Soluble Mn Research Articles

Weathering of volcanic eruption products and rivers contamination in Kamchatka

We investigated the biochemical weathering of unaltered lava and scoria samples from Tolbachik volcanic field (Kamchatka). An experimental study on leaching of main (Si, Fe, Mg, Al, and Ca) and trace element constituents (Li, Sr, Ba, V, Mn, Co, Ni, Cu, Ti, and other trace metals) was conducted. We used 0.01 M (pH 2) solutions of oxalic and acetic acids as analogs of natural bioorganic solvents. Meanwhile, a constant mass ratio of solid and liquid phases was maintained. The results suggested that the mobilization of trace elements occurs mainly as a result of the destruction of the crystalline structures of rock-forming minerals. In the case of oxalic acid solution, Fe(III) and Mn(IV) oxyhydroxides are reduced to soluble Fe(II) and Mn(II) compounds. The formation of organic complexes increases the stability of metals in solution and makes it possible to achieve significantly higher concentrations of dissolved forms than in the absence of organic ligands. For example, water that has passed through an old lava field covered with lichen may contain 2.5 times more Co than the maximum permissible concentration for fish reproduction. This study demonstrated that the spikes in concentrations of heavy metals in the Kamchatka River, observed during the 2015 – 2016 period, can be explained by the leaching of fresh products from the Tolbachik Fissure Eruption (2012 – 2013).

Reductive Dissolution Mechanisms of Manganese Oxide Mediated by Algal Extracellular Organic Matter and the Effects on 17α-Ethinylestradiol Removal.

Reductive dissolution of manganese oxide (MnOx) is a major process that improves the availability of manganese in natural aquatic environments. The extracellular organic matter (EOM) secreted by algae omnipresent in eutrophic waters may affect MnOx dissolution thus the fate of organic micropollutants. This study investigates the mechanisms of MnOx reductive dissolution mediated by EOM and examines the effects of this process on 17α-ethinylestradiol degradation. The influences of EOM concentration (1.0-20.0 mgC/L) and pH (6.0-9.0) in both dark and irradiated conditions were assessed. In the dark, EOM was found to facilitate MnOx reductive dissolution via the ligand-to-metal charge transfer (LMCT). The dissolution was further enhanced under irradiation, with the participation of superoxide ions (O2•-). Higher EOM concentrations increased the contents of available reducing substances and O2•-, accelerating the reductive dissolution. Higher pH slowed the photoreductive dissolution rates, while O2•--mediated reduction became more important. Polyphenols and highly unsaturated carbon and phenolic formulas in EOM were found to drive the reductive dissolution. Soluble reactive Mn(III) formed through reductive dissolution of MnOx effectively removed 17α-ethinylestradiol in solution. Overall, the findings regarding the mechanisms behind reductive dissolution of MnOx have broad implications for Mn geochemical cycles and organic micropollutant fate.

Evaluation of the dynamics of nutrients and potentially toxic elements along a major river in Ethiopia using multivariate statistical techniques: Implications of possible co-occurrences

Evaluation of the dynamics of nutrients and potentially toxic elements along a major river in Ethiopia using multivariate statistical techniques: Implications of possible co-occurrences

Size-segregated particulate matter oxidative potential near a ferromanganese plant: Associations with soluble and insoluble elements and their sources

Size-segregated particulate matter oxidative potential near a ferromanganese plant: Associations with soluble and insoluble elements and their sources

Cryo-EM Structure of the Mnx Protein Complex Reveals a Tunnel Framework for the Mechanism of Manganese Biomineralization.

The global manganese cycle relies on microbes to oxidize soluble Mn(II) to insoluble Mn(IV) oxides. Some microbes require peroxide or superoxide as oxidants, but others can use O2 directly, via multicopper oxidase (MCO) enzymes. One of these, MnxG from Bacillus sp. strain PL-12, was isolated in tight association with small accessory proteins, MnxE and MnxF. The protein complex, called Mnx, has eluded crystallization efforts, but we now report the 3D structure of a point mutant using cryo-EM single particle analysis, cross-linking mass spectrometry, and AlphaFold Multimer prediction. The β-sheet-rich complex features MnxG enzyme, capped by a heterohexameric ring of alternating MnxE and MnxF subunits, and a tunnel that runs through MnxG and its MnxE3F3 cap. The tunnel dimensions and charges can accommodate the mechanistically inferred binuclear manganese intermediates. Comparison with the Fe(II)-oxidizing MCO, ceruloplasmin, identifies likely coordinating groups for the Mn(II) substrate, at the entrance to the tunnel. Thus, the 3D structure provides a rationale for the established manganese oxidase mechanism, and a platform for further experiments to elucidate mechanistic details of manganese biomineralization.

Homogeneous versus heterogeneous Mn(II) oxidation in peroxymonosulfate assisting chlorination: Synergistic role for enhanced Mn(II) oxidation in water treatment

Homogeneous versus heterogeneous Mn(II) oxidation in peroxymonosulfate assisting chlorination: Synergistic role for enhanced Mn(II) oxidation in water treatment

Advances in Research on Bacterial Oxidation of Mn(II): A Visualized Bibliometric Analysis Based on CiteSpace.

Manganese (Mn) pollution poses a serious threat to the health of animals, plants, and humans. The microbial-mediated Mn(II) removal method has received widespread attention because of its rapid growth, high efficiency, and economy. Mn(II)-oxidizing bacteria can oxidize toxic soluble Mn(II) into non-toxic Mn(III/IV) oxides, which can further participate in the transformation of other heavy metals and organic pollutants, playing a crucial role in environmental remediation. This study aims to conduct a bibliometric analysis of research papers on bacterial Mn(II) oxidation using CiteSpace, and to explore the research hotspots and developmental trends within this field between 2008 and 2023. A series of visualized knowledge map analyses were conducted with 469 screened SCI research papers regarding annual publication quantity, author groups and their countries and regions, journal categories, publishing institutions, and keywords. China, the USA, and Japan published the most significant number of research papers on the research of bacterial Mn(II) oxidation. Research hotspots of bacterial Mn(II) oxidation mainly focused on the species and distributions of Mn(II)-oxidizing bacteria, the influencing factors of Mn(II) oxidation, the mechanisms of Mn(II) oxidation, and their applications in environment. This bibliometric analysis provides a comprehensive visualized knowledge map to quickly understand the current advancements, research hotspots, and academic frontiers in bacterial Mn(II) oxidation.

Accelerated manganese(II) removal by in situ mine drainage treatment system without organic substrate amendment: Metagenomic insights into chemolithoautotrophic manganese oxidation via extracellular electron transfer

Accelerated manganese(II) removal by in situ mine drainage treatment system without organic substrate amendment: Metagenomic insights into chemolithoautotrophic manganese oxidation via extracellular electron transfer

Biogenic Mn Oxide Generation and Mn(II) Removal by a Manganese Oxidizing Bacterium Bacillus sp. Strain M2.

Mn(II)-oxidizing bacteria (MOB) are widely distributed in natural environments and can convert soluble Mn(II) into insoluble Mn(III) and Mn(IV). The biogenic manganese oxides (BioMnOx) produced by MOB have been considered for remediating heavy metal pollution and degrading organic pollutants in an eco-friendly manner. In this study, a manganese-oxidizing bacterium was isolated from Mn-polluted rivulet sediment and identified as Bacillus sp. strain M2 by PCR, phylogenetic tree construction, transmission electron microscopy (TEM), and physiological and biochemical indices. Strain M2 grew well under Mn(II) stress. BioMnOx with nanosized irregular geometric shapes and loose structures generated by strain M2 were found on the surface of the bacterial cells. The content of Mn in the bacteria was as high as 5.36%. Approximately 71.24% and 47.52% of Mn(II) was oxidized to Mn(III/IV) in the cell and in the deposits, respectively, within 3 d of cultivation with Mn(II). Extracellular enzymes contributed to the Mn removal and oxidation. In conclusion, Bacillus sp. strain M2 has a high potential for use in the remediation of Mn-contaminated sites.

In situ phytoextraction of Mn and NH4+-N from aqueous electrolytic manganese residue solution by Pistia stratiotes: Effects of Fe/Co presence and rhizospheric microbe synergistic involvement

In situ phytoextraction of Mn and NH4+-N from aqueous electrolytic manganese residue solution by Pistia stratiotes: Effects of Fe/Co presence and rhizospheric microbe synergistic involvement

Modeling Interactive Effects of Manganese Bioavailability, Nitrogen Deposition, and Warming on Soil Carbon Storage

AbstractManganese (Mn) is a redox‐active micronutrient that has been shown to accelerate plant litter decomposition; however, the effect of Mn‐promoted decomposition on soil C storage is unclear. We present a novel biogeochemical model simulating how Mn bioavailability influences soil organic C (SOC) stocks in a soil profile (<50 cm) within a temperate forest. In our model, foliar Mn increased in response to increasing soluble Mn released through Mn‐oxide (birnessite) dissolution in mineral soil layers. The ensuing Mn enrichment in leaf litter redistributed Mn to the surface forest floor layer, promoted enzymatic oxidation of lignin, and decreased SOC stocks. Total SOC loss was partially mitigated by accumulation of lignin‐oxidation products as mineral‐associated organic C. We also explored how Mn‐driven changes to C storage interacted with effects of N deposition and warming. Nitrogen enrichment inhibited Mn‐dependent lignin degradation, increasing SOC stocks and weakening their dependence on Mn bioavailability. Warming stimulated decomposition and reduced C stocks but was less effective at low Mn bioavailability. Our model results suggest that SOC stocks are sensitive to Mn bioavailability because increased plant uptake redistributes Mn to surface soils where it can enhance litter decomposition. Based on our simulations, we predict that Mn becomes limiting to litter decomposition where Mn is poorly soluble. Depletion of bioavailable Mn or other cofactors that are critical to decomposition could limit the response of organic C stocks to warming over time, but quantitative projections of the role of Mn bioavailability in regulating decomposition requires additional measurements to constrain model uncertainties.

Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton-Electron Transfer Mediators for Electrocatalysis.

Iron-sulfur clusters play essential roles in biological systems, and thus synthetic [Fe4S4] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe4S4] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO2 reduction catalyst. Here, we demonstrate that incorporating these [Fe4S4] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe4S4-based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn-H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe4S4] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

Assessment of the suitability of greensand filtration for Mn removal for private wells

Greensand filtration is a common treatment option for manganese, sulfide, and iron removal; poor maintenance, however, can compromise effectiveness and even lead to increased post-treatment Mn concentrations. A private drinking-water well in exceedance of Health Canada’s maximum allowable concentration for Mn was sampled over a 1-year period to assess Mn removal via greensand filtration. Mn concentrations post-treatment were on average twofold higher than raw well water prior to media change. Reducing conditions, evidenced by negative oxidation–reduction potential (ORP) of the effluent, were central to generating soluble Mn(II). Monitoring revealed that water usage patterns caused variability in post-treatment Mn, with peak concentrations (>3.5× higher than influent water) observed after a 7-day idle period. As inadequate oxidant addition can lead to reducing conditions, monitoring ORP may facilitate proxy surveillance for Mn release. Findings underscore the importance of human factors (e.g., aesthetic concerns, barriers to maintenance, perceived risk) when evaluating overall benefits and drawbacks of treatment systems.

Algal Extracellular Organic Matter Induced Photochemical Oxidation of Mn(II) to Solid Mn Oxide: Role of Mn(III)-EOM Complex and Its Ability to Remove 17α-Ethinylestradiol.

Photosensitizer-mediated abiotic oxidation of Mn(II) can yield soluble reactive Mn(III) and solid Mn oxides. In eutrophic water systems, the ubiquitous algal extracellular organic matter (EOM) is a potential photosensitizer and may have a substantial impact on the oxidation of Mn(II). Herein, we focused on investigating the photochemical oxidation process from Mn(II) to solid Mn oxide driven by EOM. The results of irradiation experiments demonstrated that the generation of Mn(III) intermediate was crucial for the successful photo oxidization of Mn(II) to solid Mn oxide mediated by EOM. EOM can serve as both a photosensitizer and a ligand, facilitating the formation of the Mn(III)-EOM complex. The complex exhibited excellent efficiency in removing 17α-ethinylestradiol. Furthermore, the complex underwent decomposition as a result of reactions with reactive intermediates, forming a solid Mn oxide. The presence of nitrate can enhance the photochemical oxidation process, facilitating the conversion of Mn(II) to Mn(III) and then to solid Mn oxide. This study deepens our grasp of Mn(II) geochemical processes in eutrophic water and its impact on organic micropollutant fate.

The importance of the soluble and colloidal pools for trace metal cycling in deep-sea pore waters

Physical and chemical trace metal speciation are important for our understanding of metal cycling and potential toxicity to marine life. Trace metals can behave differently in diffusion processes or particle-solution interactions and have different bioavailabilities depending on their physical and chemical forms, which often depend on redox conditions. Here we investigated dissolved (< 0.2 µm) and soluble (< 0.02 µm) concentrations of Mn, Co, Ni, Fe, Cu, V, Mo, U, Cd, and As in oxic and suboxic deep-sea sediments of the central equatorial Pacific Ocean. Vanadium, Mo, U, As, and Cd showed no significant concentration differences between their dissolved and soluble forms, suggesting that they are present as inorganic ionic species or organic complexes in the truly dissolved or small colloidal fraction. In contrast, the colloidal fraction (> 0.02 µm < 0.2 µm) of Mn, Co, Ni, and Cu increased with depth in oxic pore waters and Fe had the largest but variable colloidal pool. Soluble Mn, Co, and Ni were released in the uppermost 2-4 cm in the sediment because of reductive dissolution. The increasing colloidal fraction with depth suggests a decrease in the concentration of small organic ligands with depth, that are abundant in the surface sediment pore waters, and instead an increasing importance of larger (> 0.02 µm) inorganic nanoparticles and colloids such as Mn and Fe (oxyhydr)oxides that control Mn, Fe, and Co cycling at depths > 10 cm. The distribution of Ni and Cu cannot be exclusively explained by inorganic nanoparticles and a shift from low to larger high molecular weight organic ligands might occur. These findings provide new insights into trace metal distributions in the dissolved phase, highlighting the diversity of metal complexes and the need to incorporate these in future calculations of benthic metal fluxes and ecotoxicity assessments, especially in oxic pore waters.

Unravelling the impacts of soluble Mn(III)-NOM on arsenic immobilization by ferrihydrite or goethite under aquifer conditions

Unravelling the impacts of soluble Mn(III)-NOM on arsenic immobilization by ferrihydrite or goethite under aquifer conditions

Trace mineral sources influence in vitro fermentation characteristics and trace mineral solubility.

Two experiments were conducted to determine: 1) the impact of strained rumen fluid (SRF) alone or SRF with particle-associated microorganisms (PAO) included and dilution on in vitro dry matter digestibility (DMD) and 2) the impact of trace mineral (TM) source on in vitro fermentation characteristics and TM solubility under simulated abomasal and intestinal conditions. In experiment 1, 3 cannulated steers were adapted to a diet formulated to meet the nutrient requirements for lactating dairy cows. Strained RF was obtained by straining rumen content through 2 layers of cheesecloth. Half of the remaining digesta was washed with McDougall's buffer and filtered through 2 layers of cheesecloth to obtain PAO. Both SRF and PAO were filtered again through 8 layers of cheesecloth. Strained RF was mixed with either McDougall's buffer (SRF) or PAO (SRF+ + PAO) at a ratio of 1:2 or 1:4 and incubated at 39 °C for 12h using the ground basal diet as the substrate. Digestibility of DM was greater in digestion tubes containing SRF and SRF + PAO at a 1:2 ratio. In experiment 2, 8 steers fitted with a ruminal cannula were blocked by body weight and assigned to 1 of the 2 treatment groups. Treatments consisted of 10mg Cu, 40mg Mn, and 60mg Zn/kg DM from either: 1) sulfate (STM) or 2) hydroxychloride (HTM) sources. Steers were housed in individual pens and fed the same diet as described in experiment 1. Dietary TM treatments were mixed with dried distiller grains and mixed in the diet, by hand, immediately after basal diet delivery. Dietary treatments were fed for 14 d. On day 15, SRF + PAO was collected from each steer (STM-RF and HTM-RF) and used in a series of in vitro crossover experiments. In vitro substrates (S) used were the ground diets consumed by the animals on each treatment (STM-S and HTM-S). Incubations containing HTM-S had greater (P < 0.01) total volatile fatty acid (VFA) concentration and propionic acid molar proportions, but lesser (P < 0.01) acetic acid molar proportions than STM-S. Rumen fluid from steers supplemented with HTM had a greater (P < 0.03) total VFA than STM-RF at 24h post incubation. After 12h post incubation, the molar proportion of propionic acid in HTM-RF was lesser (P = 0.04) than in STM-RF. After simulated abomasal digestion, soluble Mn concentration in HTM-S was greater (P < 0.01) than in STM-S. These data indicate that the source of TM can influence in vitro rumen fermentation characteristics and Mn solubility under simulated abomasal conditions.

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

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

Kinetics and TD-DFT calculations of base-catalyzed oxidation of acriflavine hydrochloride: Removal of dyes colors from wastewater

Kinetics and TD-DFT calculations of base-catalyzed oxidation of acriflavine hydrochloride: Removal of dyes colors from wastewater

The Effect of a Molasses Reductant on Acetic Acid Leaching of Black Mass from Mechanically Treated Spent Lithium-Ion Cylindrical Batteries

Recovery of valuable metals from end-of-life cylindrical lithium-ion batteries (LiBs) by leaching using acetic acid in the presence of an organic reductant is a promising combination to overcome environmental concerns that arise from employing inorganic reagents. This study investigated the effect of using molasses as a reductant in acetic acid leaching of a mixture of cathode and anode materials (black mass) prepared using mechanical treatments from spent LiBs. The effects of temperature, solid/liquid ratio, stirring speed, and acid concentration on the leaching of target metals (Co, Ni, Mn, and Li), current collector metal foil elements (Al and Cu), and Fe from the battery casing, with and without reductant, were investigated to obtain the optimum leaching conditions. The effect of adding the molasses at the start of leaching and after 1 h of leaching was tested. Acid leaching without molasses extracted the target metals Li, Ni, Co, and Mn with an efficiency &lt;35% for all leaching parameters. However, the Al and Fe extractions increased as the acid molarity increased. Molasses addition at the start of leaching increased the extraction of the target metals to &gt;96% at temperatures &gt;50 °C. This is likely due to oxidation of the reducing sugars in the molasses that reduced the insoluble Co(III), Ni(III), and Mn(IV) components to soluble Co(II), Ni(II), and Mn(II) species, respectively. The kinetics of Co extraction in the presence of molasses were analysed, which has indicated that the rate-determining step in the Co leaching process is the reduction of Co(III) on the surface of particles in the black mass. Excess molasses can precipitate out target metals, especially Co, due to the presence of oxalic acid in the molasses. The reducing effect precipitated Cu(II) to Cu2O, and could further reduce Co to metal, which suggests that leaching with the optimum dosage of acetic acid and molasses may selectively precipitate copper.