Formation Of Mn Oxides Research Articles

Cadmium immobilization by mercapto-palygorskite in alkaline soil: Impacts on soil microbial communities and wheat rhizosphere metabolism

Weakly alkaline cadmium (Cd) contaminated soil in China has aroused great concern regarding its impact on food security and human health. Mercapto-modified palygorskite (MP) has exhibited good potential to minimize Cd accumulation in wheat, it is imperative to understand the underlying mechanisms within the soil-wheat-microbial system for sustainable development of agrochemicals. This study evaluated the effects of various MP dosages on soil Cd bioavailability, rhizosphere metabolomics, microbial community structure and wheat growth. The results indicated that MP (0.05–0.2 %) application significantly reduced Cd accumulation in wheat grains by 59.0–83.2 % (p < 0.05) and inhibited Cd translocation from root to grain. MP also promoted Mn oxide formation and redistributed the exchangeable Cd to Fe–Mn oxide-bound forms (44.2–109.6 %), thus lowering soil Cd bioavailability by 17.9–32.5 %. Additionally, MP reduced wheat rhizosphere organic acid levels, altered rhizosphere carbon and nitrogen pools, and stimulated the growth of Cd-tolerant Alternaria and Cladosporium, while inhibiting the growth of Fusarium. These findings highlight the potential of MP to modulate soil rhizosphere metabolism and microbial communities, offering a novel perspective on its environmental implications and supporting agrochemical sustainability.

Oxides improve the strength of Zn-0.5Mn-0.5Mg alloys proceeded by laser powder bed fusion

Laser powder bed fusion has recently been adopted to fabricate biodegradable Zn alloys. But the mechanical properties need to be further improved to meet the requirements for natural bone implants. In this study, a ternary Zn-0.5Mn-0.5Mg biodegradable alloy is prepared by laser powder bed fusion technique. The as-printed sample shows a large compressive yield strength of 267 MPa and considerable ductility that the sample maintains its integrity after 50 % compression. The improved strength is mainly attributed to the formation of brittle Zn oxides, Mn oxides and Mg oxides which induce lattice distortion. These oxides fragment easily during the compression and reduce the stress concentration, resulting in significant ductility. More importantly, the as-printed sample shows a moderate degradation rate of 0.08 mm/year after immersing in the simulated body fluid solution for 7 days. In addition, the sample has MC3T3-E1 cell viabilities higher than 75 %, showing no-toxicity characteristic. This study demonstrates that laser powder bed fusion Zn-Mn-Mg alloy is a promising candidate for biodegradable materials and proposes a novel route to tailor the mechanical properties of additive-manufactured Zn alloys by oxides compositing.

The Formation of Bixbyite-Type Mn2O3 via Pyocyanin-Dependent Mn(II) Oxidation of Soil-Derived Pseudomonas aeruginosa

Bacterial Mn(II) oxidation is believed to play a dominant role in accelerating the rate of Mn biomineralization in nature. Commonly, bacteria employ two ways involving Mn(II) oxidases and reactive oxygen species to oxidize Mn(II). In this study, a new strategy for bacterial Mn(II) oxidation involving the pyocyanin, a greenish blue phenazine pigment from Pseudomonas aeruginosa, was discovered. To begin with, a bacterial strain L3 was isolated from soils and identified as Pseudomonas aeruginosa, which exhibited the ability of Mn(II) oxidation. Next, the pyocyanin was purified from strain L3 cultures and proven to be involved in Mn(II) oxidation. Particularly, the oxidation of Mn(II) by pyocyanin was dependent on its ambient pH. In comparison with pH of 5 and 7, pyocyanin (the initial value of OD387 was 0.56 at pH of 2) showed a stronger capability of oxidizing Mn(II) at pH of 9, reaching 144.03 μg L−1 of Mn oxides after 108 h of Mn(II) oxidation, while pyocyanin ultimately produced 43.81 μg L−1 at pH of 7 and 3.32 μg L−1 at pH of 5, respectively. Further, strain L3 cultures were fractionated into three parts, i.e., the cell culture solution, fermentation supernatant, and cell suspension, and the Mn(II)-oxidizing activity was found to be distributed in the cell culture solution and fermentation supernatant, as evidenced by the formation of blackish glossy Mn oxides. Specifically, in the first half, the rate of Mn(II) oxidation by the fermentation supernatant was higher than that by the cell culture solution, whereas in the second half, the cell culture solution showed the much higher Mn(II)-oxidizing activity compared to the fermentation supernatant. Last but not least, the collective results from mineral characterization demonstrated that, the Mn oxides produced by P. aeruginosa strain L3, either by the cell culture solution or by the fermentation supernatant, were bixbyite-type Mn2O3 with poor crystallinity.

Hydrological dynamics and manganese mineralization in the wake of the Sturtian glaciation

The Cryogenian Sturtian and Marinoan glaciations stand as the most extreme climate events in Earth history. Intriguingly, large-scale Mn carbonates characterize the nonglacial interlude of this period in South China. The formation mechanism of Mn carbonates and the potential correlation underlying this temporal association remain elusive. Here, we present an integrated petrographic and geochemical study of drill core materials intercepting the Mn-bearing Datangpo Formation. Rare earth element patterns of these Mn carbonates exhibit positive Ce anomalies and a lack of Y anomalies, which differ from those of modern seawater but resemble marine Mn-Fe oxides. These features, combined with negative carbonate carbon isotope compositions (δ13Ccarb as light as −9.9 ‰ VPDB), indicate the presence of oxide precursors and the incorporation of light carbon during Mn-carbonate precipitation. Phosphate oxygen isotope ratios (δ18Op) of HCl-extractable apatite reveal a ∼4 ‰ difference in the average δ18Op between Mn-rich and Mn-poor rocks. We propose that the more positive δ18Op of Mn-rich samples may result from the dominance of phosphate released by reductive dissolution of metal oxides or a heavier oxygen isotope signal of surrounding waters with which isotopic equilibrium has been reached. We further illustrate how marine invasions into coastal anoxic basins could have triggered the formation of Mn oxides and highlight the role of glaciation–deglaciation in the development of giant Mn deposits.

Controls on distributions of aluminium, manganese and cobalt in the South Atlantic Ocean along GEOTRACES transect GA10

Trace metals (TMs) manganese (Mn), cobalt (Co), and aluminium (Al) have important geochemical and biological roles in the ocean. Here, we present full depth profiles of dissolved (d) and particulate Al, Mn, and Co along the latitude of 40 °S in the South Atlantic Ocean from the GEOTRACES GA10 cruises that operated in austral spring 2010 and summer 2011. The region is characterized by enhanced primary productivity and forms a key transition zone between the Southern Ocean and South Atlantic Subtropical Gyre. The mean concentrations of dAl, dCo, and dMn (±standard deviation) were 3.36 ± 2.65 nmol kg−1, 35.3 ± 17.6 pmol kg−1, and 0.624 ± 1.08 nmol kg−1, respectively. Their distributions in surface waters were determined by external sources and complex internal biogeochemical processes. Specifically, surface ocean dCo was controlled by the interplay between phytoplankton uptake, remineralization and external inputs; dMn was likely determined by the formation and photoreduction of Mn-oxides; and dAl was supplied by atmospheric deposition and removed by scavenging onto particles. Fluvial and sedimentary inputs near the Rio de La Plata estuary and benthic sources from the Agulhas Bank resulted in elevated dTM concentrations in near-shore surface waters. These externally sourced dTMs were effectively delivered to the open ocean by offshore diffusion and/or advection, and potentially facilitated enhanced primary productivity along the transect.The distributions of dTMs at depth were predominantly controlled by the mixing of North Atlantic Deep Water (NADW) and waters of Antarctic origin (e.g., Upper Circumpolar Water (UCDW) and Antarctic Bottom Water (AABW)). The calculated endmember concentrations of dAl and dCo in NADW showed minor decreases in the SASTG following north–south transport, suggesting removal rates of 0.064 nM/year and 0.035–0.075 pM/year, respectively. The endmember concentration of dCo in AABW was maintained at ∼30 pmol kg−1 without evidence for scavenging removal in the Southern Ocean and SASTG (time frame >400 years). The concentrations of dMn in NADW and AABW were between 0.1 and 0.16 nmol kg−1, and any elevated dMn concentrations were ascribed to local external inputs (e.g., from sediments in the Argentine Basin and hydrothermal activity near the Mid-Atlantic Ridge). Hence, four controlling factors (sources, internal cycling, water mass mixing and time) need to be considered when assessing TM distributions in the global ocean, even for TMs that are vulnerable to scavenging removal processes. Because the deep waters formed in high latitude oceans are crucial components of the global thermohaline overturning system, any processes (e.g., glacier melting, upwelling and sinking, and biological activity) that impact the preformed dTM concentrations in high latitude oceans will determine the downstream dTM distributions. Therefore, the sources and sinks of TMs and associated biological activity in high latitude oceans could engender basin to global scale impacts on seawater distributions of Al, Co, and Mn and their stoichiometric relationships with macronutrients, and the global biogeochemical cycles of these scavenged-type TMs.

Pliocene subsurface fluid flow driven by rapid erosional exhumation of the Colorado Plateau, southwestern USA

Abstract Erosion may modify the architecture of subsurface flow systems by removing confining units and changing topography to influence patterns of fluid circulation or by inducing gas exsolution from subsurface fluids, influencing compositional and buoyancy patterns in flow systems. Here, we examine the geologic record of subsurface flow in the sedimentary rocks of the Paradox Basin in the Colorado Plateau (southwestern USA), including the distribution and ages of Fe- and Mn-oxide deposits and bleached, former red-bed sandstones. We compare our results to those of previous geo- and thermochronology studies that documented as much as 2 km of erosional exhumation at ca. 3–4 Ma and Fe-and Mn-oxide precipitation at 3.6 Ma along fault zones in the region. We used (U-Th)/He and K-Ar dating to document two new records of subsurface flow of reduced fluids between 3 and 4 Ma. The first is precipitation of Mn-oxides along the Moab fault (Utah, USA) at 3.9 ± 0.2 Ma. The second is clay mineralization associated with laterally extensive bleaching in the Curtis Formation, which we dated using K-Ar illite age analysis to 3.60 ± 0.03 Ma. The coincidence of the timing of bleaching, Fe- and Mn-oxide formation in multiple locations, and erosional exhumation at 3–4 Ma raises the question of how surface erosion may have induced a phase of fluid flow in the subsurface. We suggest that recent erosion of the Colorado Plateau created steep topographic gradients that enhanced regional groundwater flow, whereby meteoric water circulation flushed reduced fluids toward discharge zones. Dissolved gases, transported from hydrocarbon reservoirs, also may have been exsolved by rapid depressurization.

Proteomic insights into the response of Halomonas sp. MNB13 to excess Mn(Ⅱ) and the role of H2S in Mn(Ⅱ) resistance

Halomonas spp. are moderately halophilic bacteria with the ability to tolerate various heavy metals. However, the role of basic cellular metabolism, particularly amino acid metabolism, has not been investigated in Halomonas spp. under excess Mn(Ⅱ). The strain Halomonas sp. MNB13 was isolated from a deep-sea ferromanganese nodule and can tolerate 80 mM Mn(Ⅱ). To comprehensively explore the mechanisms underlying its resistance to excess Mn(Ⅱ), we conducted a comparative proteome analysis. The data revealed that both 10 mM and 50 mM Mn(Ⅱ) significantly up-regulated the expression of proteins involved in Mn(Ⅱ) transport (MntE), oxidative stress response (alkyl hydroperoxide reductase and the Suf system), and amino acid metabolism (arginine, cysteine, methionine, and phenylalanine). We further investigated the role of cysteine metabolism in Mn(Ⅱ) resistance by examining the function of its downstream product, H2S. Consistent with the up-regulation of cysteine desulfurase, we detected an elevated level of H2S in Halomonas sp. MNB13 cells under Mn(Ⅱ) stress, along with increased intracellular levels of H2O2 and O2•−. Upon exogenous addition of H2S, we observed a significant restoration of the growth of Halomonas sp. MNB13. Moreover, we identified decreased intracellular levels of H2O2 and O2•− in MNB13 cells, which coincided with a decreased formation of Mn-oxides during cultivation. In contrast, in cultures containing NaHS, the residual Mn(Ⅱ) levels were higher than in cultures without NaHS. Therefore, H2S improves Mn(Ⅱ) tolerance by eliminating intracellular reactive oxygen species rather than decreasing Mn(Ⅱ) concentration in solution. Our findings indicate that cysteine metabolism, particularly the intermediate H2S, plays a pivotal role in Mn(Ⅱ) resistance by mitigating the damage caused by reactive oxygen species. These findings provide new insights into the amino acid mechanisms associated with Mn(Ⅱ) resistance in bacteria.

Production of birnessite-type manganese oxides by biofilms from oxygen-supplemented biological activated carbon (BAC) filters

Biological oxidation of manganese (Mn) by bacteria results in the formation of biogenic Mn oxides (MnOx), which are known to be strong oxidants and effective catalysts. Manganese-oxidizing bacteria (MnOB) often...

Natural sunlight-driven oxidation of Mn2+(aq) and heterogeneous formation of Mn oxides on hematite

The oxidation of dissolved Mn2+(aq) plays a critical role in driving manganese cycles and regulating the fate of essential elements and contaminants in environmental systems. Based on sluggish oxidation rate, abiotic processes have been considered less effective oxidation pathway for manganese oxidation in environmental systems. Interestingly, a recent study (Jung et al., 2021) has shown that the rapid photochemical oxidation of Mn2+(aq) could be a feasible scenario to uncover the potential significance of abiotic Mn2+(aq) oxidation. Nevertheless, the significance of photochemical oxidation of Mn2+(aq) under natural sunlight exposure remains unclear. Here, we demonstrate the rapid photocatalytic oxidation of Mn2+(aq) and the heterogeneous growth of tunnel-structured Mn oxides under simulated freshwater and seawater conditions in the presence of natural sunlight and hematite. The natural sunlight-driven photocatalytic oxidation of Mn2+(aq) by hematite showed kinetic constants of 1.02 h−1 and 0.342 h−1 under freshwater and seawater conditions, respectively. The natural sunlight-driven photocatalytic oxidation rates are quite comparable to the results obtained from the previous laboratory test using artificial sunlight, which has ∼4.5 times stronger light intensity. It is likely because of ∼5.5 times larger light exposure area in the natural sunlight-driven photocatalytic oxidation than that of the laboratory test using artificial sunlight. We also elucidate the roles of cation species in controlling the oxidation rate of Mn2+(aq) and the crystalline structure of Mn oxide products. Specifically, in the presence of large amounts of cations, the oxidation rate of Mn2+(aq) was slower likely because of competitive adsorption. Furthermore, our findings highlight that Mg2+ contributes significantly to the formation of large-tunneled Mn oxides. These results illuminate the importance of abiotic photocatalytic processes in controlling the redox chemistry of Mn in real environmental aqueous systems on the oxidation of Mn2+(aq), and provide an environmentally sustainable approach to effectively remediate water contaminated with Mn2+(aq) using natural sunlight.

Effect of Predeformation on the High‐Temperature Oxidation Behavior of 436 Stainless Steel

The effect of a 30% predeformation treatment on the high‐temperature oxidation behavior of 436 stainless steel is investigated by oxidizing it at 900 °C for 100 h in air. After 48 h of oxidation, the undeformed sample primarily exhibits bilayer structures consisting of Cr‐rich oxide and outer Fe oxide, while the predeformed sample predominantly displays a single‐layer structure composed of Cr oxide. The oxidation mechanisms of predeformed and undeformed samples are clarified from the point of recrystallization through oxidation kinetic curves, surface and section micrographs, X‐ray diffraction (XRD), electron probe microanalyzer (EPMA), scanning electron microscope (SEM), energy‐dispersive spectroscopy (EDS), electron backscattered diffraction (EBSD), and line scanning characterization methods. The results show that after 1 h of oxidation, the grain size of the undeformed sample is 34.6 μm, and the grain size of the predeformed sample is 16.0 μm. This reduces the critical content required for the generation of protective Cr oxides and provides more diffusion channels for Cr elements, resulting in the formation of a greater amount of Cr oxides. Cr oxides can inhibit the formation of Fe and Mn oxides, thus delaying the onset of breakaway oxidation and improving its resistance to oxidation.

Fundamental aspects of phase formation in WC-based cemented carbides containing FeMn-based binders

The hardmetal industry is continuously seeking for (Co, Ni)-free binder alternatives. Several attempts have been made to use FeMn binders, Mn being a very effective austenite stabilizer. Substitution of Co binders for FeMn based binders comes along with many challenges such as: narrow carbon windows, evaporation of Mn during sintering or the formation of stable Mn-oxides. This work presents an overview on the phase formation in hardmetals with different carbon contents prepared from FeMn, FeMnSi and FeMnNi binders. Due to the efficient role of Mn as cementite stabilizer, it was not possible to avoid the presence of eta-carbides and cementite under the conditions studied, and samples with intermediate carbon contents presented both eta-carbides and cementite in the microstructure. Only after the addition of 25 wt% of Ni to the binder it was possible to observe materials with two phase microstructures. The challenges related to Mn evaporation and formation of stable oxides can be overcome by a proper selection of the starting materials and the sintering conditions. It is thus proved that the main challenge posed by these materials is the difficulty to obtain microstructures without detrimental phases.

The rare earth elements of sequentially leached phases in the loess-paleosol sequence at Weinan on the southeastern Chinese Loess Plateau

The rare earth elements (REEs) in loess sediments may preserve key information of paleoenvironmental changes in East Asia but remain poorly explored. Here we present the REE compositions of sequentially leached phases of loess sediments from a 16 m long loess-paleosol sequence collected from Weinan at the southern margin of the Chinese Loess Plateau (CLP). The REEs associated with carbonates, easily reducible oxides, reducible oxides, clay minerals, and the residual silicate minerals were sequentially leached with Na-acetate, hydroxylamine-HCl, Na-dithionite/Na-citrate, 12 mol L−1 HCl and concentrated HF-HNO3 solutions. The results show that the REE concentrations of different phases vary in the loess-paleosol layers and are most enriched in the easily reducible phase (except for the residual phase), which is likely explained by the association of REEs with Mn-oxides. Significant Eu anomalies can only be found in the carbonate and easily reducible phases, with the carbonate phase being characterized by appreciable positive Eu anomalies and the easily reducible phase being characterized by negative Eu anomalies, indicating the incorporation of Eu2+ into secondary carbonates that leaves the authigenic Mn-oxides with depleted Eu relative to other REEs. The carbonate phase shows significant negative Ce anomalies, which is likely due to the preferential removal of Ce4+ by Mn oxides before the formation of secondary carbonates. Nevertheless, appreciable positive Ce anomalies for the easily reducible phase can only be found at the bottom of the paleosol S1 while significant negative Ce anomalies were found within the paleosol S1, indicating the downward leaching of Ce4+ that shows stronger complexation with the organic matters than REE3+ in the soil solution. This may partly account for the negative Ce anomalies previously found in the paleosols. Overall, our results suggest a two-stage evolution of Eu and Ce anomalies of the carbonate phase, with the first stage controlled by the formation of both Mn-oxides and secondary carbonates and the second stage dominated by the precipitation of secondary carbonates. The comparison of carbonate Eu and Ce anomalies with other paleoclimatic proxies indicates that the combination of Eu and Ce anomalies of the carbonate fraction of loess may be applied as novel proxy records of climate change in East Asia.

Particle- and Light-Mediated Processes Control Seasonal Manganese Oxide Cycling in a Meromictic Pond

Manganese (Mn) oxides are strong oxidants and sorbents of nutrients and contaminants, thus their formation mechanisms impact multiple biogeochemical cycles. Manganese in oxic surface waters is often found as dissolved Mn species, such as Mn(II) and Mn(III)-ligand complexes, rather than Mn oxides. This is believed to be a result of Mn oxide reduction by hydrogen peroxide associated with photolysis of organic matter and direct organic matter-mediated reduction within sunlit waters. Nevertheless, Mn oxides can persist in some surface environments, which indicates an incomplete understanding of controls on Mn oxide distributions. Here, we couple field- and lab-based analyses to explore Mn oxide distributions, Mn oxidation rates, and underlying controls on Mn oxide formation within Siders Pond, a brackish and meromictic pond on Cape Cod (Massachusetts, USA) during the summer and fall of 2020. Manganese oxides were observed consistently in sunlit surface waters with concentrations declining to undetectable at the base of the chemocline. Surface Mn oxide concentrations were highest in late summer, reaching concentrations of ∼1 μM, and lowest in late fall, reaching only ∼50 nM. Minerals identified using synchrotron-based absorbance measurements were structurally similar to δ-MnO2 and feitknechtite. Substantial light-mediated Mn oxidation only took place in live incubations of Siders Pond water while net Mn reduction proceeded in killed incubations. Thus, total particle-mediated oxidation by microbes and minerals combined outpaced photoreduction, leading to net accumulation of Mn oxides within Siders Pond. Our results identify important roles for microbial- and mineral-mediated oxidation in determining Mn oxide distributions within surface waters of a natural setting, a finding that may help explain comparable distributions in other locations.

The effect of temperature on the release of silicon, iron and manganese into seawater from resuspended sediment particles

Sediments are considered to be refractory materials with limited influences on dissolved iron (dFe) pool in the ocean. However, recent field observations and laboratory experiments suggest that iron released from resuspended sediment particles and transported from continental margins is prone to fertilize large areas of the world ocean. Here we conducted a dissolution experiment to quantify the amount of dFe released from two types of resuspended sediments (silicate and calcite-rich) to open ocean surface seawater under two temperatures (5 and 15 °C). We followed pH, dissolved oxygen (dO2), phosphate, silicate, dissolved Fe and Mn concentrations (dFe and dMn), and bacterial abundance over 250 days. Extremely low and undetectable phosphate concentrations (<50 pmol kg−1) were measured throughout the duration of the experiment, causing limited bacteria growth and stable pH and dissolved O2 concentrations under all conditions. Silicate and dFe concentrations increased through time and high temperature (15 °C) induced more iron dissolution from the two sediments than low temperature (5 °C). Temperature had no effect on the dissolution of Mn. Our results further show that Fe and Mn are not released concurrently from the sediment source and that their distribution can be very different. Scavenging of Fe likely caused a decrease of dFe observed during the experiment, which was probably linked to the formation of Mn oxides. We also observed elevated dissolved Fe isotope ratios after dissolution, around +0.16 to +0.27‰. Isotopically heavy Fe was released from sediments to the dissolved pool during the dissolution but no difference in Fe isotope ratios was observed between the two temperature conditions. The Fe isotope fractionation can likely be attributed to ligand complexation and scavenging of Fe. These two mechanisms can be important factors not only in controlling the amount of Fe released from sediments but also in fractionating Fe isotopes at the sediment–seawater boundary.

Thallium isotope cycling between waters, particles, and sediments across a redox gradient

Thallium (Tl) isotopes are an emerging tool for tracking the history of molecular oxygen in seawater. Use of Tl isotopes in this manner requires a thorough understanding of the modern Tl isotope cycle, especially within the anoxic settings that typified Earth’s past oceans. To this end, we generated Tl concentration and isotope data for waters, particles, and sediments collected during three spring-summer-fall field seasons in Siders Pond, a salt-stratified and sulfide-rich (‘euxinic’) pond on Cape Cod (Massachusetts, USA). Over short timeframes (i.e., days to weeks), we observed a large degree of variability in the abundance (Tldiss = 9 pM–42 pM) and isotopic composition (ε205Tldiss = –3.9 ± 0.4; 2SD to –0.1 ± 0.7; 2SD) of dissolved Tl in pond surface waters. Thallium drawdown was common and favored removal of the lighter-mass Tl isotope. We surmise that biological Tl uptake plays a role in this phenomenon, but more work is warranted to confirm this hypothesis. Manganese oxides persisted in pond surface waters on many sampling days but had no obvious effect on Tldiss, only a slight effect on particulate ε205Tl values on the day of most prolific Mn oxide accumulation (driving ε205Tlpart as high as +0.9 ± 0.8; 2SD). In euxinic waters below the oxycline, rapid drawdown of dissolved Tl was observed on all sampling days together with a complimentary increase in particulate Tl (up to Tlpart = 21 pM). Strong associations between Tl and sulfide, and between Tl and other chalcophile metals (Mo and Cd), suggest that Tl is probably removed from euxinic waters in association with particulate sulfides, and seemingly with no resolvable isotopic fractionation effect despite non-quantitative Tl removal. The sediment data track the longer-term Tl cycle in the pond (i.e., across years) and reveal limited isotopic variability. Thallium isotope compositions leached from surface sediments match those predicted for contemporaneous waters, or nearly so, at all depths in the pond (above, within, and below the oxycline). Apparently, only a small fraction of the short-term Tl isotope variability found in the oxic surface waters of Siders Pond gets transferred to anoxic waters, and essentially none is transferred to sediments. Our results reaffirm the notion that Tl isotopes are uniquely capable of tracking long-term sedimentary Mn oxide burial – not mere Mn oxide formation. Our results also verify the ability of sediments formed under reducing conditions to capture the Tl isotope composition of contemporaneous waters. More broadly, the results of our investigation bolster our knowledge of the modern Tl isotope cycle and thereby permit more confident inferences of this cycle in Earth’s past.

Aqueous Co removal by mycogenic Mn oxides from simulated mining wastewaters

Naturally occurring manganese (Mn) oxide minerals often form by microbial Mn(II) oxidation, resulting in nanocrystalline Mn(III/IV) oxide phases with high reactivity that can influence the uptake and release of many metals (e.g., Ni, Cu, Co, and Zn). During formation, the structure and composition of biogenic Mn oxides can be altered in the presence of other metals, which in turn affects the minerals’ ability to bind these metals. These processes are further influenced by the chemistry of the aqueous environment and the type and physiology of microorganisms involved. Conditions extending to environments that typify mining and industrial wastewaters (e.g., increased salt content, low nutrient, and high metal concentrations) have not been well investigated thus limiting the understanding of metal interactions with biogenic Mn oxides. By integrating geochemistry, microscopic, and spectroscopic techniques, we examined the capacity of Mn oxides produced by the Mn(II)-oxidizing Ascomycete fungus Periconia sp. SMF1 isolated from the Minnesota Soudan Mine to remove the metal co-contaminant Co(II) from synthetic waters that are representative of mining wastewaters currently undergoing remediation efforts. We compared two different applied remediation strategies under the same conditions: coprecipitation of Co with mycogenic Mn oxides versus adsorption of Co with pre-formed fungal Mn oxides. Co(II) was effectively removed from solution by fungal Mn oxides through two different mechanisms: incorporation into, and adsorption onto, Mn oxides. These mechanisms were similar for both remediation strategies, indicating the general effectiveness of Co(II) removal by these oxides. The mycogenic Mn oxides were primarily a nanoparticulate, poorly-crystalline birnessite-like phases with slight differences depending on the chemical conditions during formation. The relatively fast and complete removal of aqueous Co(II) during biomineralization as well as the subsequent structural incorporation of Co into the Mn oxide structure illustrated a sustainable cycle capable of continuously remediating Co(II) from metal-polluted environments.

Physical and biogeochemical controls on seasonal iron, manganese, and cobalt distributions in Northeast Atlantic shelf seas

Dissolved (<0.2 μm) trace metals (dTMs) including iron (Fe), manganese (Mn), and cobalt (Co) are micronutrients that (co-) limit phytoplankton growth in many ocean regions. Here, we present the spatial and seasonal distributions of dFe, dMn, and dCo on the Northeast Atlantic continental margin (Celtic Sea), along a transect across the shelf and two off-shelf transects along a canyon and a spur. Waters on the continental shelf showed much higher dTM concentrations (dFe 0.07–6.50 nmol L−1, average 1.41 ± 0.96 nmol L−1, n = 138; dMn 0.868–14.8 nmol L−1, 2.75 ± 2.37 nmol L−1, n = 148; dCo 54.8–217 pmol L−1, 109 ± 32 pmol L−1, n = 144) than on the slope (dFe 0.03–1.90 nmol L−1, 0.65 ± 0.43 nmol L−1, n = 454; dMn 0.223–1.14 nmol L−1, 0.58 ± 0.20 nmol L−1, n = 458; dCo 27.3–122 pmol L−1, 71.7 ± 11.7 pmol L−1, n = 441), attributed to strong dTM contributions from a low-salinity endmember, i.e., riverine discharge. Benthic sedimentary input via reductive dissolution (especially for dFe and dMn), delineated by short-lived radium (Ra) isotopic activities (223Raxs and 224Raxs), was only prominent at a station (Site A) characterized by fine sediments. On the continental slope, dMn levels at depth were mainly determined by the formation of insoluble Mn oxides and the intrusion of Mediterranean Outflow Waters. In contrast, dFe and dCo concentrations at depth were balanced by the regeneration from remineralization of sinking organic particles and scavenging removal. In addition, bottom and intermediate nepheloid layers along the slope illustrated both elevated dTM concentrations and Ra isotopic activities. The presence of nepheloid layers is especially significant along the canyon transect relative to the spur transect, demonstrating the importance of slope topography on the off-shelf transport of dTMs into the Northeast Atlantic Ocean.As a seasonal stratified shelf sea, dTMs and nutrients showed synchronized seasonal variations on the shelf, indicating the influence of biological processes in addition to source effects. Surface dFe and dCo were depleted in summer due to enhanced biological uptake, while sub-surface dFe and dCo were elevated in summer and autumn ascribed to the remineralization of sinking organic particles. In contrast, surface dMn levels were predominantly controlled by the seasonal variations in photoreduction, while sub-surface dMn concentrations were relatively constant throughout the year. The combined effects of fluvial and benthic sources, topographical controls, and biological processes shape the seasonal variations of dTM distributions. Such seasonal variations in dTMs and biological activities can affect the biological carbon pump on the Northeast Atlantic continental margin, and may further influence the carbon cycle in the Atlantic Ocean via the dynamic dTM exchange between continental margins and the open ocean.

The Formation and Transformation of Manganese Oxide Minerals on the Surface of Kaolinite

AbstractThe formation of manganese (Mn) oxides is influenced by environmental conditions and, in some red soils, Mn oxides occur as coatings on the surface of kaolinite particles in the form of colloidal films or fine particles. The present study aimed to explore the types of formation mechanisms of Mn oxide minerals on the surface of kaolinite. Mn oxide minerals synthesized by reducing the Mn in KMnO4 with a divalent Mn salt (MnSO4) were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of various initial molar ratios of Mn2+/Mn7+ (R = 1:0.67, 1:1, 1:2, and 1:4), cationic species (Na+ or Mg2+), synthesis temperatures (30, 60, and 110°C), and amount of added kaolinite (0.25, 0.5, 1.0, 2.0, and 5.0 g) on the formation of Mn oxides were studied. The results showed that Mn oxide mineral types were affected by the initial R value and the background cation. With decreases in the initial R value, the synthesized minerals transformed from cryptomelane to birnessite. The relative mass ratios of kaolinite to Mn oxide were calculated as 1:0.92, 1:0.63, 1:1.15, and 1:1.63. The sodium cation (Na+) had a greater role than Mg2+ in promoting the dissolution–recrystallization of birnessite to cryptomelane. The synthesis temperature had no effect on mineral types, but Mn content increased as temperature increased. When the amount of added kaolinite was increased from 0.25 to 5.0 g, Mn oxide minerals formed gradually and transformed from birnessite to cryptomelane. This work revealed a possible formation process and reaction mechanism on the surface of kaolinite particles in some red soils.

Soil addition of MnSO4 reduces wheat Cd accumulation by simultaneously increasing labile Mn and decreasing labile Cd concentrations in calcareous soil: A two-year pot study

Cadmium (Cd) pollution of wheat fields is a serious environmental and health problem that warrants attention. Manganese (Mn)-containing materials are considered effective for inhibiting Cd accumulation in Cd-contaminated acidic soils. However, information on the long-term remediation effects of Mn fertilizers on Cd accumulation in wheat and on the microbial community in calcareous soils remain limited. Here, a two-year pot experiment was conducted to assess the performance of 0.05–0.2% MnSO4 addition in Cd-contaminated calcareous soils (total Cd concentration: 3.65 mg/kg) on Cd accumulation in wheat as well as on the soil bacterial community. The formation of Mn oxides and transformation of exchangeable Cd to stable Cd fractions confirmed that the application of MnSO4 significantly decreased CaCl2-extractable Cd concentrations in soil (0–47.08%). In addition, MnSO4 addition improved the antagonistic effect of Cd and Mn ions in the wheat rhizosphere by increasing the available Mn concentration in the soil (1.04–3.52 times), thereby significantly reducing wheat Cd accumulation by 24.66–54.70%. Notably, the addition of MnSO4 did not affect the richness and diversity (P > 0.05) but altered the composition and function of bacterial communities, especially those involved in metabolism and genetic information processing. Importantly, the effects of MnSO4 on Cd immobilization in soil (10.66–47.08%) and the inhibition of Cd accumulation in wheat (12.13–54.30%) can last for two years after one addition. Furthermore, the maximum decrease in Cd concentration in grains was found in the low-Cd wheat cultivar, with values of 31.39–54.70% and 19.94–54.30% in the first and second years, respectively. Based on the present findings, the combination of MnSO4 with a low-Cd wheat cultivar is effective for the safe utilization of Cd-contaminated calcareous soils.

Direct observation of Mn distribution/speciation within and surrounding a basidiomycete fungus in the production of Mn-oxides important in toxic element containment

Biogenic manganese (Mn) oxides occur ubiquitously in the environment including the uranium (U) mill tailings at the Ningyo-toge U mine in Okayama, Japan, being important in the sequestration of radioactive radium. To understand the nanoscale processes in Mn oxides formation at the U mill tailings site, Mn2+ absorption by a basidiomycete fungus, Coprinopsis urticicola, isolated from Ningyo-toge mine water samples, was investigated in the laboratory under controlled conditions utilizing electron microscopy, synchrotron-based X-ray analysis, and fluorescence microscopy with a molecular pH probe. The fungus’ growth was first investigated in an agar-solidified medium supplemented with 1.0 mmol/L Mn2+, and Cu2+ (0–200 μM), Zn2+ (0–200 μM), or diphenyleneiodonium (DPI) chloride (0–100 μM) at 25 °C. The results revealed that Zn2+ has no significant effects on Mn oxide formation, whereas Cu2+ and DPI significantly inhibit both fungal growth and Mn oxidation, indicating superoxide-mediated Mn oxidation. Indeed, nitroblue tetrazolium and diaminobenzidine assays on the growing fungus revealed the production of superoxide and peroxide. During the interaction of Mn2+ with the fungus in solution medium at the initial pH of 5.67, a small fraction of Mn2+ infiltrated the fungal hyphae within 8 h, forming a few tens of nm-sized concentrates of soluble Mn2+ in the intracellular pH of ∼6.5. After 1 day of incubation, Mn oxides began to precipitate on the hyphae, which were characterized as fibrous nanocrystals with a hexagonal birnessite-structure, these forming spherical aggregates with a diameter of ∼1.5 μm. These nanoscale processes associated with the fungal species derived from the Ningyo-toge mine area provide additional insights into the existing mechanisms of Mn oxidation by filamentous fungi at other U mill tailings sites under circumneutral pH conditions. Such processes add to the class of reactions important to the sequestration of toxic elements.