Mn Deposits Research Articles

Alleviating Mn<sup>3+</sup> Dissolution in ZnMn<sub>2</sub>O<sub>4</sub> Cathode for the Extended Cyclability via Particle Size Increase

ZnMn<sub>2</sub>O<sub>4</sub> (ZMO) cathode possesses a high theoretical capacity of 224 mAh g<sup>-1</sup> and high operating voltage (1.9 V vs. Zn<sup>2+</sup>/Zn) for aqueous Zn–ion batteries. However, the disproportionation reaction of Mn<sup>3+</sup> leads to Mn dissolution in the ZMO cathode, deteriorating lifespan. In this study, we attempted to reduce Mn dissolution by enlarging the particle size, thereby diminishing the electrode/electrolyte interfacial area. The ZMO particle grew with increasing the calcination temperatures of 400℃, 500℃, and 600℃. Higher calcination temperature created oxygen vacancies within the lattice, thereby increasing the contents of Mn<sup>3+</sup> for charge neutrality. The rate capability decreased with the increase in particle size, which is presumed to be due to the lengthening of the diffusion path of Zn ions. After a long–cycle experiment of Zn–ion batteries assembled with ZMO cathode and Zn anode, the Mn deposit amount on the anode was measured to reveal the Mn dissolution from the ZMO cathode based on the disproportionation reaction. The ZMO particle synthesized at 600℃ with the largest particle size demonstrated the highest cyclability of 48.1% at 1.0 A g<sup>-1</sup> based on the lowest Mn deposit on the anode. Hence, the ZMO electrode with a larger particle size exhibited improved cycle stability by alleviating of the disproportionation reaction from the reduced electrode/electrolyte interfacial area.

Complexed amino acid minerals vs. bis-glycinate chelated minerals: Impact on the performance of old laying hens

The present study was to evaluate the effect of trace minerals (Zn, Mn, and Cu) from complexed amino acid minerals (ZMCAA) and bis-glycinate chelated minerals (ZMCGly) in laying hen diets on performance, internal and external egg quality, yolk mineral deposition, intestinal morphometry, and bone characteristics. From 78 to 98 weeks of age, 400 White LSL-Lite strain laying hens were distributed in a randomized design with 4 treatments with 10 replicates per treatment. Treatments were distributed in a 2 × 2 factorial arrangement using either Zn, Mn, and Cu of ZMCAA or ZMCGly source at 2 levels: low (20, 20, and 3.5 mg/kg of Zn, Mn, and Cu, respectively) or high (40, 40, and 7 mg/kg of Zn, Mn, and Cu, respectively). The analysis of variance was performed, and in cases where differences were observed, the means were compared using Tukey's test (P < 0.05). The source and level of trace mineral supplementation had a significant impact on the performance of laying hens. Hens fed ZMCAA had higher egg production (P = 0.01), egg weight (P = 0.02), egg mass (P = 0.01), and lower feed conversion ratio (P = 0.05) compared to those fed ZMCGly. The ZMCAA supplementation showed higher albumen height (P = 0.01), albumen weight (P = 0.01), and eggshell thickness (P < 0.01). The deposition of Zn (P < 0.01), Mn (P < 0.01), and Cu (P < 0.01) in the egg yolk was greater for hens received ZMCAA. Tibia weight (P = 0.04) and bone densitometry (P < 0.01) in the tibia were higher with ZMCAA supplementation. In the small intestine, ZMCAA resulted in longer villi (P = 0.02) and shorter crypt depth (P = 0.01) in the duodenum. Jejunum and ileum measurements were influenced by the level and source of trace minerals (P < 0.05). Laying hens fed ZMCAA exhibited superior performance, egg quality, deposition of trace minerals in the egg yolk, and bone density compared to hens fed ZMCGly. In this study, older laying hens supplemented with ZMCAA at lower levels demonstrated adequate levels of supplementation.

Plasma-assisted deposition of Mn and Fe phases on CeO2 biomorphic fibers for soot combustion and CO oxidation

In the present work, the gliding arc (glidarc) plasma technique is for the first time explored as a novel precipitation-deposition method to generate fibrous catalysts. Precisely, Mn and Fe oxides were plasma-precipitated on a fibrous ceria support and evaluated in two reactions of environmental interest, (1) soot combustion and (2) CO oxidation. Pure CeO2 fibers (Fib Ce) were obtained via a biotemplate route with the idea of starting from a support already active in oxidation reactions, and then further improving its activity by supporting on its surface Fe and Mn oxides. The precipitates were identified by XRD, FTIR and LRS, and their loadings and distributions assessed by ICP and EDX respectively. α-Fe2O3 and Mn3O4 phases were detected. XPS confirmed the presence of Mn and Fe on the surface of Fib Ce and revealed that the deposition of Fe logically gave a superficial Fe/Ce ratio much higher than the bulk one and provoked an increase in Ce3+/Ce4+ and Oads/Ce ratios. On the contrary, Mn-supported samples did not affect considerably the Ce3+/Ce4+ and Oads/Ce ratios and presented a Mn/Ce ratio closer to that of the bulk. The latter suggests that Mn has integrated the ceria structure. For reaction (1), the deposition of Fe by plasma drastically degraded the performance of the bare support, whereas Mn deposition greatly increased the activity of Fib Ce. The same activity order was observed for reaction (2): Mn-Fib Ce > Fib Ce > Fe-Fib Ce.

Optimal dietary supplementation of phytase for red drum (Sciaenops ocellatus) based on growth and mineral utilization

A 9-week feeding trial was conducted with juvenile red drum to evaluate the potential benefits of supplementing dietary phytase on growth performance and utilization of phosphorus (P) and various trace minerals. The negative control diet (0.9% of total P and 0.57% of available P) was formulated to have inadequate available P based on the established P requirement of red drum. The positive control diet contained extra monocalcium phosphate (MCP) to provide 0.73% available phosphorus to meet the red drum's minimum P requirement. Another four phytase-supplemented diets were made via adding Quantum Blue phytase (AB Vista, Plantation, Florida) at either 1000, 2000, 4000, or 8000 phytase units (FTU)/kg to the negative control diet. Each diet was fed to quadruplicate groups of 20 juvenile red drum (initial weight of 4.99 ± 0.09 g) in 110-L aquaria operated as a brackish water (7 ppt) recirculating aquaculture system for 9 weeks. The results showed that compared to red drum fed the negative control diet, fish fed the phytase-supplemented diets had significantly (P < 0.05) increased weight gain, feed efficiency, and protein retention. In addition, significantly increased apparent availability of P was observed in red drum fed the diets containing phytase compared to those fed the negative control diet. Red drum given the phytase-supplemented diets also had significantly enhanced utilization of various minerals, except for whole-body retention of Mn and bone deposition of Fe, compared to fish fed the negative control diet. According to the results based on the orthogonal polynomial contrasts, the optimal dietary phytase dosage was found to be 5520 FTU/kg of dry diet. Consequently, the supplementation of dietary phytase significantly improved growth performance of red drum and partly substituted for dietary MCP in diets containing 40% soybean meal and insufficient available P. In addition, dietary phytase supplementation significantly enhanced the utilization of dietary protein and various minerals by red drum.

Pulp cell response to the application of silver diamine fluoride and potassium iodide on caries-like demineralized dentin.

To investigate the response of pulp cells to the application of silver diamine fluoride (SDF) and potassium iodide (KI) on demineralized dentin. The occlusal surfaces of human dentin discs (0.4mm thick) with similar permeability were subjected to an artificial caries protocol, and then the discs were adapted into artificial pulp chambers. MDPC-23 cells were seeded on the healthy pulp dentin surface, while the demineralized surface was treated with SDF, KI, SDF + KI, or hydrogen peroxide (positive control-PC) (n = 8). The negative control (NC) received ultrapure water. After 24h, cell viability (alamarBlue) and morphology (SEM) were evaluated. The extracts were then applied to new MDPC-23 cells seeded in culture plates to assess their viability and the formation of mineralized nodules (MN; Alizarin Red) after seven days. The data were analyzed using one-way analysis of variance/Tukey or Games-Howell tests (α = 5%). SDF and PC significantly reduced the viability of cells seeded on discs (45.6% and 71.0%, respectively). Only cells treated with SDF or PC detached from the dentin substrate, while the remaining cells showed altered morphology. Cells in contact with extracts showed less reduction in viability, but it was still more toxic compared to NC. Only PC reduced MN deposition. SDF + KI or KI alone did not affect the cell response. SDF applied alone showed a mild to moderate transdentinal cytotoxic effect on pulp cells. However, the combination of SDF + KI reduced the cytotoxic effects. Both materials used alone or in combination did not affect the mineralization ability of pulp cells. Besides improving esthetic results, associating potassium iodide with silver diamine fluoride may reduce the transdentinal cytotoxic effects of this cariostatic agent on pulp cells.

Carbonate-hosted manganese deposits and ocean anoxia

Late Devonian (ca. 360 Ma), Early Carboniferous (ca. 330 Ma), and Early Triassic (ca. 250 Ma) manganese deposits in the South China Block support an emerging view that some Mn carbonates form through direct synsedimentary (authigenic) precipitation. These Mn carbonates accumulated on distal shelves and are interbedded with lime mudstone and heterozoan carbonates that accumulated in coastal upwelling environments. Lithofacies, Ce anomalies combined with vanadium, uranium, and molybdenum enrichments indicate that the Mn carbonates were primarily precipitated under anoxic conditions. We provide a robust dataset to clarify the precipitation pathway of these Mn carbonates and explore the implications of using them as proxies of regional shallow water and deep-ocean anoxia. In the studied deposits, Mn calcite encases dolomite rhombs (<10 μm) or aggregates, indicating heterogenous nucleation, which is supported by similar lattice parameters of both minerals with a small lattice mismatch (<2.1%). The presence of micro-sized euhedral rhombs and subhedral aggregates of rhombs, the non-stoichiometric compositions, and characteristic organic matter Raman spectroscopy peaks near the D and G bands in the dolomite nuclei suggest an organogenic origin. Authigenic organogenic dolomite precipitation is interpreted to have preconditioned the sediment with nucleation sites for the subsequent precipitation of Mn carbonates in the shallow seafloor. This is consistent with δ13C values (−2.61‰) of Mn carbonate bulk samples that are slightly lower than coeval seawater (0.31‰, from host rocks), suggesting incorporation of 12C during microbial respiration of sedimentary organic matter during the precipitation of organogenic dolomite and hydrothermal sourced inorganic carbon. The absence of Mn in shallow facies suggests terrestrial input of Mn was minimal. Geochemical and sedimentologic evidence suggests that coastal upwelling delivered manganous anoxic deep waters to the shelves. Eu/Eu⁎ ratios (<1.5) and decoupling of Fe and Mn imply long-range transport of hydrothermal Mn, during which hydrothermal fingerprints were muted through mixing with ambient seawater. The transport of hydrothermal Mn to shelves indicates that the regional deep oceans at the time must have been anoxic, as Mn2+ would be easily oxidized and become insoluble under oxygen-rich conditions, preventing its long-distance transport. This precipitation pathway and depositional model implies that Mn carbonates are a largely unrecognized proxy for tracking ancient oceanic redox fluctuations, particularly during times of well-oxygenated global oceans. Hence, these Mn deposits record at least transient regional deep-ocean oxygen depletion in the generally well-oxygenated Late Paleozoic and Early Triassic oceans. The recognition that this periodic anoxia was broadly coeval with the anoxia-related Hangenberg, Serpukhovian, and Permian-Triassic biotic crises suggests a potential relationship between Mn carbonate accumulation and extinction events.

Magmatic Native Gold: Composition, Texture, Genesis, and Evolution in the Earth’s Crust

Abstract —Here we report results of microforms’ studies of native gold and its alloys in igneous rocks, modified to varying degrees by secondary processes. We discuss the composition and occurrence of both the deep-seated magmatic gold-bearing alloys and the products of their transformation under conditions of the upper Earth’s crust. Gold-bearing Kamchatka adakites and ankaramites, Ildeus massif mafic-ultramafic intrusions and adakites from the Stanovoy fold system as well as dacites from the Bolivian Andes were formed during melting of either the suprasubduction mantle wedge or the subducted oceanic crust. In depleted peridotites from the Avachinsky Volcano in Kamchatka as well as suprasubduction ophiolites from Polar Urals, Eastern Sayan and the Western Mediterranean Betic–Rifean belt, the gold-bearing mantle was hybridized by subduction-related melts and high-temperature fluids. Volcanic rocks associated with the Lesser Khingan Fe–Mn deposits and Zolotaya Gora Au deposit in Southern Urals as well as Taragai ultramafic rocks in the South Khingan Range display subduction-related geochemical characteristics. Gold-bearing trachytes in the Virginian Appalachians (USA) represent felsic differentiates of mafic intraplate magmas. We propose that one of the principal forms of gold transport into the upper crustal environments is represented by Cu–Ag–Au alloys, which precipitated from mantle-derived silicate melt enriched in chalcophile and siderophile elements. Such Cu–Ag–Au alloy-rich magmatic rocks can either constitute primary sources of precious metals in the mantle-crust system or serve as geochemical precursors to the formation of native gold assemblages in epithermal and mesothermal ore deposits. Presence of magmatic gold particles in subduction-related igneous rocks and mantle restites hybridized by subduction-derived melts and high-temperature fluids suggest the existence of gold-rich horizons in the Earth’s mantle at depths comparable to typical depths of generation of primary convergent zone and some within-plate magmas.

Studying The Impact of Electrolyte, Li Excess, NMC Blending, and Cycling Conditions on The Lifetime and Degradation of LMO/AG Cells Using UHPC Cycling, XRF, and Isothermal Microcalorimetry

The impact of electrolyte, Li excess, NMC blending, and cycling conditions on the performance of Li1+xMn2-xO4 (LMO)/Artificial Graphite (AG) cells was studied using ultra-high precision coulometry (UHPC), X-ray fluorescence (XRF), and isothermal microcalorimetry (IMC). Decreasing the Li excess resulted in severe capacity fade which was greatly improved by blending LMO with NMC622. The known synergy between NMC and LMO is electrolyte-dependant and was more significant at elevated temperatures. We showed with XRF that Mn deposition on the negative electrode occurs primarily during the early cycles and is reduced by increasing the Li excess in LMO or by blending with NMC622. IMC experiments demonstrates a correlation between parasitic heat flow and Mn loading on the negative electrode and gas generation. Finally, LiFSI co-salts were examined to suppress Al corrosion while retaining the beneficial role of LiFSI in improving cell performance.

Interpretation of Geothermal Magnetic Depths, Physicochemical Parameters and Heavy Metals Determination of Lamurde Hot-spring in the North-Eastern Benue Trough, Nigeria

An integrated interpretation of the magnetic data and the analysis of physicochemical parameters and heavy metals from Lamurde hot spring has been done for the first time. The temperature of the hot spring was measured to be at 44 °C while the normal surface temperature is 25 °C. Three prominent magnetic anomalies were found at bottom depths of 11.379 ± 0.253 km, 13.015 ± 2.120 km and 9.161 ± 1.200 km suggesting that the Lamurde hot-spring is heated at deep mantle (13.015 ± 2.120 km) and issued to the surface through either local or regional fault system or both. The physicochemical analysis gave pH (7.93 ± 0.06), total chlorine (125.0 ± 2.89 µg/L), total dissolved solids TDS (202.0 ± 2 ppm), hardness (64 ± 1.73 µg/L), alkalinity (210 ± 4 µg/L) and nitrate (1.3 ± 0.3 µg/L). In comparison with that of WHO standards, the results indicated that all the physicochemical parameters studied except for alkalinity fall within the permissible limits. Heavy metals were identified and analyzed in the sampled water: lead (0.1501 ± 0.0007 mg/L), chromium (0.0729 ± 0.0007 mg/L), nickel (0.1987 ± 0.1476 mg/L), cadmium (0.0115 ± 0.0003 mg/L), copper (0.0442 ± 0.0008 mg/L), arsenic (0.0456 ± 0.0003 mg/L), iron (0.8016 ± 0.0005 mg/L), cobalt (0.0274 ± 0.0004 mg/L), selenium (undetectable), manganese (5.31 ± 0.0361 mg/L) and zinc (0.1629 ± 0.0004 mg/L). The concentrations of heavy metals observed in the area with the exception of Zn, Cu and Se are all above the standards for drinking water. Their concentrations are in the order of Mn &gt; Fe &gt; Ni &gt; Zn &gt; Pb &gt; Cr &gt; As &gt; Cu &gt; Co &gt; Cd &gt; Se. These results suggest that the Lamurde hot spring is a potential zone for Mn, Fe, Ni, Zn and Pb deposit.

Removal of Disperse Yellow-42 Dye by Catalytic Ozonation Using Iron and Manganese-Loaded Zeolites

In this research, the efficiency of the catalytic activity of iron and manganese-loaded (bimetallic) sodium zeolite was investigated for the ozonation-based removal of disperse yellow 42 dye. The impregnation method was used to deposit Fe and Mn on the surface of sodium zeolite. The morphological analysis of sodium zeolite before and after Fe and Mn deposition was conducted by SEM, EDX, and FTIR. It was found that several variables, including the ozone dose, contact time, pH, catalyst dose, and hydroxyl radical scavenger action, greatly influenced the efficiency of dye removal. The chemical oxygen demand (COD) removal by catalytic ozonation using Fe and Mn-loaded sodium zeolite from real dye textile wastewater was also investigated. After 30 min of treatment with catalytic ozonation at pH 6, the maximum 73% removal of disperse yellow 42 dye was achieved with a catalyst dose of 0.5 g and an ozone dose supply of 1.8 mg/min. In catalytic ozonation with the hydroxyl radical scavenger effect (HRSE), the decline in removal efficiency from 73% to 61% demonstrated that removal efficiency was highly dependent on hydroxyl radical production. The COD removal efficiency in the real textile wastewater was 59% with the ozonation process, which increased to 79% after catalytic ozonation.

Metal speciation in sediments and bioaccumulation in edible bivalves to assess metal toxicity in a sand mining impacted tropical (Aghanashini) estuary, southern India

The study aims to understand the metal toxicity through the relationship between bioavailability in sediments and bioaccumulation in edible bivalves in an estuary subjected to extensive sand mining. The higher deposition of total Fe, Mn, Ni and Zn in the middle region (core M) was ascribed to estuarine processes and proximity to anthropogenic sources. EF revealed moderate to severe enrichment of Ni and Cu in sediments. Igeo showed moderate degree of pollution from Co, moderate to strong pollution from Ni and strong to extreme level of pollution from Cu. In core N, the average bioavailable concentration of Fe, Mn, Zn, Cu, Co and Ni was 1.76 %, 43.18 %, 59.14 %, 62.11 %, 60.42 % and 27.33 % respectively. The average bioavailable concentration of Fe (61.23 %), Mn (56.87 %), Cu (67.98 %), Co (69.77 %) and Ni (40.99 %) was higher in the core M as compared to core N except for Zn (56.98 %). The significant (>25.00 %) proportion of metals in bioavailable fractions in cores N and M construed their non-natural sources. Metal speciation study indicated bioavailability to fauna that likely to enhance by extensive sand mining. The level of Fe, Mn, Zn, Cu and Ni in Saccostrea cucullate, Meretrix casta and Villorita cyprinoides revealed toxicity to bivalves and probably to humans.

Paleo–Mesoarchean sedimentary record in the Dharwar Craton, India: Implications for Archean ocean oxygenation

The early Archean oceans were marked by significant redox changes which have subsequently shaped the Earth’s biosphere. Archean chemical sediments of banded Iron and Manganese formations provide important geochemical proxies for these historical shifts in the redox conditions and to trace the ancient sedimentation patterns and protoliths. In this study, we investigate the proto-ore of the Archean Mn-formations of the Sandur, Chitradurga and Shimoga greenstone belts of Dharwar Craton of southern Peninsular India, which is geochemically characterised as quartz arenites, Mn-arenites, Fe-arenites, Mn-argillites and Fe-argillites. The geochemical systematics suggest their deposition in shallow to deeper shelf in the Archean proto-ocean. The detrital zircon U-Pb systematics of Mn arenites and argillites indicate their maximum depositional age of 3230 ± 52 Ma representing the oldest onset of sedimentation during the Paleo–Mesoarchean timeframe in the Chitradurga Group of Dharwar Supergroup. The detrital influx proxies suggest variations in sedimentation rates associated with the Archean transgressive–regressive cycles and fluctuating hydrodynamic conditions, together reflecting an increasing trend in the contributions of recycled sediment from Sandur to Chitradurga and Shimoga greenstone belts. The available detrital zircon ages of the Mn arenites and argillites from these greenstone belts indicate a ∼ 600 Ma prolonged period of Mn deposition for which high-T hydrothermal fluids from Archean mid-oceanic ridges supplied the manganese. The trace element compositions of the concordant detrital zircons suggest 3.3–3.1 Ga Dharwar basement TTG/granitoid source which is corroborated by the zircon crystallization temperatures of 690–820 °C. The source-normalised α-dose rates of the detrital zircons signify greater degrees of sediment transport and multi-cycle nature which correspond to the earliest episode of crustal growth in the Indian sub-continent associated with the Mesoarchean Ur supercontinent. The clastic-chemogenic sedimentation attained through concomitant detrital sediment–seawater-metalliferous hydrothermal fluid mixing at an epicontinental passive margin resulted in the deposition of Mn-arenites and argillites closer to the higher Eh shore, while the Fe-rich sediments formed at a relatively deeper shelf characterised by comparatively lower Eh and more alkaline conditions. The comprehensive geochemical and geochronological data of the Archean Mn arenite-argillite sequences reveal the significance of regional episodes of ocean oxygenation at the shallow shelves of Archean oceans prior to great oxygenation event (GOE) that was mediated by the prolific growth of ancient microbiota which transformed the Earth to a more habitable planet.

Geochemistry of Cryogenian Datangpo manganese deposits in the southeastern Yangtze Platform of South China: implications for the origin of metallogenesis and depositional environment

ABSTRACT Sedimentary manganese (Mn) deposits in the southeastern Yangtze Platform of China have been newly discovered with considerable potential for resource exploration. Such deposits formed due to dynamic changes in the global environment, including the break-up of the supercontinent Rodinia, Snowball Earth glaciation, and the Neoproterozoic Oxygenation Event. The Mn-bearing sequences are hosted in the basal Datangpo Formation and are interbedded with black carbonaceous shale in a series of graben sub-basins in the Nanhua Rift Basin. We investigated the origin of these Mn deposits by analysing the major and trace elements, total organic carbon, and stable carbon and oxygen isotopes. Positive Eu anomalies were observed, indicating that the Mn was derived from a hydrothermal system. Redox-related elements, including Ce, Mo, U, V, S, and P, indicated that the depositional environment of the Mn layers was oxidative and that Mn2+ was initially oxidized to Mn oxides. However, the host rock (i.e. black carbonaceous shale) was deposited under dysoxic – anoxic and even sulfidic water conditions. The alternating distribution of Mn ore and host rock suggested alternating redox conditions in the sub-basins. A negative correlation between the Mn content and δ 13Ccarb values (−10‰–−7‰) and a deficiency of sulphide minerals indicate that the diagenetic degradation of organic matter (δ 13Corg from − 34‰ to − 31.9‰) took place through Mn oxide reduction rather than microbial sulphate reduction and can contribute to a considerable source of bicarbonates. The approximately homogeneous δ 13Ccarb depletion and their apparent discrepancy with δ 13Corg indicate that the post-depositional genesis of the Mn carbonate ore occurred in a relatively open early diagenetic pore water system with a considerable contribution from seawater-derived carbon sources.

The interaction of ammonia and manganese in abnormal metabolism of minimal hepatic encephalopathy: A comparison metabolomics study.

This study was to investigate the effects of ammonia and manganese in the metabolism of minimal hepatic encephalopathy (MHE). A total of 32 Sprague-Dawley rats were divided into four subgroups: chronic hyperammonemia (CHA), chronic hypermanganese (CHM), MHE and control group (CON). 1H-NMR-based metabolomics was used to detect the metabolic changes. Sparse projection to latent structures discriminant analysis was used for identifying and comparing the key metabolites. Significant elevated blood ammonia were shown in the CHA, CHM, and MHE rats. Significant elevated brain manganese (Mn) were shown in the CHM, and MHE rats, but not in the CHA rats. The concentrations of γ-amino butyric acid (GABA), lactate, alanine, glutamate, glutamine, threonine, and phosphocholine were significantly increased, and that of myo-inositol, taurine, leucine, isoleucine, arginine, and citrulline were significantly decreased in the MHE rats. Of all these 13 key metabolites, 10 of them were affected by ammonia (including lactate, alanine, glutamate, glutamine, myo-inositol, taurine, leucine, isoleucine, arginine, and citrulline) and 5 of them were affected by manganese (including GABA, lactate, myo-inositol, taurine, and leucine). Enrichment analysis indicated that abnormal metabolism of glutamine and TCA circle in MHE might be affected by the ammonia, and abnormal metabolism of GABA might be affected by the Mn, and abnormal metabolism of glycolysis and branched chain amino acids metabolism might be affected by both ammonia and Mn. Both ammonia and Mn play roles in the abnormal metabolism of MHE. Chronic hypermanganese could lead to elevated blood ammonia. However, chronic hyperammonemia could not lead to brain Mn deposition.

The Perturbation of the Guadalupian Marine Environment Triggered by Early-Stage Eruption of the Emeishan Large Igneous Province: Rare Earth Element and Sr-Nd Isotope Evidence from Zunyi Manganese Deposit, South China

Pure marine chemical sediments are archives of geochemical proxies for the composition of seawater and may provide information about the ancient hydrosphere–atmosphere system. The early stage of the Emeishan large igneous province (ELIP) was characterized by the subaqueous eruption of mafic igneous rocks around the J. altudaensis zone of the Capitanian Stage that has been proposed to have contributed to the Guadalupian mass extinction. However, detailed mechanisms and the impact of the eruption on the Guadalupian marine environment have yet to be assessed. Here, to examine the Guadalupian marine environment, we studied major and trace element concentrations, particularly rare earth element and yttrium data, along with high-precision Sr-Nd isotope ratios, of three types of Mn ores (i.e., clastic, massive, and oolitic) and siliceous limestones from the Zunyi Mn deposit in South China formed following the early-stage eruption of the ELIP. Our results indicate that the clastic Mn ores contain notable detrital mafic aluminosilicates. In contrast, the massive and oolitic Mn ores and siliceous limestones preserved the pristine geochemical signatures of the Middle–Late Permian seawater characterized by distinctly low (87Sr/86Sr)i and high εNd(t) values. These data indicate a strong impact of the early-stage submarine eruptions of the ELIP on the marine environment in South China and worldwide, likely through intensive seawater–rock interaction.

Manganiferous clays of Dharwar Craton, southern peninsular India: Insights on Archean weathering and ore formation processes

Vast clay deposits of Chitradurga and Sandur greenstone belts of the Dharwar Craton, southern peninsular India, hosting pockets of high‐grade manganese (Mn) ore, provide remarkable clues related to the ore‐forming processes and palaeo‐environmental conditions. In this study these Fe–Mn‐rich clays were investigated through mineralogical and geochemical characteristics to comprehend their palaeo‐weathering and genetic constraints and their role in the supergene accumulation of Mn ore. Their mineralogy is characterized by predominant kaolinite, muscovite, birnessite, haematite, goethite, halloysite along with quartz and traces of ilmenite. Chemical indices of alteration and weathering indicate intense weathering conditions under high palaeo‐precipitation rates in a humid, tropical climate under shallow burial conditions and K‐metasomatism. The presence of authigenic kaolinite and absence of illite reflect on diagenesis up to mesodiagenetic stage. Positive to negative Ce anomalies (Ce/Ce* = 0.67–5.93) of these clays suggest varying oxic‐anoxic conditions during their genesis, whereas conspicuous negative Eu anomalies (Eu/Eu* = 0.61–0.99) are attributed to precursor sediment signatures and hydrothermal imprints of the Mn ore. These kaolinite‐rich clays are suggested to have been formed by in situ chemical alteration, whereas kaolinitization of the Fe–Mn‐rich arenaceous and argillaceous sediments was derived from predominant tonalite and felsic provenance in a shallow marine passive margin setting. Based on the morphologies of birnessite, haematite and goethite in the investigated clays, we propose that these clays have played a key role in the oxidation and deposition of Mn (II) from the migrating aqueous solutions and acted as organo‐polymerization templates for the proliferation of ancient microbial life on the planet Earth.

Mineralogy of the 1.45 Ga Wafangzi manganese deposit in North China: Implications for pulsed Mesoproterozoic oxygenation events

Abstract Ancient manganese (Mn) deposits are primarily characterized by the presence of Mn(II) carbonates that likely formed by the diagenetic reduction of precursor Mn(IV) oxides. As such, Precambrian sedimentary Mn deposits have been used as a line of evidence for the evolution of oxygen in Earth’s surface environments. However, recent studies have shown that these Mn(II)-carbonates have the ability to directly accumulate within anoxic water columns, where free oxygen does not play a role in their formation. This alternative pathway casts uncertainty on the robustness of using ancient Mn deposits to constrain the redox fabric of the past marine water columns. Here, we investigate the Wafangzi Mn and Fe ore deposit from the 1.45 billion-year-old Tieling Formation, North China. The deposit contains Mn(II, III) mineral phases (hausmannite, braunite) as inclusions, or unreacted residues, trapped within Mn(II) carbonate (Ca-rhodochrosite). Some nodules and oolites of Mn(II) and Fe(II)-carbonate phases are also present and display a banded structure with concentric rings. Mn(III) oxide (manganite) is present in a paragenetic assemblage along with hematite and replacement textures with braunite. The negative carbon isotope composition (δ13C, –7‰ to –4‰) from Mn(II) carbonate samples in the Wafangzi Mn deposit which are distinct from that of contemporaneous seawater (~0‰), along with petrographic and speciation analyses, collectively suggest that the Mn(II, III)- and Fe(II)-bearing mineral phases formed through the diagenetic reduction of primary Mn(IV)/Fe(III) minerals coupled to the oxidation of organic matter. Therefore, the Wafangzi Mn deposit suggests the presence of sufficiently oxygenated marine waters, overlying anoxic ferruginous deeper waters with a transitional manganous water layer that could have driven the redox cycling of Mn, Fe, and C. Given the contemporaneous economic Mn deposits in the 1.45 Ga Ullawarra Formation in Western Australia, our findings imply the existence of a transient, and perhaps widespread, pulsed oxygenation event in the mid-Proterozoic oceans.

Strong positive fractionation of chromium isotopes in iron formation of the Jacadigo Group (Brazil) – A link to enhanced atmospheric oxygenation during the Late Neoproterozoic

Cr isotopes recorded in iron formations (IF) are considered to have the potential to reflect the isotope signatures in respective ambient surface seawater. The ∼600 Ma Fe and Mn deposits pertaining to the Banda Alta Formation (Urucum district, Mato Grosso do Sul, Brazil), comprise the world’s youngest and largest Neoproterozoic sedimentary Fe and Mn formations (MnF). Shale normalized Rare Earth Element and Yttrium (REY) patterns of drillcore samples show flat, positively sloped patterns with absent Europium anomalies and near- to supra-chondritic Yttrium-Holmium ratios with negative Cerium anomalies, which imply intermittent mixing of freshwater with seawater. Redox sensitive element enrichment factors (MoEF, UEF, CrEF) show positive correlation, indicating varying redox conditions across the Jacadigo Basin, with ephemeral euxinic conditions. The Cr isotope signatures across the Urucum IF (δ53Crauth at: Morraria Grande + 0.93 ± 0.34 ‰, 2σ, n = 28; Morro do Rabichão + 0.5 ± 0.4 ‰, 2σ, n = 3; and Morro do Urucum ca. + 0.64 ‰, n = 1) are statistically indistinguishable from previously published surface outcrop samples at Morro do Urucum. Our new data support: (1) a stable supply of oxidized Cr potentially from continental sources at the time of deposition, implying high atmospheric O2 levels in the Late Neoproterozoic; (2) insignificant alteration of the authigenic Cr isotope signals by tropical weathering despite surface iron up-concentration and leaching of carbonates, and (3) lack of isotope effects that would be associated with non-quantitative reduction processes and accompanying particulate transport to the chemical sediments in the Jacadigo Basin. The combined information from (isotope)geochemical data presented herein speak for a deposition of the Urucum IFs in restricted, periodically ice-covered and stratified sub-basins with partial connection to the open ocean, and for the presence of a sufficiently oxidative atmosphere which promoted a continuous supply of the surface waters with isotopically heavy Cr from the weathering landmasses at this time.

Chemical Treatment of Banana Blossom Peels Adsorbent as New Approach for Manganese Removal: Isotherm and Kinetic Studies

This research aimed to investigate the potential of chemically modified banana blossom peels (BBP) as an adsorbent for removing manganese (Mn) from water. Zeta potential, field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Brunauer–Emmet–Teller (BET) were used to characterise the BBP adsorbent. Batch adsorption studies were used to assess the effects of the solution pH, adsorbent dosage, initial manganese concentration, and contact time of the adsorption process. Zeta potential of BBP with a value of −9.87 to −21.1 mV and FESEM analysis revealed deeper dents and rough internal surfaces conducive to Mn deposition, whereas EDX analysis revealed the presence of C, O, and Na elements (before adsorption); C, O, and Mn (after adsorption). The presence of hydroxyl, carboxylic, and amino groups, which are responsible for the adsorption process, was discovered using FTIR analysis. Furthermore, XRD analysis revealed that the BBP adsorbent structure is amorphous. The BBP adsorbent has a BET surface area of 2.12 m2/g, a total pore volume of 0.0139 cm3/g, and an average pore diameter of 64.35 nm. The BBP adsorbent demonstrated remarkable results of 98% Mn removal under the optimum pH 7, 0.5 g (adsorbent dosage), and 10 mg/L of Mn initial concentration in 150 min of contact time. The linear Langmuir and Freundlich isotherm models best fit the adsorption isotherm data with the R2 &gt; 0.98. In contrast, the adsorption process occurs as a function of the chemisorption as determined by linear pseudo-second-order kinetics. Using 0.1 M HCI, the maximal desorption rate of Mn was 92% in the first cycle, with a recovery rate of 94.18% Mn removal in 30 min. These findings support the use of BBP as a natural adsorbent for Mn removal as a treatment option for improving wastewater quality.

Thermochemical oxidation of methane by manganese oxides in hydrothermal sediments

Microbial anaerobic oxidation of methane coupled to the reduction of Mn(IV)-oxides, typically MnO2, derived from continental weathering and riverine transport has been proposed as a globally important sink of methane. However, the potential role of hydrothermal Mn(IV) oxide-rich sediments as a methane sink, and the mechanisms of underpinning methane oxidation at high-temperature hydrothermal fields remain poorly understood. Here, we report the occurrence of almost pure rhodochrosite with extremely negative δ13CPDB values (as low as –76.4‰) in direct association with hausmannite formed through hydrothermal activity in the Late Triassic Heqing Mn deposit in Southern China. Based on detailed petrography and geochemistry, this rhodochrosite is interpreted as the result of the thermochemical oxidation of methane by hausmannite during early diagenesis. Given high hydrothermal Mn2+ and CH4 release coupled to low sulfate concentration observed in the Archean oceans, we propose that hydrothermal Mn(IV) oxides may have been effective methane sinks in Earth’s ancient oceans.