Microbial green synthesis of luminescent terbium sulfide nanoparticles using E. Coli: a rare earth element detoxification mechanism.

BACKGROUND: Rare-earth sulfide nanoparticles (NPs) could harness the optical and magnetic features of rare-earth ions for applications in nanotechnology. However, reports of their synthesis are scarce and typically require high temperatures and long synthesis times. RESULTS: Here we present a biosynthesis of terbium sulfide (TbS) NPs using microorganisms, identifying conditions that allow Escherichia coli to extracellularly produce TbS NPs in aqueous media at 37 °C by controlling cellular sulfur metabolism to produce a high concentration of sulfide ions. Electron microscopy revealed ultrasmall spherical NPs with a mean diameter of 4.1 ± 1.3 nm. Electron diffraction indicated a high degree of crystallinity, while elemental mapping confirmed colocalization of terbium and sulfur. The NPs exhibit characteristic absorbance and luminescence of terbium, with downshifting quantum yield (QY) reaching 28.3% and an emission lifetime of ~ 2 ms. CONCLUSIONS: This high QY and long emission lifetime is unusual in a neat rare-earth compound; it is typically associated with rare-earth ions doped into another crystalline lattice to avoid non-radiative cross relaxation. This suggests a reduced role of nonradiative processes in these terbium-based NPs. This is, to our knowledge, the first report revealing the advantage of biosynthesis over chemical synthesis for Rare Earth Element (REE) based NPs, opening routes to new REE-based nanocrystals.

Rare earth metallic elements in plants: assessing benefits, risks and mitigating strategies.

Rare earth elements (REEs) comprises of a uniform group of lanthanides and scandium (Sc) and yttrium (Y) finding their key importance in agriculture sectors, electronic and defense industries, and renewable energy production. The immense application of REEs as plant growth promoters has led to their undesirable accumulation in the soil system raising concerns for REE pollution as upcoming stresses. This review mainly addresses the chemistry of REEs, uptake and distribution and their biphasic responses in plant systems and possible plausible techniques that could mitigate/alleviate REE contamination. It extends beyond the present understanding of the biphasic impacts of rare earth elements (REEs) on physio-biochemical attributes. It not only provides landmarks for further exploration of the interrelated phytohormonal and molecular biphasic nature but also introduces novel approaches aimed at mitigating their toxicities. By delving into innovative strategies such as recycling, substitution, and phytohormone-assisted mitigation, the review expands upon existing knowledge of REEs whilst also offering pathways to tackle the challenges associated with REE utilization.

From screens to seas: Tech contaminants in tiger sharks.

The potential negative impacts of Technology-Critical Elements (TCEs) on the environment and wildlife, despite increasingly recognized, remain largely overlooked. In this sense, this study aimed to investigate the concentrations of several TCEs, including rubidium (Rb), titanium (Ti) and various Rare Earth Elements (REEs), in different tissues of tiger sharks. Sharks incidentally caught by artisanal fleets in southern Brazil were opportunistically sampled and liver, gills, kidneys, heart, muscle, eyes, brain, skin, and teeth were analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Significant Rb concentration variations were observed across different tissues, with higher levels detected in kidneys and lower levels in the liver. Titanium concentrations also exhibited significant differences, with higher levels detected in teeth and lower levels in liver. Although no statistical differences were observed for the analyzed REEs, a trend of higher accumulation in the liver, gills, and skin was noted. Light Rare Earth Elements (LREEs) were found predominantly in all organs, with neodymium, lanthanum, and cerium as the most significant REEs detected. Several statistically significant correlations were identified between Rb and REEs, as well as between Ti and REEs, indicating systemic transport of these elements across different tissues. These findings indicate that the growing extraction and disposal of metallic elements, driven by technological advancements, may lead to their assimilation by marine fauna, particularly at higher trophic levels. The potential harmful effects on these organisms remain unknown and require urgent investigation. Additionally, as mining activities intensify globally, precise legislative measures are essential to address environmental concerns, species conservation, and human health considerations.

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.

Study on the role of microbial metabolites in in-situ noncontact bioleaching of ion-adsorption rare earth ore.

Ion adsorption rare earth ore nearly satisfy global market demand for heavy rare earth elements (HREEs). Bio-leaching has important potential for the clean and efficient extraction of ion-adsorption rare earth ore. However, the complexities of in-situ mining restrict the use of contact/direct bio-leaching, and non-contact/indirect bio-leaching would be the best choice. This study explore the potential of fermentation broths prepared by Yarrowia lipolytica (ATCC 30162) for the bio-leaching of ion-adsorption rare earth ore, and three typical metabolites (potassium citrate (K3Cit), sodium citrate (Na3Cit) and ammonium citrate ((NH4)3Cit) of Yarrowia lipolytica were further evaluated in simulated bioleaching (non-contact bioleaching) of ion-adsorption rare earth ore, including leaching behavior, seepage rule and rare earth elements (REEs) morphological transformation. The column leaching experiments shown that direct leaching of REEs using fermentation broths results in incomplete leaching of REEs due to the influence of impurities. Using the purified and prepared metabolites as lixiviant, REEs can be effectively extracted (leaching efficiency >90%) at cation concentration was only 10 % of the commonly used ammonium sulfate concentration (45 mM). Cation type had less effect on leaching efficiency. During the ion-adsorption rare earth ore leaching process, rare earth ions form a variety of complex chelates with citrate, thus transferring rare earth elements from the mineral surface to the leachate. Experimental results showed that pH and concentration together determined the type and form of rare earth chelates, which in turn affect the leaching behavior of REEs and solution seepage rule. This study helps to provide a theoretical basis for the regulation and enhancement of ion-adsorption rare earth ore non-contact bioleaching process.

Biomining using microalgae to recover rare earth elements (REEs) from bauxite.

Biomining using microalgae has emerged as a sustainable option to extract rare earth elements (REEs). This study aims to (i) explore the capability of REEs recovery from bauxite by microalgae, (ii) assess the change of biochemical function affected by bauxite, and (iii) investigate the effects of operating conditions (i.e., aeration rate, pH, hydraulic retention time) to REEs recovery. The results showed that increasing bauxite in microalgae culture increases REEs recovery in biomass and production of biochemical compounds (e.g., pigments and Ca-Mg ATPase enzyme) up to 10 %. The optimum pulp ratio of bauxite in the microalgae culture ranges from 0.2 % to 0.6 %. Chlorella vulgaris was the most promising, with two times higher in REEs recovery in biomass than the other species. REEs accumulated in microalgae biomass decreased with increasing pH in the culture. This study establishes a platform to make the scaling up of REEs biomining by microalgae plausible.

Rare earth elements as a tool to study the foliar nutrient uptake phenomenon under ambient and elevated atmospheric CO2 concentration.

The ability of plants to uptake nutrients from mineral dust lying on their foliage may prove to be an important mechanism by which plants will cope with increasing CO2 levels in the atmosphere. This mechanism had only recently been reported and was shown to compensate for the projected dilution in plants ionome. However, this phenomenon has yet to be thoroughly studied, particularly in terms of the expected trends under different dust types and varying atmospheric CO2 concentrations, as projected by the IPCC. We treated plants grown under ambient (415 ppm) and elevated CO2 (850 ppm) conditions with either desert dust, volcanic ash, and fire ash analogues by applying it solely on plant foliage and studied their Rare Earth Elements concentrations and patterns. The Rare Earth Elements compositions of the treated plants originated from the dust application, and their incorporation into the plants led to a significant increase in plants vitality, evident in increased photosynthetic activity and biomass. Two trends in the foliar nutrient uptake mechanism were revealed by the Rare Earth Elements, one is that different treatments affected the plant in decreasing order volcanic ash > desert dust > fire ash. The second trend is that foliar intake becomes more significant under elevated CO2, an observation not previously seen. This testifies that the use of Rare Earth Elements in the study of foliar nutrient uptake, and other biological mechanisms is fundamental, and that foliar pathways of nutrient uptake will indeed become more dominant with increasing CO2 under expected atmospheric changes.

A temperature-resilient anammox process for efficient treatment of rare earth element tailings wastewater via synergistic nitrite supply of partial nitritation and partial denitrification.

Rare earth elements result in substantial tailings wastewater with high ammonium and nitrate during extraction. In this study, a temperature-resilient Anammox process was employed for efficient treatment of rare earth element tailings wastewater through implementing synergistic nitrite supply by partial nitritation (PN) and partial denitrification (PD). Enhancing temperature resilience of Anammox process relies on dynamic management of DO and COD inputs to shift the dominant nitrite supplier from PN to PD, stable PD (NAR ≥ 90 %) can boost nitrogen removal by Anammox to 97.8 %. The nitrogen removal rate and nitrogen removal efficiency at 10.6 °C could maintain at 0.12 kgN/m3·d-1 and 92.5 %, respectively. Microbial analysis reveals that Nitrosomonas, Thauera, and Candidatus_Kuenenia are the predominant genera responsible for nitrite supply and nitrogen removal, localized within the gas channels of granules, flocs, and micro-granules, respectively. Keeping the influent C/NO3--N ratio below 1.7 is ideal to prevent overgrowth of Thauera and maintain system stability.

Rare earth elements in biology: From biochemical curiosity to solutions for extractive industries.

Rare earth elements (REEs) are critical for our modern lifestyles and the transition to a low-carbon economy. Recent advances in our understanding of the role of REEs in biology, particularly methylotrophy, have provided opportunities to explore biotechnological innovations to improve REE mining and recycling. In addition to bacterial accumulation and concentration of REEs, biological REE binders, including proteins (lanmodulin, lanpepsy) and small molecules (metallophores and cofactors) have been identified that enable REE concentration and separation. REE-binding proteins have also been used in several mechanistically distinct REE biosensors, which have potential application in mining and medicine. Notably, the role of REEs in biology has only been known for a decade, suggesting their considerable scope for developing new understanding and novel applications.

Microbial recovery of rare earth elements from various waste sources: a mini review with emphasis on microalgae.

Rare Earth Elements (REEs) are indispensable in contemporary technologies, influencing various aspects of our daily lives and environmental solutions. The escalating demand for REEs has led to increased exploitation, resulting in the generation of diverse REE-bearing solid and liquid wastes. Recognizing the potential of these wastes as secondary sources of REEs, researchers are exploring microbial solutions for their recovery. This mini review provides insights into the utilization of microorganisms, with a particular focus on microalgae, for recovering REEs from sources such as ores, electronic waste, and industrial effluents. The review outlines the principles and distinctions of bioleaching, biosorption, and bioaccumulation, offering a comparative analysis of their potential and limitations. Specific examples of microorganisms demonstrating efficacy in REE recovery are highlighted, accompanied by successful methods, including advanced techniques for enhancing microbial strains to achieve higher REE recovery. Moreover, the review explores the environmental implications of bio-recovery, discussing the potential of these methods to mitigate REE pollution. By emphasizing microalgae as promising biotechnological candidates for REE recovery, this mini review not only presents current advances but also illuminates prospects in sustainable REE resource management and environmental remediation.

Molding the future: Optimization of bioleaching of rare earth elements from electronic waste by Penicillium expansum and insights into its mechanism.

The recovery of rare earth elements (REE) from electronic waste is crucial for ensuring future demand security, as there is a high supply risk for this group of elements, and mitigating the environmental impacts of conventional mining. This research focuses on extracting REE from waste printed circuit boards through bioleaching, addressing the limited attention given to this source. A strain of Penicillium expansum demonstrated efficient bioleaching under optimal conditions of 7.5 initial pH, 0.1 mM phosphate concentration, and excluding a buffering agent. The study achieved significant improvements in La and Tb extraction and enhancements in Pr, Nd, and Gd recovery, approaching 70 % within 24 h. Fungal mechanisms involved in REE extraction included fungal pH control, organic acid biosynthesis, phosphate bioavailability, and potential fungal proton pump involvement. This approach offers a promising solution for sustainable REE recovery from e-waste, contributing to resource security and circular economy.

Rare earth elements applied to phytoremediation: Enhanced endocytosis promotes remediation of antimony contamination with different valence levels in Solanum nigrum L.

Antimony (Sb) pollution poses a noteworthy risk to human health and ecosystem sustainability, therefore effective, eco-friendly, and widely accepted restoration methods are urgently needed. This study introduces a new approach of using La(III) foliar application on Solanum nigrum L. (S. nigrum), a cadmium hyperaccumulator, to improve its photosynthetic and root systems under Sb stress, resulting in a higher biomass. Notably, La(III) also enhances endocytosis in root cells, facilitating efficient and non-selective remediation of both Sb(III) and Sb(V) forms. The absorption of Sb by root cell endocytosis was observed visually with a confocal laser scanning microscope. The subcellular distribution of Sb in the cell wall of S. nigrum is reduced. And the antioxidant enzyme activity system is improved, resulting in an enhanced Sb tolerance in S. nigrum. Based on the existing bibliometric analysis, this paper identified optimal conditions for S. nigrum to achieve maximum translocation and bioconcentration factor values for Sb. The foliar application of La(III) on plants treated with Sb(III), Sb(V), and a combination of both resulted in translocation factor values of 0.89, 1.2, 1.13 and bioconcentration factor values of 11.3, 12.81, 14.54, respectively. Our work suggests that La(III)-enhanced endocytosis of S. nigrum root cells is a promising remediation strategy for Sb-contaminated environments.

Hyperaccumulator extracts promoting the phytoremediation of rare earth elements (REEs) by Phytolacca americana: Role of active microbial community in rhizosphere hotspots.

The increased usage of rare earth elements (REEs) leads to the extensive exploitation of rare earth mines, and the REEs pollution in soil caused by the legacy mine tailings has brought great harm to environment and human health. Although Phytolacca americana can remove REEs from contaminated soil to some extent, there is still an urgent problem to improve its efficiency. Hyperaccumulator extract is a new organic material with potential in metal phytoextraction, but its role in REEs phytoremediation and the related underlying processes remain unclear. In this study, hyperaccumulator extracts from P. americana root (PR), stem (PS), leaf (PL) and EDTA were used to improve the phytoremediation efficiency of REEs with P. americana. Soil zymography was applied to assess the enzyme hotspots' spatial distribution in the rhizosphere, and the hotspots' microbial communities were also identified. The results indicated that the application of hyperaccumulator extracts improved the biomass and REEs uptake of P. americana, and the highest REEs content in plant was observed in the treatment of PS, which increased 299% compared to that of the control. Hotspots area of ß-glucosidase, leucine aminopeptidase and acid phosphatase were concentrated in the pant rhizosphere along the roots and increased 2.2, 5.3 and 2.2 times after PS application compared to unamended soils. The PS application increased the relative abundance of Proteobacteria, Cyanobacteria, Bacteroidota and Firmicutes phyla in rhizosphere. Soil fungi have a higher contribution on promoting REEs activation than that of bacteria. Available P and extractable REEs were leading predictors for the plant biomass and REEs concentrations. The co-occurrence network showed that the application of PS creates a more efficient and stable microbial network compared to other treatments. In conclusion, stem-derived hyperaccumulator extract is excellent in stimulating REEs phytoremediation with P. americana by improving hotspots microbial activities and form a healthy rhizosphere microenvironment.

Roles of pH and phosphate in rare earth element biosorption with living acidophilic microalgae.

The increasing demand for rare earth elements (REEs) has spurred interest in the development of recovery methods from aqueous waste streams. Acidophilic microalgae have gained attention for REE biosorption as they can withstand high concentrations of transition metals and do not require added organic carbon to grow, potentially allowing simultaneous sorption and self-replication of the sorbent. Here, we assessed the potential of Galdieria sulphuraria for REE biosorption under acidic, nutrient-replete conditions from solutions containing ≤ 15 ppm REEs. Sorption at pH 1.5-2.5 (the growth optimum of G. sulphuraria) was poor but improved up to 24-fold at pH 5.0 in phosphate-free conditions. Metabolic activity had a negative impact on REE sorption, additionally challenging the feasibility of REE biosorption under ideal growth conditions for acidophiles. We further examined the possibility of REE biosorption in the presence of phosphate for biomass growth at elevated pH (pH ≥ 2.5) by assessing aqueous La concentrations in various culture media. Three days after adding La into the media, dissolved La concentrations were up to three orders of magnitude higher than solubility predictions due to supersaturation, though LaPO4 precipitation occurred under all conditions when seed was added. We concluded that biosorption should occur separately from biomass growth to avoid REE phosphate precipitation. Furthermore, we demonstrated the importance of proper control experiments in biosorption studies to assess potential interactions between REEs and matrix ions such as phosphates. KEY POINTS: • REE biosorption with G. sulphuraria increases significantly when raising pH to 5 • Phosphate for biosorbent growth has to be supplied separately from biosorption • Biosorption studies have to assess potential matrix effects on REE behavior.

Boosting plant resilience: The promise of rare earth nanomaterials in growth, physiology, and stress mitigation.

Rare earth elements (REE) have been extensively used in a variety of applications such as cell phones, electric vehicles, and lasers. REEs are also used as nanomaterials (NMs), which have distinctive features that make them suitable candidates for biomedical applications. In this review, we have highlighted the role of rare earth element nanomaterials (REE-NMs) in the growth of plants and physiology, including seed sprouting rate, shoot biomass, root biomass, and photosynthetic parameters. In addition, we discuss the role of REE-NMs in the biochemical and molecular responses of plants. Crucially, REE-NMs influence the primary metabolites of plants, namely sugars, amino acids, lipids, vitamins, enzymes, polyols, sorbitol, and mannitol, and secondary metabolites, like terpenoids, alkaloids, phenolics, and sulfur-containing compounds. Despite their protective effects, elevated concentrations of NMs are reported to induce toxicity and affect plant growth when compared with lower concentrations, and they not only induce toxicity in plants but also affect soil microbes, aquatic organisms, and humans via the food chain. Overall, we are still at an early stage of understanding the role of REE in plant physiology and growth, and it is essential to examine the interaction of nanoparticles with plant metabolites and their impact on the expression of plant genes and signaling networks.

Prospecting for rare earth element (hyper)accumulators in the Paris Herbarium using X-ray fluorescence spectroscopy reveals new distributional and taxon discoveries.

BACKGROUND: Rare earth elements (REEs) are increasingly crucial for modern technologies. Plants could be used as a biogeochemical pathfinder and a tool to extract REEs from deposits. However, a paucity of information on suitable plants for these tasks exists. METHODS: We aimed to discover new REE-(hyper)accumulating plant species by performing an X-ray fluorescence (XRF) survey at the Herbarium of the Muséum national d'Histoire naturelle (MNHN, Paris, France). We selected specific families based on the likelihood of containing REE-hyperaccumulating species, using known taxa that accumulate REEs. A total of 4425 specimens, taken in the two main evolutionary lineages of extant vascular plants, were analysed, including the two fern families Blechnaceae (n = 561) and Gleicheniaceae (n = 1310), and the two flowering plant families Phytolaccaceae (n = 1137) and Juglandaceae (n = 1417). KEY RESULTS: Yttrium (Y) was used as a proxy for REEs for methodological reasons, and a total of 268 specimens belonging to the genera Blechnopsis (n = 149), Dicranopteris (n = 75), Gleichenella (n = 32), Phytolacca (n = 6), Carya (n = 4), Juglans (n = 1) and Sticherus (n = 1) were identified with Y concentrations ranging from the limit of detection (LOD) >49 µg g-1 up to 1424 µg g-1. Subsequently, analysis of fragments of selected specimens by inductively coupled plasma atomic emission spectroscopy (ICP-AES) revealed that this translated to up to 6423 µg total REEs g-1 in Dicranopteris linearis and up to 4278 µg total REEs g-1 in Blechnopsis orientalis which are among the highest values ever recorded for REE hyperaccumulation in plants. It also proved the validity of Y as an indicator for REEs in XRF analysis of herbarium specimens. The presence of manganese (Mn) and zinc (Zn) was also studied by XRF in the selected specimens. Mn was detected in 1440 specimens ranging from the detection limit at 116 µg g-1 up to 3807 µg g-1 whilst Zn was detected in 345 specimens ranging from the detection limit at 77 µg g-1 up to 938 µg g-1. CONCLUSIONS AND IMPLICATIONS: This study led to the discovery of REE accumulation in a range of plant species, substantially higher concentrations in species known to be REE hyperaccumulators, and records of REE hyperaccumulators outside of the well-studied populations in China.

Role of indigenous microbial communities in the mobilization of potentially toxic elements and rare-earth elements from alkaline mine waste.

This study aims to evaluate the role of indigenous microorganisms in the mobilization of potentially toxic elements (PTE) and rare-earth elements (REE), the influence of the bioavailability of carbon sources that might boost microbial leaching, and the generation of neutral/alkaline mine drainage from alkaline tailings. These tailings, with significant concentrations of total organic carbon (TOC), were mainly colonized by bacteria belonging to the genera Sphingomonas, Novosphingobium and Solirubrobacter, and fungi of the genera Alternaria, Sarocladium and Aspergillus. Functionality analysis suggests the capability of these microorganisms to leach PTE and REE. Bio-/leaching tests confirmed the generation of neutral mine drainage, the influence of organic substrate, and the leaching of higher concentrations of PTE and REE due to the production of organic acids and siderophores by indigenous microorganisms. In addition, this study offers some insights into a sustainable alternative for reprocessing PMC alkaline tailings to recover REE.

The stimulatory effect and mechanism of low-dose lanthanum on soybean leaf cells.

Light rare earth elements (LREEs) have been long used in agriculture (i.e., mainly via aerially applied LREE fertilizers) based on the fact that low-dose LREEs promote plant growth. Meanwhile, the toxic effects of low-dose LREEs on organisms have also been found. However, the cellular and molecular mechanism of low-dose LREEs acting on organisms remain unclear. Plants are at the beginning of food chains, so it is critical to uncover the cellular and molecular mechanism of low-dose LREEs on plants. Here, lanthanum (La) and soybean were the representatives of LREEs and plants, respectively. The effects of low-dose La on soybean leaves were investigated, and the stimulatory effect and mechanism of low-dose LREEs on leaf cells were revealed. Specifically, clathrin-mediated endocytosis (CME) activated by low-dose La is an influx channel for La in soybean leaf cells. The intracellular La and La-activated CME jointly disturbed multiple forms of intracellular homeostasis, including metallic element homeostasis, redox homeostasis, gene expression homeostasis. The disturbed homeostasis either stimulated cell growth or caused damage to the plasma membrane of soybean leaf cells. These results provide new insights for clarifying the cellular and molecular mechanisms of low-dose LREEs as a class of stimulators instead of nutrients to stimulate plants.