Enhanced rare-earth separation with a metal-sensitive lanmodulin dimer.

Technologically critical rare-earth elements are notoriously difficult to separate, owing to their subtle differences in ionic radius and coordination number1-3. The natural lanthanide-binding protein lanmodulin (LanM)4,5 is a sustainable alternative to conventional solvent-extraction-based separation6. Here we characterize a new LanM, from Hansschlegelia quercus (Hans-LanM), with an oligomeric state sensitive to rare-earth ionic radius, the lanthanum(III)-induced dimer being >100-fold tighter than the dysprosium(III)-induced dimer. X-ray crystal structures illustrate how picometre-scale differences in radius between lanthanum(III) and dysprosium(III) are propagated to Hans-LanM's quaternary structure through a carboxylate shift that rearranges a second-sphere hydrogen-bonding network. Comparison to the prototypal LanM from Methylorubrum extorquens reveals distinct metal coordination strategies, rationalizing Hans-LanM's greater selectivity within the rare-earth elements. Finally, structure-guided mutagenesis of a key residue at the Hans-LanM dimer interface modulates dimerization in solution and enables single-stage, column-based separation of a neodymium(III)/dysprosium(III) mixture to >98% individual element purities. This work showcases the natural diversity of selective lanthanide recognition motifs, and it reveals rare-earth-sensitive dimerization as a biological principle by which to tune the performance of biomolecule-based separation processes.

Structure-driven development of a biomimetic rare earth artificial metalloprotein.

The 2011 discovery of the first rare earth-dependent enzyme in methylotrophic Methylobacterium extorquens AM1 prompted intensive research toward understanding the unique chemistry at play in these systems. This enzyme, an alcohol dehydrogenase (ADH), features a La3+ ion closely associated with redox-active coenzyme pyrroloquinoline quinone (PQQ) and is structurally homologous to the Ca2+-dependent ADH from the same organism. AM1 also produces a periplasmic PQQ-binding protein, PqqT, which we have now structurally characterized to 1.46-Å resolution by X-ray diffraction. This crystal structure reveals a Lys residue hydrogen-bonded to PQQ at the site analogously occupied by a Lewis acidic cation in ADH. Accordingly, we prepared K142A- and K142D-PqqT variants to assess the relevance of this site toward metal binding. Isothermal titration calorimetry experiments and titrations monitored by UV-Vis absorption and emission spectroscopies support that K142D-PqqT binds tightly (Kd = 0.6 ± 0.2 µM) to La3+ in the presence of bound PQQ and produces spectral signatures consistent with those of ADH enzymes. These spectral signatures are not observed for WT- or K142A-variants or upon addition of Ca2+ to PQQ ⸦ K142D-PqqT. Addition of benzyl alcohol to La3+-bound PQQ ⸦ K142D-PqqT (but not Ca2+-bound PQQ ⸦ K142D-PqqT, or La3+-bound PQQ ⸦ WT-PqqT) produces spectroscopic changes associated with PQQ reduction, and chemical trapping experiments reveal the production of benzaldehyde, supporting ADH activity. By creating a metal binding site that mimics native ADH enzymes, we present a rare earth-dependent artificial metalloenzyme primed for future mechanistic, biocatalytic, and biosensing applications.

Weathered granites and soils harbour microbes with lanthanide-dependent methylotrophic enzymes.

BACKGROUND: Prior to soil formation, phosphate liberated by rock weathering is often sequestered into highly insoluble lanthanide phosphate minerals. Dissolution of these minerals releases phosphate and lanthanides to the biosphere. Currently, the microorganisms involved in phosphate mineral dissolution and the role of lanthanides in microbial metabolism are poorly understood. RESULTS: Although there have been many studies of soil microbiology, very little research has investigated microbiomes of weathered rock. Here, we sampled weathered granite and associated soil to identify the zones of lanthanide phosphate mineral solubilisation and genomically define the organisms implicated in lanthanide utilisation. We reconstructed 136 genomes from 11 bacterial phyla and found that gene clusters implicated in lanthanide-based metabolism of methanol (primarily xoxF3 and xoxF5) are surprisingly common in microbial communities in moderately weathered granite. Notably, xoxF3 systems were found in Verrucomicrobia for the first time, and in Acidobacteria, Gemmatimonadetes and Alphaproteobacteria. The xoxF-containing gene clusters are shared by diverse Acidobacteria and Gemmatimonadetes, and include conserved hypothetical proteins and transporters not associated with the few well studied xoxF systems. Given that siderophore-like molecules that strongly bind lanthanides may be required to solubilise lanthanide phosphates, it is notable that candidate metallophore biosynthesis systems were most prevalent in bacteria in moderately weathered rock, especially in Acidobacteria with lanthanide-based systems. CONCLUSIONS: Phosphate mineral dissolution, putative metallophore production and lanthanide utilisation by enzymes involved in methanol oxidation linked to carbonic acid production co-occur in the zone of moderate granite weathering. In combination, these microbial processes likely accelerate the conversion of granitic rock to soil.

Lanpepsy is a novel lanthanide-binding protein involved in the lanthanide response of the obligate methylotroph Methylobacillus flagellatus.

Lanthanides were recently discovered as metals required in the active site of certain methanol dehydrogenases. Since then, the characterization of the lanthanome, that is, proteins involved in sensing, uptake, and utilization of lanthanides, has become an active field of research. Initial exploration of the response to lanthanides in methylotrophs has revealed that the lanthanome is not conserved and that multiple mechanisms for lanthanide utilization must exist. Here, we investigated the lanthanome in the obligate model methylotroph Methylobacillus flagellatus. We used a proteomic approach to analyze differentially regulated proteins in the presence of lanthanum. While multiple known proteins showed induction upon growth in the presence of lanthanum (Xox proteins, TonB-dependent receptor), we also identified several novel proteins not previously associated with lanthanide utilization. Among these was Mfla_0908, a periplasmic 19 kDa protein without functional annotation. The protein comprises two characteristic PepSY domains, which is why we termed the protein lanpepsy (LanP). Based on bioinformatic analysis, we speculated that LanP could be involved in lanthanide binding. Using dye competition assays, quantification of protein-bound lanthanides by inductively coupled plasma mass spectrometry, as well as isothermal titration calorimetry, we demonstrated the presence of multiple lanthanide binding sites that showed selectivity over the chemically similar calcium ion. LanP thus represents the first member of the PepSY family that binds lanthanides. Although the physiological role of LanP is still unclear, its identification is of interest for applications toward the sustainable purification and separation of rare-earth elements.

Rapid Propagation of Ca2+ Waves and Electrical Signals in the Liverwort Marchantia polymorpha.

In response to both biotic and abiotic stresses, vascular plants transmit long-distance Ca2+ and electrical signals from localized stress sites to distant tissues through their vasculature. Various models have been proposed for the mechanisms underlying the long-distance signaling, primarily centered around the presence of vascular bundles. We here demonstrate that the non-vascular liverwort Marchantia polymorpha possesses a mechanism for propagating Ca2+ waves and electrical signals in response to wounding. The propagation velocity of these signals was approximately 1-2 mm s-1, equivalent to that observed in vascular plants. Both Ca2+ waves and electrical signals were inhibited by La3+ as well as tetraethylammonium chloride, suggesting the crucial importance of both Ca2+ channel(s) and K+ channel(s) in wound-induced membrane depolarization as well as the subsequent long-distance signal propagation. Simultaneous recordings of Ca2+ and electrical signals indicated a tight coupling between the dynamics of these two signaling modalities. Furthermore, molecular genetic studies revealed that a GLUTAMATE RECEPTOR-LIKE (GLR) channel plays a central role in the propagation of both Ca2+ waves and electrical signals. Conversely, none of the three two-pore channels were implicated in either signal propagation. These findings shed light on the evolutionary conservation of rapid long-distance Ca2+ wave and electrical signal propagation involving GLRs in land plants, even in the absence of vascular tissue.

The deposition of lanthanum carbonate may activate macrophages to induce gastrointestinal mucosal injury in patients with chronic kidney disease: an in vitro caco-2/THP-1 macrophage coculture model study.

The aim of this study was to investigate the effect and possible underlying mechanism of La2(CO3)3 deposition on GI mucosal inflammation. Our results showed that La2(CO3)3 can dissolve in artificial gastric fluids and form lanthanum phosphate (LaPO4) precipitates with an average size of about 1 µm. To mimic the intestinal mucosa and epithelial barrier, we established a Caco-2/THP-1 macrophage coculture model and a Caco-2 monoculture model, respectively. Our findings demonstrated that the medium of THP-1 macrophages stimulated by LaPO4 particles can damage the Caco-2 monolayer integrity in the coculture model, while the particles themselves had no direct impact on the Caco-2 monolayer integrity in the monoculture model. We measured values of trans-epithelial electrical resistance and detected images using a laser scanning confocal microscope. These results indicate that continuous stimulation of LaPO4 particles on macrophages can lead to a disruption of intestinal epithelium integrity. In addition, LaPO4 particles could stimulate THP-1 macrophages to secrete both IL-1ß and IL-8. Although LaPO4 particles can also promote Caco-2 cells to secrete IL-8, the secretion was much lower than that produced by THP-1 macrophages. In summary, the deposition of La2(CO3)3 has been shown to activate macrophages and induce damage to intestinal epithelial cells, which may exacerbate inflammation in patients with chronic kidney disease. Therefore, patients taking lanthanum carbonate, especially those with gastrointestinal mucosal inflammation, should be mindful of the potential for drug deposition in the GI system.

Mechanisms of Lanthanum-mediated mitigation of salt stress in soybean (Glycine max L.).

Salinity is considered one of the abiotic stresses that have the greatest impact on soybean production worldwide. Lanthanum (La) is a rare earth element that can reduce adverse conditions on plant growth and productivity. However, the regulatory mechanism of La-mediated plant response to salt stress has been poorly studied, particularly in soybeans. Therefore, our study investigated the mechanisms of La-mediated salt stress alleviation from the perspectives of the antioxidant system, subcellular structure, and metabolomics responses. The results indicated that salt stress altered plant morphology and biomass, resulting in an increase in peroxidation, inhibition of photosynthesis, and damage to leaf structure. Exogenous La application effectively promoted the activity of superoxide dismutase (SOD) and peroxidase (POD), as well as the soluble protein content, while decreasing the Na+ content and Na+/K+ ratio in roots and leaves, and reducing oxidative damage. Moreover, transmission electron microscopy (TEM) demonstrated that La prevented the disintegration of chloroplasts. Fourier-transform infrared spectroscopy (FTIR) analysis further confirmed that La addition mitigated the decline in protein, carbohydrates, and pectin levels in the leaves. Lanthanum decreased the leaf flavonoid content and synthesis by inhibiting the content of key substances in the phenylalanine metabolism pathway during NaCl exposure. Collectively, our research indicates that La reduces cell damage by regulating the antioxidant system and secondary metabolite synthesis, which are important mechanisms for the adaptive response of soybean leaves, thereby improving the salt tolerance of soybeans.

Lanthanum and Indium intermetallics nanomaterial for thermal photovoltaic applications - A full potential study.

In this work Full Potential study performed on Lanthanum compounds to analyze its photovoltaic properties. Five different combinations of Lanthanum and Indium with phosphorus are chosen in this study are La3P, La2InP, LaIn2P, LaP and InP. The optical, structural, thermoelectric, thermal, and electronic properties of all the above-mentioned compounds are analyzed using Density Functional Theory (DFT) applied in the WIEN2k software. Based on the analysis of electronic properties is concluded that La3P, LaP, La2InP and LaIn2P are conductors whereas InP is semiconductor (direct band gap) with band gap (energy) value 0.39 eV. The optical properties analysis shows these materials have desirable properties in the near UV or in the UV region. The low value of Gibbs energy indicates high thermodynamic stability. Power factor values for La2InP, LaP, InP and La3P are found to be in agreement with existing thermoelectric material, rendering them as potential thermal photovoltaic materials.

Simultaneous immobilization of sediment internal phosphorus, arsenic and tungsten by lanthanum carbonate capping.

In this study, lanthanum carbonate (LC) was selected as a capping agent to examine its effectiveness in immobilizing sediment internal phosphorus (P), arsenic (As) and tungsten (W). With a 180-day incubation experiment, it was determined that LC capping efficiently reduced the concentrations of soluble reactive P (SRP), soluble As and soluble W in pore water, with the highest reduction rate of 83.39%, 56.21% and 68.52%, respectively. The primary mechanisms involved in the adsorption of P, As and W by LC were precipitation reactions and ligand exchange. Additionally, P, As and W were immobilized by LC capping through the transformation of fractions from mobile and less stable forms to more stable forms. Furthermore, LC capping led to an increase in the Eh value, which promoted the oxidation of soluble Fe (Ⅱ) and soluble Mn. The significantly positive correlation and synchronized variations observed between SRP, soluble As, soluble W, and soluble Fe (II) indicated that the effects of LC on Fe redox played a crucial role in immobilizing sediment internal P, As and W. However, the oxidation of Mn, promoted by LC, played a more significant role in immobilizing sediment internal As than P and W. These effects resulted in LC capping achieving the highest reduction of SRP, soluble As and soluble W flux at 145.22, 22.19, and 0.58 µg m-2d-1. It is of note that LC capping did not lead to an elevated release hazard of Co, Ni, Cu, and Pb, barring Cd. Besides, LC capping did not modify the entire microbial communities in the sediment, but altered the proportional representation of specific microorganisms. Generally, LC has potential as a capping agent capable of simultaneously immobilizing sediment internal P, As and W.

Amendment of Sargassum oligocystum bio-char with MnFe2O4 and lanthanum MOF obtained from PET waste for fluoride removal: A comparative study.

The use of biomass and waste to produce adsorbent reduces the cost of water treatment. The bio-char of Sargassum oligocystum (BCSO) was modified with MnFe2O4 magnetic particles and La-metal organic framework (MOF) to generate an efficient adsorbent (BCSO/MnFe2O4@La-MOF) for fluoride ions (F-) removal from aqueous solutions. The performance of BCSO/MnFe2O4@La-MOF was compared with BCSO/MnFe2O4 and BCSO. The characteristics of the adsorbents were investigated using various techniques, which revealed that the magnetic composites were well-synthesized and exhibited superparamagnetic properties. The maximum adsorption efficiencies (BCSO: 97.84%, BCSO/MnFe2O4: 97.85%, and BCSO/MnFe2O4@La-MOF: 99.36%) were achieved under specific conditions of pH 4, F- concentration of 10 mg/L, and adsorbent dosage of 3, 1.5, and 1 g/L for BCSO, BCSO/MnFe2O4, and BCSO/MnFe2O4@La-MOF, respectively. The results demonstrated that the experimental data adheres to a pseudo-second-order kinetic model. The enthalpy, entropy, and Gibbs free energy were determined to be negative; thus, the F- adsorption was exothermic and spontaneous in the range of 25-50 °C. The equilibrium data of the process exhibited conformity with the Langmuir model. The maximum adsorption capacities of F- ions were determined as 10.267 mg/g for BCSO, 14.903 mg/g for the BCSO/MnFe2O4, and 31.948 mg/g for BCSO/MnFe2O4@La-MOF. The KF and AT values for the F- adsorption were obtained at 21.03 mg/g (L/mg)1/n and 100 × 10+9 L/g, indicating the pronounced affinity of the BCSO/MnFe2O4@La-MOF towards F- than other samples. The significant potential of the BCSO/MnFe2O4@La-MOF magnetic composite for F- removal from industrial wastewater, makes it suitable for repeated utilization in the adsorption process.

Rare earth contamination of edible vegetation: Ce, La, and summed REE in fungi.

The increasing and diversified use of rare earth elements (REE) is considered a potential source of pollution of environmental media including soils. This work documents critically overview data on the occurrence of REE in the fruiting bodies of wild and farmed species of edible and medicinal mushrooms, as this was identified as the largest published dataset of REE occurrence in foodstuff. Most of the literature reported occurrences of cerium (Ce) and lanthanum (La), but a number of studies lacked data on all lanthanides. The Ce, La, and summed REE occurrences were assessed through the criteria of environmental geochemistry, analytical chemistry, food toxicology, mushroom systematics, and ecology. Ce and La accumulate similarly in fruiting bodies and are not fractionated during uptake, maintaining the occurrence patterns of their growing substrates. Similarly, there is no credible evidence of variable REE uptake because the evaluated species data show natural, unfractionated patterns in accordance with the Oddo-Harkins' order of environmental lanthanide occurrence. Thus, lithosphere occurrence patterns of Ce and La as the first and the third most abundant lanthanides are reflected in wild and farmed mushrooms regardless of substrate and show that Ce is around twice more abundant than La. The current state of knowledge provides no evidence that mushroom consumption at these REE occurrence levels poses a health risk either by themselves or when included with other dietary exposure. Macromycetes appear to bio-exclude lanthanides because independently reported bioconcentration factors for different species and collection sites, typically range from < 1 to 0.001. This is reflected in fruiting body concentrations which are four to two orders of magnitude lower than growing substrates. KEY POINTS: •Original REE occurrence patterns in soils/substrates are reflected in mushrooms •No evidence for the fractionation of REE during uptake by fungi •Mushrooms bio-exclude REE in fruiting bodies.

Lanthanum nitrate demonstrated no genotoxicity in the conducted tests.

Given the widespread applications in industrial and agricultural production, the health effects of rare earth elements (REEs) have garnered public attention, and the genotoxicity of REEs remains unclear. In this study, we evaluated the genetic effects of lanthanum nitrate, a typical representative of REEs, with guideline-compliant in vivo and in vitro methods. Genotoxicity assays, including the Ames test, comet assay, mice bone marrow erythrocyte micronucleus test, spermatogonial chromosomal aberration test, and sperm malformation assay were conducted to assess mutagenicity, chromosomal damage, DNA damage, and sperm malformation. In the Ames test, no statistically significant increase in bacterial reverse mutation frequencies was found as compared with the negative control. Mice exposed to lanthanum nitrate did not exhibit a statistically significant increase in bone marrow erythrocyte micronucleus frequencies, spermatogonial chromosomal aberration frequencies, or sperm malformation frequencies compared to the negative control (P > 0.05). Additionally, after a 24-h treatment with lanthanum nitrate at concentrations of 1.25, 5, and 20 µg/ml, no cytotoxicity was observed in CHL cells. Furthermore, the comet assay results indicate no significant DNA damage was observed even after exposure to high doses of lanthanum nitrate (20 µg/ml). In conclusion, our findings suggest that lanthanum nitrate does not exhibit genotoxicity.

Effect of lanthanum nitrate on adipogenesis in mice.

Lanthanum (La) is widely used in modern industry and agriculture because of its unique physicochemical properties and is broadly exposed in the population. Some studies have shown that La may have some effects on adipogenesis, but there is a lack of related in vivo evidence. In this study, the effects of La(NO3 )3 on adipogenesis and its associated mechanism were studied using C57BL/6J mouse model. The results showed that La(NO3 )3 exposure caused a decrease in body weight and the percentage of fat content in mice. In addition, the adipose marker molecules and specific adipogenic transcription factors decreased in both white adipose tissue (WAT) and brown adipose tissue (BAT). Detection of signaling pathway-related molecules revealed that canonical wnt/ß-catenin pathway-related molecules were upregulated in both adipose tissues. In summary, in vivo exposure to La(NO3 )3 might inhibited adipogenesis in mice, possibly through upregulation of the canonical Wnt/ß-catenin signaling pathway.

Assessment of osteopontin as an early nephrotoxicity indicator in human renal proximal tubule cells and its application in evaluating lanthanum-induced nephrotoxicity.

Nephrotoxicity is a common adverse effect induced by various chemicals, necessitating the development of reliable toxicity screening models for nephrotoxicity assessment. In this study, we assessed a group of nephrotoxicity indicators derived from different toxicity pathways, including conventional endpoints and kidney tubular injury biomarkers such as clusterin (CLU), kidney injury molecule-I (KIM-1), osteopontin (OPN), and neutrophil gelatinase-associated lipocalin (NGAL), using HK-2 and induced pluripotent stem cells (iPSCs)-derived renal proximal tubular epithelial-like cells (PTLs). Among the biomarkers tested, OPN emerged as the most discerning and precise marker. The predictive potential of OPN was tested using a panel of 10 nephrotoxic and 5 non-nephrotoxic compounds. The results demonstrated that combining OPN with the half-maximal inhibitory concentration (IC50) enhanced the diagnostic accuracy in both cellular models. Additionally, PTLs cells showed superior predictive efficacy for nephrotoxicity compared to HK-2 cells in this investigation. The two cellular models were utilized to evaluate the nephrotoxicity of lanthanum. The findings indicated that lanthanum possesses nephrotoxic properties; however, the degree of nephrotoxicity was relatively low, consistent with the outcomes of in vivo experiments.

Biodegradation enhancement of high concentrations formaldehyde waste gas and verification of the metabolic mechanism.

The enhanced effects of formaldehyde biodegradation in a biofilm packing tower are investigated in this study. Three experimental groups were established: a blank control group, a biochar addition group, and a lanthanum addition group. The inlet gas flow rate, the inlet gas concentration, and the structural succession characteristics of the microbial community in the tower were investigated by regular sampling. The intracellular metabolites and key enzymes of the dominant functional bacteria, Pseudomonas P1 and Methylobacterium Q1, in the tower were analyzed. The results indicated that with the biochar addition, the formaldehyde purification efficiency increased significantly from 91.67-94.67 % to 94.12 96.85 %, and the bio-elimination capacity increased with an increase in the inlet gas flow rate from 2.314 to 13.988 mg L-1h-1 to 2.697-15.051 mg L-1h-1. With the addition of lanthanum, the purification efficiency increased significantly from 90.80-93.98 % to 94.36-96.78 %, and the bio-elimination capacity increased with an increase in the inlet gas concentration from 1.099-11.284 mg L-1h-1 to 1.266-11.961 mg L-1h-1. The microbial community structure in the tower changed with system operation, and the formaldehyde degrading functional bacteria formed the dominant bacteria. It was verified that P1 and Q1 metabolized high concentrations of formaldehyde by the serine cycle and the ribulose monophosphate (RuMP) cycle.

Lanthanum interferes with the fundamental rhythms of stomatal opening, expression of related genes, and evapotranspiration in Arabidopsis thaliana.

The accumulation of rare earth elements (REEs) in the global environment poses a threat to plant health and ecosystem stability. Stomata located on leaves serve as the primary site for plant responses to REE-related threats. This study focused on lanthanum [La(III)], a prevalent REE in the atmospheric environment. Using interdisciplinary techniques, it was found that La(III) (≤80 µM) interfered with the fundamental rhythms of stomatal opening, related gene expression, and evapotranspiration in plants. Specifically, when exposed to low concentrations of La(III) (15 and 30 µM), the expression levels of six genes were increased, stomatal opening was enhanced, and the evapotranspiration rate was accelerated. The interference on stomatal rhythms was enhanced with higher concentrations of La(III) (60 and 80 µM), increasing the expression levels of six genes, stomatal opening, and evapotranspiration rate. To counter the interference of low concentrations of La(III) (15 and 30 µM), plants accelerated nutrient replenishment through La(III)-induced endocytosis, which the redundant nutrients enhanced photosynthesis. However, replenished nutrients failed to counter the disruption of plant biological rhythms at higher concentrations of La(III) (60 and 80 µM), thus inhibiting photosynthesis due to nutrient deficit. The interference of La(III) on these biological rhythms negatively affected plant health and ecosystem stability.

A plasmid containing the human metallothionein-II gene selectively distinguishes trivalent lanthanum from several divalent heavy metal cations during monoclonal antibody-assisted agarose gel electrophoresis.

Trivalent lanthanide ions are known for their ability to interact with calcium-binding sites in various proteins. There is a need to assess the bioavailability of lanthanides and other heavy metals introduced into the body as components of implants or as contrast agents. This study aimed to develop a method to address bioavailability and/or presence of trivalent lanthanide ions by examining electrophoretic mobility in an agarose gel of a plasmid harboring the human metallothionein-II gene (hMT-II). Mobility of the plasmid was specifically altered by a monoclonal antibody raised against the zinc-binding transcription factor that controls the activity of the hMT-II gene. This study showed that the plasmid acquired a lanthanide-specific mobility pattern that allowed the presence of lanthanide ions to be readily determined in a 0.8% agarose gel. These findings suggest that this plasmid/monoclonal antibody combination under selected conditions may be useful in industrial, environmental, and biomedical settings to identify, separate, or capture lanthanide ions in complex mixtures that contain an array of metal ions.

Understanding the effects of A-site Ag-doping on LaCoO3 perovskite for NO oxidation: Structural and magnetic properties.

The partial substitution of A-site in perovskites is a major strategy to enhance the catalytic oxidation activity. This study explores the use of silver (Ag) to partially replace the lanthanum (La) ion at the A-site in LaCoO3 perovskite, investigating the role of Ag in the ABO3 perovskite structure, elucidating the nitric oxide (NO) oxidation mechanism over La1-xAgxCoO3 (x = 0.1-0.5) perovskites. La0.7Ag0.3CoO3 with an Ag-doping amount of 0.3, exhibited the highest NO oxidation activity of 88.5% at 275 °C. Characterization results indicated that Ag substitution enhanced the perovskite, maintaining its original phase structure, existing in the form of a mixture of Ag0 and Ag+ in the La1-xAgxCoO3 (x = 0.1-0.5) perovskites. Notably, Ag substitution improved the specific surface area, reduction performance, Co3+, and surface adsorption oxygen content. Additionally, the study investigated the relationship between magnetism and NO oxidation from a magnetism perspective. Ag-doping strengthened the magnetism of La-Ag perovskite, resulting in stronger adsorption of paramagnetic NO. This study elucidated the NO oxidation mechanism over La-Ag perovskite, considering structural and magnetic properties, providing valuable insights for the subsequent development and industrial application of high oxidation ability perovskite catalysts.

The effects of different doses of lanthanum-modified bentonite in combination with a submerged macrophyte (Vallisneria denseserrulata) on phosphorus inactivation and macrophyte growth: A mesocosm study.

The combination of chemical phosphorus (P) inactivation and submerged macrophyte transplantation has been widely used in lake restoration as it yields stronger effects than when applying either method alone. However, the dose effect of chemical materials on P inactivation when used in combination with submerged macrophytes and the influences of the chemicals used on the submerged macrophytes growth remain largely unknown. In this study, we investigated P inactivation in both the water column and the sediment, and the responses of submerged macrophytes to Lanthanum modified bentonite (LMB) in an outdoor mesocosm experiment where Vallisneria denseserrulata were transplanted into all mesocosms and LMB was added at four dosage levels, respectively: control (LMB-free), low dosage (570 g m-2), middle dosage (1140 g m-2), and high dosage (2280 g m-2). The results showed that the combination of LMB dosage and V. denseserrulata reduced TP in the water column by 32%-38% compared to V. denseserrulata alone, while no significant difference was observed among the three LMB treatments. Porewater soluble reactive P, two-dimensional diffusive gradient in thin films (DGT)-labile P concentrations, and P transformation in the 0-1 cm sediment layer exhibited similar trends along the LMB dosage gradient. Besides, LMB inhibited plant growth and reduced the uptake of mineral elements (i.e., calcium, manganese, iron, and magnesium) in a dosage-dependent manner with LMB. LMB may reduce plant growth by creating a P deficiency risk for new ramets and by interfering with the uptake of mineral elements. Considering both the dose effect of LMB on P inactivation and negative effect on macrophyte growth, we suggest a "small dosage, frequent application" method for LMB application to be used in lake restoration aiming to recover submerged macrophytes and clear water conditions.

High-performance electrosorption of lanthanum ion by Mn3O4-loaded phosphorus-doped porous carbon electrodes via capacitive deionization.

Transition-metal-oxide@heteroatom doped porous carbon composites have attracted considerable research interest because of their large theoretical adsorption capacity, excellent electrical conductivity and well-developed pore structure. Herein, Mn3O4-loaded phosphorus-doped porous carbon composites (Mn3O4@PC-900) were designed and fabricated for the electrosorption of La3+ in aqueous solutions. Due to the synergistic effect between Mn3O4 and PC-900, and the active sites provided by Mn-O-Mn, C/PO, C-P-O and Mn-OH, Mn3O4@PC-900 exhibits high electrosorption performance. The electrosorption value of Mn3O4@PC-900 was 45.34% higher than that of PC-900, reaching 93.02 mg g-1. Moreover, the adsorption selectivity reached 87.93% and 89.27% in La3+/Ca2+ and La3+/Na+ coexistence system, respectively. After 15 adsorption-desorption cycles, its adsorption capacity and retention rate were 50.34 mg g-1 and 54.12%, respectively. The electrosorption process is that La3+ first accesses the pores of Mn3O4@PC-900 to generate an electric double layer (EDL), and then undergoes further Faradaic reaction with Mn3O4 and phosphorus-containing functional groups through intercalation, surface adsorption and complexation. This work is hoped to offer a new idea for exploring transition-metal-oxide @ heteroatom doped porous carbon composites for separation and recovery of rare earth elements (REEs) by capacitive deionization.