High Zn Research Articles

Zinc and silicon fertilizers in conventional and nano‐forms: Mitigating salinity effects in maize (Zea mays L.)

AbstractBackgroundSalinity stress, an escalating concern in the realm of agriculture, significantly hampers crop productivity worldwide. In recent years, nano‐fertilizers have been identified as an innovative and promising avenue for improving nutrient use efficiency and mitigating salt stress in plants.AimsThis study delves into the comparative efficacy of nano‐fertilizers (Zn and Si) and their conventional sources in bolstering maize's resilience against salt stress.MethodsThe hydroponic experiment was conducted to test maize plants under salt stress along with Zn and Si nanoparticles (NPs) application. The analysis extends to their impacts on ionic homeostasis, specifically focusing on potassium and sodium concentrations, K/Na ratio, stomatal conductance, chlorophyll content, and the osmotic potential (OP) within the shoots and roots of maize.ResultsNanoparticles relatively helped plants better under stress, compared to their respective bulk mode of applications. Nano‐Zn treatment considerably boosts the K+ concentration and enhanced K/Na ratio, as a key physiological trait in salt‐resistant species, while nano‐Si demonstrates a prominent role in modulating OP and limiting Na+ accumulation along with higher Zn and Si accumulation in plants. The salt tolerance index confirmed the contribution of these ionic and osmotic adjustments in helping maize plant against salt stress.ConclusionsOur findings confirm that the application of nutrients as nano‐fertilizers, particularly nano‐Zn, enhanced K/Na ratio and improved nutrient availability and uptake of the plant. Si nanoparticles are also attributed to better osmotic adjustment and facilitating water movement, thus highlighting the potential of nano‐fertilizers in improving overall agricultural productivity and related environmental issues.

Identification and quantification of trace metal(loid)s in water-extractable road dust nanoparticles using SP-ICP-MS

Resuspension of road dust is a major source of airborne particulate matter (PM) in urban environments. Inhalation of ultrafine particles (UFP; < 0.1 μm) represents a health concern due to their ability to reach the alveoli and be translocated into the blood stream. It is therefore important to characterize chemical properties of UFPs associated with vehicle emissions. We investigated the capability of Single-Particle ICP-MS (SP-ICP-MS) to quantify key metal(loid)s in nanoparticles (NPs; < 0.1 μm) isolated from road dust collected in Toronto, Canada. Water extraction was performed to separate the <1-μm fraction from two different road dust samples (local road vs. arterial road) and a multi-element SP-ICP-MS analysis was then conducted on the samples' supernatants. Based on the particle number concentrations obtained for both supernatants, the metal(loid)-containing NPs could be grouped in the following categories: high (Cu and Zn, > 1.3 × 1011 particles/L), medium (V, Cr, Ba, Pb, Sb, Ce, La), low (As, Co, Ni, < 4.6 × 109 particles/L). The limit of detection for particle number concentration was below 5.5 × 106 particles/L for most elements, except for Cu, Co, Ni, Cr, and V (between 0.9 and 7.7 × 107 particles/L). The results demonstrate that road dust contains a wide range of readily mobilizable metal(loid)-bearing NPs and that NP numbers may vary as a function of road type. These findings have important implications for human health risk assessments in urban areas. Further research is needed, however, to comprehensively assess the NP content of road dust as influenced by various factors, including traffic volume and speed, fleet composition, and street sweeping frequency. The described method can quickly characterize multiple isotopes per sample in complex matrices, and offers the advantage of rapid sample scanning for the identification of NPs containing potentially toxic transition metal(loid)s at a low detection limit.

Towards a self-healing aluminum metal matrix composite: Design, fabrication, and demonstration

This paper presents a novel approach to designing and synthesizing a self-healing aluminum-based metal matrix composite (MMC) at the macro-scale. The composite comprises an Al 5083 matrix embedded with low melting point particles (LMPPs) that act as healing agents. A two-step electroless micro-encapsulation process is developed to create LMMPs with a diffusion and thermal barrier designed to protect the Zn-8Al core with a Co-P shell. The MMC is fabricated using spark plasma sintering. Following controlled total fracture under tension, external compressive force is applied during heat treatment to heal the fracture effectively. The evolution of phases and interfaces is characterized using electron microscopy, and transient liquid phase bonding (TLPB) is identified as the fracture-healing mechanism, facilitated in areas with sufficiently high Zn concentration to fill the crack. The design can be expanded to incorporate other matrix and LMMP materials, mechanical crack volume reduction by integrating shape memory alloy (SMA) reinforcement during MMC synthesis, and processing of the self-healing MMC using Directed Energy Deposition additive manufacturing.

Enhanced Methanol Synthesis from CO2 Hydrogenation Achieved by Tuning the Cu-ZnO Interaction in ZnO/Cu2O Nanocube Catalysts Supported on ZrO2 and SiO2.

The nature of the Cu-Zn interaction and especially the role of Zn in Cu/ZnO catalysts used for methanol synthesis from CO2 hydrogenation are still debated. Migration of Zn onto the Cu surface during reaction results in a Cu-ZnO interface, which is crucial for the catalytic activity. However, whether a Cu-Zn alloy or a Cu-ZnO structure is formed and the transformation of this interface under working conditions demand further investigation. Here, ZnO/Cu2O core-shell cubic nanoparticles with various ZnO shell thicknesses, supported on SiO2 or ZrO2 were prepared to create an intimate contact between Cu and ZnO. The evolution of the catalyst's structure and composition during and after the CO2 hydrogenation reaction were investigated by means of operando spectroscopy, diffraction, and ex situ microscopy methods. The Zn loading has a direct effect on the oxidation state of Zn, which, in turn, affects the catalytic performance. High Zn loadings, resulting in a stable ZnO catalyst shell, lead to increased methanol production when compared to Zn-free particles. Low Zn loadings, in contrast, leading to the presence of metallic Zn species during reaction, showed no significant improvement over the bare Cu particles. Therefore, our work highlights that there is a minimum content of Zn (or optimum ZnO shell thickness) needed to activate the Cu catalyst. Furthermore, in order to minimize catalyst deactivation, the Zn species must be present as ZnOx and not metallic Zn or Cu-Zn alloy, which is undesirably formed during the reaction when the precatalyst ZnO overlayer is too thin.

Application of machine learning and statistical approaches for optimization of heavy metals (Cd2+, Pb2+, Cu2+, and Zn2+) adsorption onto carbonized char prepared from PET plastic bottle waste

ABSTRACT This study focuses on the probable use of carbonized char prepared from PET plastic bottles for heavy metals (HMs) adsorption (Cd2+, Pb2+, Cu2+, and Zn2+). The prepared adsorbent is characterized by field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy (FTIR). Batch adsorption experiments were conducted with the influencing of different operational conditions: contact time (1–180 min), adsorbate concentration (25–300 mg/L), adsorbent dose (0.5–6 g/L), pH (3–7), and temperature (25–60 ºC). High coefficient value [Cd2+ (R2 = 0.99), Pb2+ (R2 = 0.97), Cu2+ (R2 = 0.94), and Zn2+ (R2 = 0.98)] of process optimization model suggest that this model was significant, where pH and adsorbent dose expressively stimulus removal efficiency including 86.68, 73.66, 67.10, and 57.04% for Cd2+, Pb2+, Cu2+, and Zn2+ at pH (7), respectively. Furthermore, ANN and BB-RSM revealed a good association between the tested and projected values. The maximum monolayer adsorption capacity of Cd2+, Pb2+, Cu2+, and Zn2+ was 263.157, 78.740, 196.078, and 84.745 mg/g, respectively. Pseudo-second-order was the well-suited kinetics, where Langmuir and Freundlich isotherm could explain better for equilibrium adsorption data. Thermodynamic study shows HMs adsorption is favorable, exothermic, and spontaneous.

Towards a comprehensive understanding of zinc tolerance in Limonium brasiliense as a useful tool for environmental remediation and monitoring.

Heavy metal pollution is a serious environmental problem worldwide, creating the necessity to find eco-friendly strategies for monitoring and remediating environments. This study aimed to evaluate morphological, physiological, and biochemical responses as indicative of Zn tolerance in Limonium brasiliense and to determine the ability of this halophyte to accumulate different concentrations of Zn (0, 100, and 200 μM) in hydroponic conditions. The leaf shape at high Zn concentration showed enlarged petioles and lanceolate blades, whereas the leaf size was reduced. Water content, chlorophyll fluorescence parameters, and pigment content decreased with Zn addition. Of the antioxidant activities, only APx increased 75% compared to the control by Zn stress. Zn concentration was higher in aerial structures than in roots (BAC>1 and TF>1), suggesting that L. brasiliense could function as an accumulator of Zn. Its great ability to resist metal stress and its strong capacity to protect itself against high Zn concentration postulate it as a good phytoremediation of environments enriched with Zn. The study emphasizes using leaf morphology as an early biomonitoring tool for detecting Zn pollution, providing more evidence of their potential use as a biomarker for evaluating and assessing ecosystem health in biomonitoring programs.

Unravelling the impact of soil types on zinc, iron, and selenium concentrations in grains and straw of wheat/Amblyopyrum muticum and wheat/Triticum urartu doubled haploid lines

The concentration of mineral nutrients in plants is associated with bioavailabilities of soil mineral nutrients, which are regulated by various soil physio-chemical properties. A pot experiment was conducted to investigate the effects of soil type on grain and straw zinc (Zn), iron (Fe) and selenium (Se) concentrations of wheat/Amblyopyrum muticum and wheat/Triticum urartu doubled haploid lines. A set of 42 treatments in a factorial combination with 21 genotypes and two soil types collected from Ngabu and Chitedze Research Stations in Malawi was laid in a randomised complete block design (RCBD) in three replicates. Pre-experiment soil Zn and Fe were extracted using DTPA extraction method followed by analysis with inductively coupled plasma-mass spectrometry (ICP-MS). Aqua-regia hotplate acid digestion was used to extract soil Se and analysis was done using ICPM-MS. Grain and straw samples were digested using nitric acid digestion (HNO3) and analysed using ICP-MS. Soil analysis results showed that the two soils had the same textural class (Sandy clay loam), but different mineral concentrations, pH levels and percentage organic matter. Analysis of variance revealed a ~two-fold higher Zn concentration in grains grown in low pH, high Zn soils (Chitedze soils) compared to grains grown in high pH, low Zn soils (Ngabu soils). Variation in grain Zn concentration was associated with the genotypes (p = 0002), soil type (p = &amp;lt;0.0001), and their interaction (p = 0.035). Grain Fe was 1.3-fold higher in low pH than in high pH soils, and it was influenced by genotypes (p = &amp;lt; 0.0001) and soil type (p = &amp;lt;0.0001). Grain Se was highly associated with soil type (p = &amp;lt;0.0001), and it was 30-fold higher in high pH than in low pH soils. Straw Zn was generally higher in plants grown in Chitedze soils than Ngabu soils, whilst straw Se was higher in plants grown in Ngabu soils than Chitedze soils. The findings demonstrate the significance of soil physio-chemical properties for mineral accumulation and distribution to plant parts, thus informing future breeding programs on important considerations on crop genetic biofortification with the three mineral elements.

Association between preoperative serum zinc level and prognosis in patients with advanced esophageal cancer in the neoadjuvant treatment era

AbstractBackgroundZinc (Zn), an essential trace element, has an adverse influence on the prognosis of several cancers. However, the association between the preoperative serum Zn level and outcomes in patients with advanced esophageal cancer in the current neoadjuvant treatment era remains unclear.MethodsThis study involved 185 patients with esophageal cancer who underwent R0 surgery after neoadjuvant chemotherapy from August 2017 to February 2021. We retrospectively investigated the relationship between the preoperative serum Zn level and the patients' outcomes.ResultsThe patients were divided into a low Zn group (&lt;64 μg/dL) and a high Zn group (≤64 μg/dL) according to the mean preoperative serum Zn level. Low Zn had significantly worse overall survival (OS) (2‐year OS rate: 76.2% vs. 83.3% in low vs. high Zn; p = 0.044). A low Zn in pathological non‐responders (Grade ≤ 1a) was significantly associated with a shorter 2‐year recurrence‐free survival (RFS) rate (39.6% vs. 64.1% in low vs. high Zn; p = 0.032). The multivariate analysis identified low BMI and Zn level among preoperative nutritional status indices as an independent risk factor for worse RFS in non‐responders. Compared with responders, pathological non‐responders comprised significantly more males and a performance status of ≥1, and there was no difference in Zn level according to pathological response.ConclusionA preoperative low Zn level had a negative impact on early recurrence in esophageal cancer patients who underwent neoadjuvant chemotherapy. This suggests the need to administer Zn supplementation to patients with esophageal cancer who have preoperative Zn deficiency.

An in-situ SbF3/Zn3Sb2 protective layer for dendrite-free zinc metal anode

Zinc-ion batteries are considered as one of the most promising electrochemical energy storage devices in the field of electrochemical energy storage due to their low cost and high safety. However, the development of zinc ion batteries using metal zinc anodes is limited by the existence of hydrogen evolution, dendrite growth, serious side reactions, low coulomb efficiency and poor cycling performance. In this work, an ultrathin ZnF2/Zn3Sb2 hybrid interfacial layer is constructed by spraying commercial Zn metal with SbF3 as the precursor. Due to the high Zn ionic conductivity of ZnF2 and Zn3Sb2, this interfacial layer can effectively enhance the uniform deposition of Zn ions and improve the stability of the solid electrolyte/anode interface. A low current density of 1 mA cm−2 and a high current density of 1 mA cm−2 can be obtained by assembling symmetric batteries with Zn@SbF3 as the anode for more than 500 h. In addition, the CuSCoS//Zn@SbF3 full battery maintains a CE rate of up to 99.2% after 1000 cycles at a current density of 2 A g−1. These results indicate that the modified Zn anode holds a large potential for Zinc-ion batteries applications.

Zinc toxicity and tolerance-related responses in Inga marginata and Allophylus edulis seedlings

Although zinc (Zn) is a micronutrient, excessive amounts in the soil can have toxic effects on plants. Fertilizers, limestone materials, pesticides, and fungicides added with Zn have contributed to increasing the concentration of this element in agricultural soils. Accordingly, it is necessary to find Zn-tolerant plant species to be properly used in degraded soil restoration programs. Thus, the current study aims to investigate the influence of different Zn concentrations on photosynthetic variables, antioxidant activity, and growth of I. marginata and A. edulisseedlings to determine their potential to be used as phytoremediation species. The experiment was installed in a 2×5 factorial scheme, with the first factor being two species (Allophylus edulis and Inga marginata), and the second factor: five concentrations of Zn (2, 75, 150, 225, and 300 μM), with three replications per treatment. Each sampling unit consisted of a pot with five plants. Photosynthetic, morphological variables of the shoot and root systems, chlorophyll a fluorescence, photosynthetic pigments, antioxidant enzyme activity, lipid peroxidation, hydrogen peroxide concentration, and Zn accumulated in the roots and shoot were evaluated. Zn stress has activated an efficient antioxidant system, which reduced oxidative damage in the leaves of both species; consequently, it did not decrease shoot biomass production in Inga marginata and Allophylus edulis seedlings. High Zn accumulation in plant tissues and lack of negative effects on Inga marginata and Allophylus edulis shoot have suggested that these plant species are tolerant to Zn and may be indicated for Zn-polluted soil phytoremediation purposes.

Differences in mineral and osmotic balances enhance zinc translocation in an aquaporin overexpressing poplar

Zinc (Zn) is an essential micronutrient for plants, but it is toxic beyond a certain threshold. Populus alba (L.) ‘Villafranca’ clone is known for its good tolerance to high Zn concentration compared to other poplar species. A line of this species overexpressing the tonoplast intrinsic aquaporin AQUA1 gene has showed an improved tolerance to Zn excess in comparison to the wild-type (wt) line. The aims of this work were to: 1) verify if AQUA1 plants can uptake Zn more efficiently after a longer period of exposure; 2) evaluate if a higher Zn uptake in transgenic lines can have negative effects; 3) assess Zn competing elements (iron and manganese), soluble sugars, osmolytes, and potassium to investigate differences in water and osmotic homeostasis between lines. Under Zn excess, AQUA1 plants showed a twofold Zn translocation factor and a higher xylem sap Zn concentration than the wt plants. Transgenic plants preferentially allocated Zn in aerial biomass and this different behaviour matched with modified manganese and iron balances suggesting that the increased Zn uptake might be related to a decrease in iron transport in the transgenic line. Moreover, a higher instantaneous water use efficiency in control conditions and an increase in bark soluble sugars under Zn excess could allow a higher resistance of AQUA1 plants to the water and osmotic perturbations caused by Zn. Indeed, the Zn excess increased the xylem osmolyte content only in wt plants. Further investigations are required to understand the role of AQUA1 in osmotic regulation.

Association of Zinc Intake, Tobacco Smoke Exposure, With Metabolic Syndrome: Evidence from NHANES 2007-2018.

The objective was to explore the effect modification of zinc (Zn) intake levels on the relationship of tobacco smoke exposure and risk of metabolic syndrome (MetS) in children and adolescents. We used data from 2007-2018 National Health and Nutrition Examination Survey (N = 3701). MetS was considered as main endpoint. Weighted multivariable logistic regression models showed that high cotinine level (≥ 0.05ng/mL) was associated with increased odds of MetS [odds ratio = 1.54, 95% confidence interval: 1.01, 2.36], and the association between Zn intake levels and MetS did not demonstrate statistical significance. Importantly, the multiplicative interaction term between low Zn intake (≤ 4.89mg/1000kcal) and high cotinine level was related to higher odds of MetS (p-value for interaction 0.018). For the group with low Zn intake, high cotinine level was associated with increased odds of MetS. However, there was no significant relationship between cotinine levels and MetS risk in the group with high Zn intake. The effect modification by Zn intake on the relationship of tobacco smoke exposure and risk of MetS is significant in individuals who had a sedentary time of ≥ 6h, identified as non-Hispanic White, or resided in households with smokers. In short, low Zn intake may potentiate the association of tobacco smoke exposure and MetS risk in children and adolescents.

The interaction effects of zinc and polygenic risk score with benzo[a]pyrene exposure on lung cancer risk: A prospective case-cohort study among Chinese populations

The relationship of exposure to benzo[a]pyrene (BaP) with lung cancer risk has been firmly established, but whether this association could be modified by other environmental or genetic factors remains to be explored. To investigate whether and how zinc (Zn) and genetic predisposition modify the association between BaP and lung cancer, we performed a case-cohort study with a 5.4-year median follow-up duration, comprising a representative subcohort of 1399 participants and 359 incident lung cancer cases. The baseline concentrations of benzo[a]pyrene diol epoxide-albumin adduct (BPDE-Alb) and Zn were quantified. We also genotyped the participants and computed the polygenic risk score (PRS) for lung cancer. Our findings indicated that elevated BPDE-Alb and PRS were linked to increased lung cancer risk, with the HR (95%CI) of 1.54 (1.36, 1.74) per SD increment in ln-transformed BPDE-Alb and 1.27 (1.14, 1.41) per SD increment in PRS, but high plasma Zn level was linked to a lower lung cancer risk [HR (95%CI)=0.77 (0.66, 0.91) per SD increment in ln-transformed Zn]. There was evidence of effect modification by Zn on BaP-lung cancer association (P for multiplicative interaction = 0.008). As Zn concentrations increased from the lowest to the highest tertile, the lung cancer risk per SD increment in ln-transformed BPDE-Alb decreased from 2.07 (1.48, 2.89) to 1.33 (0.90, 1.95). Additionally, we observed a significant synergistic interaction of BPDE-Alb and PRS [RERI (95%CI) = 0.85 (0.03, 1.67)], with 42% of the incident lung cancer cases among individuals with high BPDE-Alb and high PRS attributable to their additive effect [AP (95%CI) = 0.42 (0.14, 0.69)]. This study provided the first prospective epidemiological evidence that Zn has protective effect against BaP-induced lung tumorigenesis, whereas high genetic risk can enhance the harmful effect of BaP. These findings may provide novel insight into the environment-environment and environment-gene interaction underlying lung cancer development, which may help to develop prevention and intervention strategies to manage BaP-induced lung cancer.

Grain iron and zinc content is independent of anthocyanin accumulation in pigmented rice genotypes of Northeast region of India

The traditional rice genotypes of Assam are considered to have biological value due to the presence of several bioactive compounds like flavonoids, polyphenols, and anthocyanins, which have antioxidant, anti-cancer, anti-diabetic, and anti-aging properties. The pigmented genotypes are considered to have high iron (Fe) content. However, the effect of Fe and Zinc (Zn) accumulation on anthocyanin content is yet to be studied in pigmented rice of Assam. We studied the Fe, Zn, and anthocyanin content in grains of 204 traditional rice of Assam, which are traditionally preferred for their nutraceutical properties. We performed phenotypic and biochemical compositional analyses of 204 genotypes to identify those having high Fe, Zn, and anthocyanin. We also carried out the differential expression of a few selected Fe and Zn transporter genes along with the expression of anthocyanin biosynthesis genes. Interestingly, all pigmented rice genotypes contained a higher amount of phenolic compound than the non-pigmented form of rice. We found the highest (32.73 g) seed yield per plant for genotype Jengoni followed by Kajoli chokuwa and Khau Pakhi 1. We also listed 30 genotypes having high levels of Fe and Zn content. The genotype Jengoni accumulated the highest (186.9 μg g−1) Fe, while the highest Zn (119.9 μg g−1) content was measured in genotype Bora (Nagaon), The levels of Ferritin 2 gene expression were found to be significantly higher in Bora (Nagaon) (> 2-fold). For Zn accumulation, the genotype DRR Dhan-45, which was released as a high Zn content variety, showed significant up-regulation of the ZIP4 gene at booting (> 7-fold), post-anthesis (7.8-fold) and grain filling (> 5-fold) stages followed by Bora (Nagaon) (> 3-fold) at post-anthesis. Anthocyanidin synthase gene, Flavanone 3-dioxygenase 1-like (FDO1), and Chalcone-flavanone isomerase-like genes were up-regulated in highly pigmented genotype Bora (Nagaon) followed by Jengoni. Based on our data there was no significant correlation between iron and zinc content on the accumulation of anthocyanin. This challenges the present perception of the higher nutritive value in terms of the micronutrient content of the colored rice of Assam. This is the first report on the detailed characterization of traditional rice genotypes inclusive of phenotypic, biochemical, nutritional, and molecular attributes, which would be useful for designing the breeding program to improve Fe, Zn, or anthocyanin content in rice.

Concentrated weak hydrated electrolytes towards ultra-stable high-voltage zinc ion batteries

Hydrogen evolution reactions (HER), dendritic growth, narrow electrochemical windows, and dissolution of cathode materials severely limit the development of aqueous zinc metal batteries. Herein, the unique bisphenylsulfonamide anion (BBI−) is employed to reduce the ion-dipole interaction between Zn2+ and H2O by complexing Zn2+ to suppress H2O decomposition. Meanwhile, the solvent sheath structure of Zn2+-BBI− coordination can provide a large nucleation overpotential, thus producing uniform deposition to suppress dendrites. The hydrogen bonds between BBI− and H2O effectively limit the diffusion of H2O, thereby reducing the dissolution of the water-soluble cathode material into the electrolyte. Both experimental and simulated results are carried out and quantitively confirm the ion paring, hydrogen bond and solvent effect evolution of Zn(BBI)2 electrolytes. This concentrated electrolyte enables Zn||Zn symmetric cells to achieve a superlong cycling life of over 7100 h even at a current of 2 mA cm−2 and capacity of 2 mAh cm−2, while the high mass loading Zn||NaV3O8·1·5H2O and Zn||Zn3(Fe(CN)6)2 cells also exhibit excellent cycling performance at a cut-off voltage of 2.1 V. The findings of this work point to a very promising strategy for the development of long-life aqueous batteries.

Mn–Fe-rich genthelvite from pegmatites associated with the Madeira Sn–Nb–Ta deposit, Pitinga, Brazil: new constraints on the magmatic-hydrothermal transition in the albite-enriched granite system

AbstractGenthelvite from pegmatite veins hosted by the albite-enriched granite (ca.1.8 Ga) corresponding to the Sn–Nb–Ta (F, REE, Li, Zr, U, Th) Madeira deposit, Amazonas, Brazil was studied. Genthelvite, the exclusive Be-bearing mineral within the deposit, occurs as massive crystals of up to 4.7 cm in size. Compositions are homogeneous within individual crystals, although there is moderate variation in the overall composition reflecting relatively limited substitutions within the helvine–genthelvite–danalite solid-solution series, with relatively high Zn contents (36.96 to 49.45 wt.% ZnO), lower Mn contents (0.61 to 3.03 wt.% MnO), and variable Fe contents (2.10 to 10.94 wt.% FeO), completing an existing compositional gap in this system. Genthelvite formed in an alkaline and subaluminous environment, under stable conditions within the late-evolved fluids, at relatively high temperature (&gt;400°C), in a reducing environment. The extremely high concentration of fluorine in the magma and the crystallisation of magmatic galena resulted in an effective reduction of H2S fugacity. This resulted in the stabilisation of genthelvite during the transition from the late magmatic to early hydrothermal stages of the albite-enriched granite evolution. The variability in Fe content within genthelvite is associated primarily with localised variations in the mineral assemblage (e.g. the presence of riebeckite and polylithionite). Genthelvite was altered by low-temperature aqueous fluids rich in F which resulted in the incorporation of Fe, Mn, Mg, Pb, Ba, Na, K, U and REE into the Zn2+ structural site and the allocation of excess Si, Al, Ti and P in the IVSi and IVBe structural sites. The substantial content of U and REE substituting for Zn, together with Si substituting for Be, is charge balanced by the presence of vacancies at the A site.

Vanadium rich Fe-Ti oxide and Cu-sulphide mineralization in Paleoproterozoic Mangikhuta volcanics, Central Indian Craton: metallogenic and petrogenetic implications

This study reports for the first time, Fe-Ti-V oxide and Cu-sulphide mineralization in Paleoproterozoic Mangikhuta basalt Formation, central Indian craton. Electron microprobe and laser ablation analyses of Fe-oxides reveal high FeO (45–69 wt %), TiO2 (19–53 wt %), V (1860 - 4990 ppm), Zr (394–3130 ppm), Nb (55–285 ppm) and Zn (324–668 ppm). Interelemental relationships of Fe-oxides reveal their magmatic origin. High concentration of lithophile elements in Fe-oxides besides V and Ni trends in incompatible element plots indicate their origin from mafic melt. High Cu content (269 and 314 ppm) in the host basalt samples along with chalcopyrite mineralization observed during ore petrography indicates sulphide saturation of Mangikhuta magma. The chondrite normalized rare earth element (REE) plots of the host rock samples are overall similar to the earlier reported Mangikhuta REE patterns, which indicates genetic relation of Fe-oxides and Cu-sulphides with Mangikhuta volcanism. Fe-oxide and Cu-sulphide mineralization in Mangikhuta basalt is related to hydrous and oxygen rich arc related mafic melt intrusion into the Khairagarh back arc basin. Sulphide saturation in Mangikhuta basalt was initiated due to precipitation of Fe-oxides from the evolved melt whereas addition of fresh batch of hydrous and oxygen rich melt derived from the arc-related mantle source increased oxygen fugacity of residual melt that resulted in alternate phases of high oxygen and Sulphur fugacity and precipitation of Fe-oxide and Cu-sulphides from the melt.

Bio‐Inspired Trace Hydroxyl‐Rich Electrolyte Additives for High‐Rate and Stable Zn‐Ion Batteries at Low Temperatures

AbstractHigh‐rate and stable Zn‐ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost‐resistant plants, we report trace hydroxyl‐rich electrolyte additives that implement a dual remodeling effect for high‐performance low‐temperature Zn‐ion batteries. The additive with high Zn absorbability not only remodels Zn2+ primary solvent shell by alternating H2O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn2+ de‐solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α‐D‐glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of −55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm−2 under −25 °C, with a high cumulative capacity of 5000 mAh cm−2. A full battery that stably operates for 10000 cycles at −50 °C is also demonstrated.

Green Deep Eutectic Solvents (DESs) for Sustainable Metal Recovery from Thermally Treated PCBs: A Greener Alternative to Conventional Methods.

Waste PCBs the core of e-waste is rich in copper, tin, zinc, iron, and nickel. Leaching base metals from PCB used to be done in toxic, corrosive acidic/alkali mediums. In this work, an environmentally friendly method for leaching metals from thermally treated PCBs (TPCBs) of mobile phones was proposed using choline chloride based deep eutectic solvents (DES). DES selectivity and solubility of metals from metal oxides were the main screening criteria. FA-ChCl had the maximum solubility of Cu, Fe, and Ni, while Urea-ChCl had high Zn selectivity and solubility. Oxalic acid has high selectivity for Sn. FA-ChCl extracted Cu and Fe best at 16 h, 100 °C, and 1/30 g/mL. Urea-ChCl extracted Zn (90.4±2.9 %) from TPCBs at 100 °C, 21 h, 1/20 g/mL, and 400 rpm. Oxalic acid (1 M) removed 92.3±2.1 % Sn from TPCBs in 1 h at 80 °C and 1/20 g/mL. The shrinking core model-based kinetic investigation of FA-ChCl for Cu extraction showed a diffusion-controlled process. The proposed method is greener than mineral acids utilized for metal extraction.

Bio-Inspired Trace Hydroxyl-Rich Electrolyte Additives for High-Rate and Stable Zn-Ion Batteries at Low Temperatures.

High-rate and stable Zn-ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost-resistant plants, we report trace hydroxyl-rich electrolyte additives that implement a dual remodeling effect for high-performance low-temperature Zn-ion batteries. The additive with high Zn absorbability not only remodels Zn2+ primary solvent shell by alternating H2 O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn2+ de-solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α-D-glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of -55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm-2 under -25 °C, with a high cumulative capacity of 5000 mAh cm-2 . A full battery that stably operates for 10000 cycles at -50 °C is also demonstrated.