stress.

The utilization of symbiosis with beneficial microorganisms has considerable potential for increasing growth and resistance under abiotic stress. The endophytic root fungus Piriformospora indica has been shown to improve plant growth under salt and drought stress in diverse plant species, while there have been few reports of the interaction of P. indica with soybean under salt stress. In this study, the symbiotic system of P. indica and soybean (Glycine max L.) was established, and the effect of P. indica on soybean growth and salt tolerance was investigated. The colonized and non-colonized soybeans were subjected to salt stress (200 mmol/L NaCl), and the impairments in chlorophyll and increasing relative conductivity that can be caused by salt stress were alleviated in the P. indica-colonized plants. The accumulation of malondialdehyde (MDA), hydrogen peroxide (H2O2), and superoxide anion (O2−) were lower than that in non-colonized plants under salt treatment, whereas the activities of antioxidant enzymes were significantly increased by P. indica colonization, including superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), and glutathione reductase (GR). Importantly, without salt treatment, the Na+ concentration was lower, and the K+ concentration was higher in the roots compared with non-colonized plants. Differential expressions of ion transporter genes were found in soybean roots after P. indica colonization. The P. indica colonization positively regulated the transcription level of PM H+-ATPase, SOS1, and SOS2. The study shows that P. indica enhances the growth and salt tolerance of soybean, providing a strategy for the agricultural production of soybean plants in saline-alkali soils.

Overexpression of MsRCI2D and MsRCI2E Enhances Salt Tolerance in Alfalfa (Medicago sativa L.) by Stabilizing Antioxidant Activity and Regulating Ion Homeostasis.

Rare cold-inducible 2 (RCI2) genes from alfalfa (Medicago sativa L.) are part of a multigene family whose members respond to a variety of abiotic stresses by regulating ion homeostasis and stabilizing membranes. In this study, salt, alkali, and ABA treatments were used to induce MsRCI2D and MsRCI2E expression in alfalfa, but the response time and the expression intensity of the MsRCI2D,-E genes were different under specific treatments. The expression intensity of the MsRCI2D gene was the highest in salt- and alkali-stressed leaves, while the MsRCI2E gene more rapidly responded to salt and ABA treatment. In addition to differences in gene expression, MsRCI2D and MsRCI2E differ in their subcellular localization. Akin to MtRCI2D from Medicago truncatula, MsRCI2D is also localized in the cell membrane, while MsRCI2E is different from MtRCI2E, localized in the cell membrane and the inner membrane. This difference might be related to an extra 20 amino acids in the C-terminal tail of MsRCI2E. We investigated the function of MsRCI2D and MsRCI2E proteins in alfalfa by generating transgenic alfalfa chimeras. Compared with the MsRCI2E-overexpressing chimera, under high-salinity stress (200 mmol·L-1 NaCl), the MsRCI2D-overexpressing chimera exhibited a better phenotype, manifested as a higher chlorophyll content and a lower MDA content. After salt treatment, the enzyme activities of SOD, POD, CAT, and GR in MsRCI2D- and -E-overexpressing roots were significantly higher than those in the control. In addition, after salt stress, the Na+ content in MsRCI2D- and -E-transformed roots was lower than that in the control; K+ was higher than that in the control; and the Na+/K+ ratio was lower than that in the control. Correspondingly, H+-ATPase, SOS1, and NHX1 genes were significantly up-regulated, and the HKT gene was significantly down-regulated after 6 h of salt treatment. MsRCI2D was also found to regulate the expression of the MsRCI2B and MsRCI2E genes, and the MsRCI2E gene could alter the expression of the MsRCI2A, MsRCI2B, and MsRCI2D genes. MsRCI2D- and -E-overexpressing alfalfa was found to have higher salt tolerance, manifested as improved activity of antioxidant enzymes, reduced content of reactive oxygen species, and sustained Na+ and K+ ion balance by regulating the expression of the H+-ATPase, SOS1, NHX1, HKT, and MsRCI2 genes.

The Impurity Removal and Comprehensive Utilization of Phosphogypsum: A Review.

Phosphogypsum (PG), a byproduct during the phosphoric acid production process, also known as the wet process, contains complex and diverse impurities, resulting in low utilization and considerable accumulation. This leads to a massive waste of land resources and a series of environmental pollution problems. Given the current urgent ecological and environmental situation, developing impurity removal processes with low energy consumption and high efficiency, exploring valuable resource recovery, preparing high value-added PG products, and broadening the comprehensive utilization ways of PG are significant strategies to promote the sustainable consumption of PG and sustainable development of the phosphorus chemical industry. This review comprehensively summarizes the advantages and disadvantages of existing PG impurity removal and utilization technologies and probes into the future development direction, which provides references and ideas for subsequent PG research.

Large-area grown ultrathin molybdenum oxides for label-free sensitive biomarker detection.

The rise of two-dimensional (2D) materials has provided a confined geometry and yielded methods for guiding electrons at the nanoscale level. 2D material-enabled electronic devices can interact and transduce the subtle charge perturbation and permit significant advancement in molecule discrimination technology with high accuracy, sensitivity, and specificity, leaving a significant impact on disease diagnosis and health monitoring. However, high-performance biosensors with scalable fabrication ability and simple protocols have yet to be fully realized due to the challenges in wafer-scale 2D film synthesis and integration with electronics. Here, we propose a molybdenum oxide (MoOx)-interdigitated electrode (IDE)-based label-free biosensing chip, which stands out for its wafer-scale dimension, tunability, ease of integration and compatibility with the complementary metal-oxide-semiconductor (CMOS) fabrication. The device surface is biofunctionalized with monoclonal anti-carcinoembryonic antigen antibodies (anti-CEA) via the linkage agent (3-aminopropyl)triethoxysilane (APTES) for carcinoembryonic antigen (CEA) detection and is characterized step-by-step to reveal the working mechanism. A wide range and real-time response of the CEA concentration from 0.1 to 100 ng mL-1 and a low limit of detection (LOD) of 0.015 ng mL-1 were achieved, meeting the clinical requirements for cancer diagnosis and prognosis in serum. The MoOx-IDE biosensor also demonstrates strong surface affinity towards molecules and high selectivity using L-cysteine (L-Cys), glycine (Gly), glucose (Glu), bovine serum albumin (BSA), and immunoglobulin G (IgG). This study showcases a simple, scalable, and low-cost strategy to create a nanoelectronic biosensing platform to achieve high-performance cancer biomarker discrimination capabilities.

Correlation Analysis between Residual Pain after Vertebral Augmentation and the Diffusion Distribution of Bone Cement: A Retrospective Cohort Study.

Objective: To explore the influence and potential factors of the bone cement dispersion state on residual pain after vertebral augmentation. Methods: The cases included in this retrospective cohort study were patients treated with vertebral augmentation (VA) for osteoporotic vertebral compression fractures (OVCFs) between July 2018 and June 2021. According to the type of cement diffusion distribution, the patients were divided into a sufficient diffusion group (Group A) and an insufficient diffusion group (Group B). The differences in the baseline data, visual analog scale (VAS), Oswestry disability index score (ODI), injured vertebral height (IVH), and local kyphosis angle (LKA) between the two groups were analyzed. Assessments were performed preoperatively on the 2nd day postoperation and at the last follow-up. The imaging data of injured vertebrae were accurately reconstructed by a GE AW4.7 workstation, and the differences in the vertebral body volume, bone cement volume, and bone cement volume ratio were compared between the groups. Result: After screening, 36 patients were included. (1) The postoperative VAS and ODI scores of the two groups were significantly improved compared with the preoperative scores. (2) On the 2nd day postoperation and the last follow-up, the VAS and ODI scores of Group A were significantly different from those of Group B, and Group A outperformed Group B. (3) The IVH and LKA of the two groups were improved after the operation, and no significant difference was found between the groups. (4) Significant differences were found in the bone cement volume and bone cement volume ratio between the groups, and Group A was larger than Group B. Conclusions: Sufficient bone cement diffusion can reduce residual pain after vertebral augmentation.

Synergistic leaching process for ion-exchange ammonium from weathered crust elution deposited rare earth tailings with potassium magnesium compound eluent.

The ion-exchangeable ammonium (IE-A) that accounts for 60-90% of the total residual ammonium in rare earth tailings has great potential to pollute the surrounding environment, and much research has been done to seek an effective elution method. However, the current study mainly focused on the single salt solution, which made it hard to reach the desired elution efficiency. In this study, the efficient binary compound eluent was prepared, and the response surface experiments and dynamic elution were performed to optimize the elution condition and evaluate the practical application prospect. Batch experimental results showed that the best IE-A elution efficiency could be achieved at the K:Mg molar ratio of 8:2, the liquid-solid ratio of 26:1, and the concentration of 0.1 mol/L at the natural solution pH. Dynamic experimental results indicated that a higher concentration, flow rate, and elution temperature could all accelerate the elution process, and the highest elution efficiency could reach 99%. The fitting results by shrinking core models show that the apparent activation energy of IE-A was 4.24 kJ/mol in the temperature range of 288-328 K, and the reaction order was 0.16. XPS and FTIR revealed that IE-A was effectively eluted by a potassium and magnesium compound leaching agent via an ion-exchange reaction. Overall, the developed compound solution with potassium and magnesium is a candidate for an elution agent that could be used to remove residual ammonium in a closed field of rare earth ores.

Preparation of a Novel Organic Phosphonic Acid Intercalated Phosphate Tailings Based Hydrotalcite and Its Application in Enhancing Fire Safety for Epoxy Resin.

Phosphate tailings (PTs) are solid waste, which is produced by phosphate flotation. In this work, PTs were used as raw materials for the preparation of diethylenetriamine pentamethronic acid (DTPMP) intercalated trimetal (Ca-Mg-Al) layered double hydroxides (TM-DTPMP LDHs) by co-precipitation method. TM-DTPMP LDHs were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, scanning electron microscopy, differential thermal gravimetric analysis, X-ray photoelectron spectroscopy and applied as a flame retardant to improve the fire safety of epoxy resin (EP). The results showed that the composite materials exhibited obvious layered structure. After intercalation, layer spacing increased from 0.783 to 1.78 Å. When the amount of TM-DTPMP LDH in EP was 8%, the limitted oxygen index of the composite material increased from the original 19.2% to 30.2%. In addition, Cone calorimeter (CC) and Raman spectrum results indicated that with the addition of TM-DTPMP LDHs, the value of heat release rate peak (pHRR) and total heat release (THR) were reduced by more than 43% and 60%, while the value of smoke formation rate (pSPR) and the total smoke production (TSP) decreased nearly 64% and 83%, respectively. The significant reduction in the release of combustion heat and harmful smoke during EP combustion may be attributed to the synergistic flame-retardant effect between hydrotalcite and DTPMP. This work exhibited great potential for the green recycling of PTs and the enhancement of the fire safety of EP.

Leaching Process of Weathered Crust Elution-Deposited Rare Earth Ore With Formate Salts.

To strengthen the rare earth leaching process and weaken the hydration of clay minerals for preventing landslides, it is of great importance to adopt a green and sustainable leaching agent in the industry. In this work, the leaching process of weathered crust elution-deposited rare earth ores with formate salts (ammonium formate, potassium formate, and sodium formate) was investigated. The effects of formate salts on the linear swelling ratio and zeta potential of the clay minerals were studied. The experimental results showed that ammonium formate could effectively recover the rare earth elements from weathered crust elution-deposited rare earth as well as inhibit the leaching of impurity aluminum. At room temperature, when the ammonium formate concentration was 1% wt, the leaching efficiencies of rare earth and aluminum were 87 and 37%, respectively. Compared with traditional inorganic ammonium salts, the inhibition effect of impurity aluminum was obvious. In addition, the results of the linear swelling ratio in the clay minerals showed that the inhibit ability of formate salts on the hydration of clay minerals enhanced with the increase of the formate concentration, and the order of the inhabitation on the clay minerals followed: 1% ammonium formate > 1.5% potassium formate > 2.5% sodium formate > distilled water. Based on the double layer theory, ammonium formate and potassium formate could effectively compress clay mineral particles to avoid water intake, which could increase the interaction between clay mineral particles and greatly reduce the electronegative property of the clay minerals, so as to effectively reduce the surface hydration of clay minerals to decrease the swelling of rare earth ore. The results of this experiment have important and practical significance in guiding the prevention of landslides, promoting the in-situ leaching technology, and effectively protecting the ecological environment in mining areas.

Effects of Ion Characteristics on the Leaching of Weathered Crust Elution-Deposited Rare Earth Ore.

To reveal the ion-exchange mechanism in the leaching process of weathered crust elution-deposited rare earth ores with different leaching agents, the effects of a variety of cations and anions at different concentrations on the leaching process were investigated, including Al3+, Fe3+, Ca2+, Mg2+, Na+, K+, NH 4 + and Cl-, NO 3 - , and SO 4 2 - . Meanwhile, the relationships between different concentrations of cations and anions and leaching efficiency were investigated, as was the relationship between different concentrations of cations and anions and zeta potential. The effect of different ions on the swelling of clay minerals during leaching process was also investigated. The results shown that NH 4 + was the most affected electrolyte cation in terms of rare earth leaching efficiency during the leaching process of weathered crust elution-deposited rare earth ore among three different cationic valence states, and the leaching efficiency was 86.93% at the optimal leaching concentration. The influence of the three anions on the leaching efficiency of rare earth was NO 3 - > Cl - > SO 4 2 - , and the leaching efficiency of rare earth were 83.21, 81.52, and 80.12% at the optimal leaching concentration, respectively. The NH 4 + had the greatest effect on the zeta potential of weathered crust elution-deposited rare earth ore, and the zeta potential was -18.1 mV at the optimal leaching concentration. Additionally, the order of the effect of three anions on zeta potential was SO 4 2 - > NO 3 - > Cl - . Combined with the effect on the rare earth leaching process, anions and cations were considered separately, and NH 4 + and Cl- were selected; the relationship between the rare earth leaching efficiency and zeta potential conforms to the follow equations: NH 4 + :Y = -0.48X2 - 13.51X - 1.58, R 2 = 0.98133 and Cl-:Y= -1.22X2 - 17.64X + 23.29, R 2 = 0.99010. It was also found in the swelling experiment of the weathered crust elution-deposited rare earth ore that the swelling ratio of clay minerals was the lowest when the cation and anion were NH 4 + and Cl- and the swelling ratios were 1.874 and 2.015%, respectively.

Characterization of the Wheat-Psathyrostachys huashania Keng 2Ns/2D Substitution Line H139: A Novel Germplasm With Enhanced Resistance to Wheat Take-All.

Take-all is a devastating soil-borne disease that affects wheat production. The continuous generation of disease-resistance germplasm is an important aspect of the management of this pathogen. In this study, we characterized the wheat-Psathyrostachys huashania Keng (P. huashania)-derived progeny H139 that exhibits significantly improved resistance to wheat take-all disease compared with its susceptible parent 7182. Sequential genomic in situ hybridization (GISH) and multicolor fluorescence in situ hybridization (mc-FISH) analyses revealed that H139 is a stable wheat-P. huashania disomic substitution line lacking wheat chromosome 2D. Expressed sequence tag-sequence tagged site (EST-STS) marker and Wheat Axiom 660K Genotyping Array analysis further revealed that H139 was a novel wheat-P. huashania 2Ns/2D substitution line. In addition, the H139 line was shown to be cytologically stable with a dwarf phenotype and increased spikelet number. These results indicate that H139, with its enhanced wheat take-all disease resistance and desirable agronomic traits, provides valuable genetic resources for wheat chromosome engineering breeding.

Semi-Supervised Domain Adaptation by Covariance Matching.

Transferring knowledge from a source domain to a target domain by domain adaptation has been an interesting and challenging problem in many machine learning applications. The key problem is how to match the data distributions of the two heterogeneous domains in a proper way such that they can be treated indifferently for learning. We propose a covariance matching approach DACoM for semi-supervised domain adaptation. The DACoM embeds the original samples into a common latent space linearly such that the covariance mismatch of the two mapped distributions is minimized, and the local geometric structure and discriminative information are preserved simultaneously. The KKT conditions of DACoM model are given as a nonlinear eigenvalue equation. We show that the KKT conditions could at least ensure local optimality. An efficient eigen-updating algorithm is then given for solving the nonlinear eigenvalue problem, whose convergence is guaranteed conditionally. To deal with the case when homogeneous information could only be matched nonlinearly, a kernel version of DACoM is further considered. We also analyze the generalization bound for our domain adaptation approaches. Numerical experiments on simulation datasets and real-world applications are given to comprehensively demonstrate the effectiveness and efficiency of the proposed approach. The experiments show that our method outperforms other existing methods for both homogeneous and heterogeneous domain adaptation.

Low-rank matrix approximation with manifold regularization.

This paper proposes a new model of low-rank matrix factorization that incorporates manifold regularization to the matrix factorization. Superior to the graph-regularized nonnegative matrix factorization, this new regularization model has globally optimal and closed-form solutions. A direct algorithm (for data with small number of points) and an alternate iterative algorithm with inexact inner iteration (for large scale data) are proposed to solve the new model. A convergence analysis establishes the global convergence of the iterative algorithm. The efficiency and precision of the algorithm are demonstrated numerically through applications to six real-world datasets on clustering and classification. Performance comparison with existing algorithms shows the effectiveness of the proposed method for low-rank factorization in general.

Adaptive manifold learning.

Manifold learning algorithms seek to find a low-dimensional parameterization of high-dimensional data. They heavily rely on the notion of what can be considered as local, how accurately the manifold can be approximated locally, and, last but not least, how the local structures can be patched together to produce the global parameterization. In this paper, we develop algorithms that address two key issues in manifold learning: 1) the adaptive selection of the local neighborhood sizes when imposing a connectivity structure on the given set of high-dimensional data points and 2) the adaptive bias reduction in the local low-dimensional embedding by accounting for the variations in the curvature of the manifold as well as its interplay with the sampling density of the data set. We demonstrate the effectiveness of our methods for improving the performance of manifold learning algorithms using both synthetic and real-world data sets.