Formation Of Mn Oxides Research Articles

Effects of Mn on the mechanical properties and high temperature oxidation of 9Cr2WVTa steel

The mechanical properties and high temperature oxidation behaviors of 9Cr2WVTa steels with Mn contents in the range of 0.04–0.93 wt% were investigated. There are no obvious differences in the tensile properties at room temperature and high temperature, only a slight reduction in the impact toughness when Mn content reaches 0.93 wt%. Remarkably, the high temperature oxidation resistance is significantly improved with an increase of Mn content. After 500 h of oxidation, a (Fe0.6Cr0.4)2O3 oxide scale is developed on the steel with 0.04 wt% Mn, Mn1.5Cr1.5O4 oxides are occasionally detected when Mn content reaches 0.47 wt%, while a thin compact scale with a mixture of Mn1.5Cr1.5O4 and Cr1.3Fe0.7O3 oxides is formed on the steel containing 0.93 wt% Mn. Addition of Mn promotes the formation of Mn-oxides, which lowers oxygen partial pressure and accelerates external oxidation of Cr. At last, the presence of Mn-Cr spinels and Cr-rich oxides improves the oxidation resistance.

Biogenic manganese oxides generated by green algae Desmodesmus sp. WR1 to improve bisphenol A removal

Biogenic manganese oxides (BioMnOx) have attracted considerable attention as active oxidants, adsorbents, and catalysts. This study investigated the characteristics of algae-generated BioMnOx and determined its oxidative activity towards bisphenol A (BPA), an endocrine disrupter. Amorphous nanoparticles with a primary Mn valency of +3 were found in BioMnOx produced by Desmodesmus sp. WR1. The mechanism might be that algal growth created conditions favorable to Mn oxidation through increasing DO and pH. Initial Mn2+ concentrations of 6, 30, and 50mgL−1 produced a maximum of 5, 13, and 11mgL−1 of BioMnOx, respectively. Mn2+-enriched cultures exhibited the highest BPA removal efficiency (∼78%), while controls only reached about 27%. BioMnOx may significantly promote BPA oxidation in algae culture, enhancing the accumulation of substrates for glycosylation. Moreover, continuous BioMnOx increase and Mn2+ decrease during BPA oxidation confirmed Mn oxide regeneration. In conclusion, Mn oxide formation by microalgae has the potential to be used for environmental remediation.

Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6–24mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite>goethite>ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O2 on ferrihydrite surfaces should include an electrochemical pathway, i.e., electron transfer (ET) in the Mn(II)-Conduction Band (CB)Ferrihydrite-O2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e., ET in the Mn(II)-Fe(II, III)-O2 complexes and direct ET in the Mn(II)-O2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments.

Diverse manganese(II)-oxidizing bacteria are prevalent in drinking water systems.

Manganese (Mn) oxides are highly reactive minerals that influence the speciation, mobility, bioavailability and toxicity of a wide variety of organic and inorganic compounds. Although Mn(II)-oxidizing bacteria are known to catalyze the formation of Mn oxides, little is known about the organisms responsible for Mn oxidation in situ, especially in engineered environments. Mn(II)-oxidizing bacteria are important in drinking water systems, including in biofiltration and water distribution systems. Here, we used cultivation dependent and independent approaches to investigate Mn(II)-oxidizing bacteria in drinking water sources, a treatment plant and associated distribution system. We isolated 29 strains of Mn(II)-oxidizing bacteria and found that highly similar 16S rRNA gene sequences were present in all culture-independent datasets and dominant in the studied drinking water treatment plant. These results highlight a potentially important role for Mn(II)-oxidizing bacteria in drinking water systems, where biogenic Mn oxides may affect water quality in terms of aesthetic appearance, speciation of metals and oxidation of organic and inorganic compounds. Deciphering the ecology of these organisms and the factors that regulate their Mn(II)-oxidizing activity could yield important insights into how microbial communities influence the quality of drinking water.

Bioleaching of manganese by Aspergillus sp. isolated from mining deposits

A comprehensive study on fungus assisted bioleaching of manganese (Mn) was carried out to demonstrate Mn solubilization of collected low grade ore from mining deposits of Sanindipur, Odisha, India. A native fungal strain MSF 5 was isolated and identified as Aspergillus sp. by Inter Transcribed Spacer (ITS) sequencing. The identified strain revealed an elevated tolerance ability to Mn under varying optimizing conditions like initial pH (2, 3, 4, 5, 6, 7), carbon sources (dextrose, sucrose, fructose and glucose) and pulp density (2%, 3%, 4%, 5% and 6%). Bioleaching studies carried out under optimized conditions of 2% pulp density of Mn ore at pH 6, temperature 37 °C and carbon dosage (dextrose) resulted with 79% Mn recovery from the ore sample within 20 days. SEM-EDX characterization of the ore sample and leach residue was carried out and the micrographs demonstrated porous and coagulated precipitates scattered across the matrix. The corresponding approach of FTIR analysis regulating the Mn oxide formation shows a distinctive peak of mycelium cells with and without treated Mn, resulting with generalized vibrations like MnOx stretching and CH2 stretch. Thus, our investigation endeavors’ the considerate possible mechanism involved in fungal surface cells onto Mn ore illustrating an alteration in cellular Mn interaction.

Cyclic-oxidation behaviours of the powder-metallurgy TiAl–4Nb–3Mn and TiAl–2Nb–2Mo beta-gamma alloys

ABSTRACTFor this study, cyclic-oxidation tests for the powder-metallurgy TiAl–4Nb–3Mn and TiAl–2Nb–2Mo alloys were carried out in air between room temperature and 900°C, and the oxidation behaviours under cyclic oxidation were compared with those under isothermal oxidation. The morphologies and structures of the oxides are identical to those from isothermal oxidation, except for the Mn-oxide formation on the top surface in the case of the TiAl–4Nb–3Mn alloy. The growth rate of the oxides in the TiAl–2Nb–2Mo alloy is slower and more stable than that of the oxides in the TiAl–4Nb–3Mn alloy, and severe internal oxidation is also evident in the latter alloy; however, the weight gain showed a sudden drop in the TiAl–2Nb–2Mo alloy that is mainly due to the enhanced formation of titanium nitrides at the interface.

Cerium sequestration and accumulation in fractured crystalline bedrock: The role of Mn-Fe (hydr-)oxides and clay minerals

This study focuses on the mechanisms of Ce sequestration and accumulation in the fracture network of the upper kilometer of the granitoid bedrock of the Baltic Shield in southeast Sweden (Laxemar area, Sweden). The material includes 81 specimens of bulk secondary mineral precipitates (“fracture coatings”) collected on fracture walls identified in 17 drill cores, and 66 groundwater samples collected from 21 deep boreholes with equipment designed for retrieval of representative groundwater at controlled depths. The concentrations of Ce in the fracture coatings, although varying considerably (10–90th percentiles: 67–438mgkg−1), were frequently higher than those of the wall rock (10–90th percentiles: 70–118mgkg−1). Linear combination fitting analysis of Ce LIII-edge X-ray absorption near-edge structure (XANES) spectra, obtained for 19 fracture coatings with relatively high Ce concentrations (⩾145mgkg−1) and a wide range of Ce-anomaly values, revealed that Ce(IV) occurs frequently in the upper 10m of the fracture network (Ce(IV)/Cetotal=0.06–1.00 in 8 out of 11 specimens) and is mainly associated with Mn oxides (modeled as Ce oxidatively scavenged by birnessite). These features are in line with the strong oxidative and sorptive capacities of Mn oxide as demonstrated by previous studies, and abundant todorokite and birnessite-like Mn oxides identified in 3 out of 4 specimens analyzed by Mn K-edge X-ray absorption spectroscopy (XAS) in the upper parts of the fracture network (down to 5m). For a specimen with very high Ce concentration (1430mgkg−1) and NASC-normalized Ce anomaly (3.63), the analysis of Ce XANES and Mn XAS data revealed (i) a predominance of Ce oxide in addition to Ce scavenged by Mn oxide; and (ii) a large fraction of poorly-crystalline hexagonal birnessite and aqueous Mn2+, suggesting a recent or on-going oxidation of Mn2+ in this fracture. In addition, the Ce oxide precipitates on this fracture observed by in situ SEM-EDS contained considerable amounts of Mn. These spectroscopic and microscopic features led us to suggest that the remarkable accumulation of Ce(IV) in this fracture is a result of repeated formation and dissolution of Mn oxides, that is, formation of Mn oxide followed by oxidative scavenging of Ce as Ce oxide nanoparticles, which largely remained during the subsequent reductive dissolution of the Mn oxides. In addition, the XANES data indicate that goethite has the capability to oxidize Ce at near-neutral pH under our experimental conditions (goethite reacted with 0.001M Ce for 48h in a glove box with O2 <1ppm). This previously unrecognized Ce oxidation pathway also seems to contribute to a minor extent to the oxidative scavenging of Ce in the fracture network. Trivalent Ce in the fracture coatings, in particular below 2.5m, is mainly sorbed as inner-sphere complexes on clay minerals. Taking into account the facts that Ce in the present groundwater is scarce and modeled to be largely complexed with humic substance, it is argued that the inner-sphere complexes were mainly formed from past (Paleozoic) hydrothermal fluids.

A new discrimination scheme for oceanic ferromanganese deposits using high field strength and rare earth elements

Ferromanganese (Fe-Mn) deposits constitute a ubiquitous mineral type in oceanic settings, with metal (Cu, Ni, Zn, Co, Pt) and rare earth element (REE) enrichments of potential economic interest. Routine analysis of trace elements by ICP-MS has advanced our understanding of the impact of hydrogenetic, diagenetic and hydrothermal processes on the mobility and interaction of high field strength elements (HFSE: Zr and Ti) and REE and yttrium (REY) with Fe-Mn oxyhydroxides. Recent discoveries in the French exclusive economic zone (EEZ) of Wallis and Futuna (southwest Pacific Ocean) have brought new insight into the formation of low temperature (LT) hydrothermal Mn deposits and lead us to reconsider the classification and discrimination diagrams for Fe-Mn deposits and ore-forming processes. Using a suite of LT hydrothermal Fe-Mn crusts from Wallis and Futuna, we investigate how contrasting genetic processes influence the distribution of metals (Mn, Fe, Cu, Ni, and Co), HFSE and REY in hydrogenetic, diagenetic, hydrothermal and mixed-type deposits from different environments in the global ocean. The interaction of the different metal oxide-forming processes indicates that: (i) enrichment of Co, HFSE and REY is favored by hydrogenetic precipitation, (ii) diagenetic processes produce higher Mn, Cu, and Ni concentrations with oxic remobilization in the sedimentary column, while suboxic conditions promote greater Mn and Fe remobilization that competes with the incorporation of Cu and Ni ions in nodules. HFSE and REY derived from seawater are usually low in diagenetic precipitates, which discriminate between hydrogenetic and diagenetic inputs within nodules, (iii) hydrothermal Fe-Mn deposits show strong depletion in HFSE and REY due to rapid formation and high contents of either Fe or Mn oxides. We present a new discrimination scheme for the genetic types of Fe-Mn deposits using a 10∗(Cu+Ni+Co)−100∗(Zr+Y+Ce)−(Fe+Mn)/4 ternary diagram. The use of HFSE and REY in the classification allows for a more robust discrimination of: (i) each ore-forming process with well-delimited fields, without overlap of metal-rich hydrothermal samples and hydrogenetic samples, (ii) oxic and suboxic diagenesis within nodules, (iii) trends between hydrogenetic and diagenetic end-members forming a continuum, and (iv) mixed genetic types such as the presence of hydrothermal particles within hydrogenetic crust layers. Alternatives are also explored to adapt our discriminative diagram to elements measurable by on-board instruments to aid in exploration at sea.

Removal of manganese in batch and fluidized bed systems using beads of zeolite a as adsorbent

In this study the uptake capacity of Mn(II) ions by zeolite A beads was investigated for different initial Mn concentration (100–400 mg Mn dm−3) in batch mode at 25–55 °C. The obtained adsorption capacity varying from 30 to 50 mg Mn g−1 demonstrated a high affinity of zeolite A towards Mn(II) present in solutions. Kinetic studies indicated the intra-particle diffusion as the rate limiting step up to 45 °C with apparent diffusivities in the range (1.2–2.0) × 10−13 m2 s−1 and the activation energy of 21.9 kJ mol−1, which implies strong interactions between the zeolite A and Mn ions. At 55 °C ion-exchange became the rate limiting step. The adsorption isotherms were studied at 25 °C showing that the Mn adsorption is the best described by the Langmuir model suggesting a homogenous zeolite surface. XPS analysis of the Mn-loaded beads showed that there is no surface accumulation of Mn but an almost uniform Mn distribution inside zeolite A, whereas XANES and EXAFS suggested that the adsorption of Mn(II) was followed by the Mn(II) oxidation and oxide formation. Regeneration of the spent zeolite was examined in 8 adsorption/desorption cycles by a chelating Na2EDTA in a fluidized column. It has been found that zeolite A beads could be reused for at least 4 cycles with satisfactory Mn(II) adsorption efficiencies of about 70%.

Evidence for the biogenic origin of manganese-enriched layers in Lake Superior sediments.

Manganese (Mn) and iron (Fe)-enriched sediment layers were discovered in Lake Superior within, above and below the oxic-anoxic interface. While the role of bacteria in redox reactions with Mn is known to be significant, little information exists about indigenous microbial communities in many freshwater environments. This study examined the bacterial communities of Mn-enriched layers in Lake Superior to identify the potential Mn(II) oxidizers responsible for the formation of Mn oxides. Anaerobic Mn(II) oxidation occurring in the Mn-enriched layers at the oxic-anoxic interface was investigated using Mn(II)-enriched cultures. High-resolution microscopic and spectroscopic investigations provided evidence of the biogenic formation of Mn oxides on cell surfaces. Spectroscopic mapping confirmed high levels of Mn in structures resembling biogenic Mn oxides. These structures were observed in enrichment cultures and in Mn-enriched layer sediment samples, indicating the significance of biogenic Mn oxidation occurring in situ. 16S ribosomal DNA pyrosequencing was used to identify the bacteria potentially responsible for Mnoxide formation in the enrichment cultures and Mn-enriched layers, revealing that the Mn-enriched layer contains classes with known Mn(II)-oxidizing members. Pyrosequencing of bacterial cultures suggested that these bacteria may be Bacillus strains, and that anaerobic microbial-mediated Mn(II) oxidation contributes to the formation of the layers.

Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH)2.

The early formation of manganese (hydr)oxide nanoparticles at mineral-water interfaces is crucial in understanding how Mn oxides control the fate and transport of heavy metals and the cycling of nutrients. Using atomic force microscopy, we investigated the heterogeneous nucleation and growth of Mn (hydr)oxide under varied ionic strengths (IS; 1-100 mM NaNO3). Experimental conditions (i.e., 0.1 mM Mn(2+) (aq) concentration and pH 10.1) were chosen to be relevant to Mn remediation sites. We found that IS controls Mn(OH)2 (aq) formation, and that the controlled Mn(OH)2 (aq) formation can affect the system's saturation and subsequent Mn(OH)2 (s) and further Mn3O4 (s) nanoparticle formation. In 100 mM IS system, nucleated Mn (hydr)oxide particles had more coverage on the quartz substrate than those in 1 mM and 10 mM IS systems. This high IS also resulted in low supersaturation ratio and thus favor heterogeneous nucleation, having better structural matching between nucleating Mn (hydr)oxides and quartz. The unique information obtained in this work improves our understanding of Mn (hydr)oxide formation in natural as well as engineered aqueous environments, such as groundwater contaminated by natural leachate and acid mine drainage remediation.

Coupled sulfur, iron and molybdenum isotope data from black shales of the Teplá-Barrandian unit argue against deep ocean oxygenation during the Ediacaran

The Earth’s atmosphere and hydrosphere changed from an Archean anoxic to a modern oxygenated world in two major steps, the Paleoproterozoic Great Oxidation Event (2.4–2.3 billion years ago) and the Neoproterozoic Oxidation Event (0.8–0.5 billion years ago). Both events had a strong influence on the availability of redox sensitive and bio-essential metals within the ocean and are, thus, strongly linked to fundamental biological innovations and diversification. Biological diversification during the Precambrian–Cambrian transition between 555 and 540 million years ago may have been driven by ocean–atmosphere oxygenation. The exact timing and the extent of (deep) ocean oxygenation within this time period remains unresolved though.Here we present major and trace element compositions as well as Mo, S and Fe isotopic data of organic-rich black shales from the Teplá-Barrandian unit, Czech Republic. New in situ zircon U–Pb ages provide a maximum depositional age of 559.8±3.8 million years. Black shales with strong metal enrichment show low δ56Fe values due to the dominance of authigenic pyrite-Fe with δ56Fe values around −0.6‰ over detrital Fe with δ56Fe values around 0.1‰. Samples with lower authigenic metal enrichment show relatively low Mo/TOC ratios and increasing δ34S values, which is interpreted to reflect basinal restriction and longer seawater renewal times. In analogy to the modern Black Sea, the accompanied depletion of basinal Moaq due to near quantitative Mo removal might have led to the preservation of the seawater δ98Mo in the respective black shales. Our best estimate for this seawater Mo isotopic composition <560 million years ago is +1.2‰ in δ98Mo, which is nearly identical to seawater δ98Mo values inferred from Mid-Proterozoic black shales. The lack of higher δ98Mo values in black shales (and seawater) argues against contemporaneous Mn oxide formation in well oxygenated deep sea settings, which would preferentially adsorb isotopically light Mo leaving behind an isotopically heavy ocean. By contrast, the deep ocean might have remained ferruginous with the hydrothermal Fe still outbalancing surficial oxygen production. Our results therefore contribute to a growing data set, which suggests limited deep water oxygenation during major biological innovations in the late Ediacaran period.

Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1.

Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

The age of supergene manganese deposits in Katanga and its implications for the Neogene evolution of the African Great Lakes Region

Supergene manganese deposits commonly contain K-rich Mn oxides with tunnel structure, such as cryptomelane, which are suitable for radiometric dating using the 39Ar–40Ar method. In Africa, Mn deposits have been dated by this method for localities in western and southern parts of the continent, whereas only some preliminary data are available for Central Africa. Here we present new 39Ar–40Ar ages for Mn oxide samples of the Kisenge deposit, in southwestern Katanga, Democratic Republic of the Congo. The samples represent supergene Mn oxide deposits that formed at the expense of primary Paleoproterozoic rhodochrosite-dominated carbonate ores. Main phases of Mn oxide formation are dated at c. 10.5Ma, 3.6Ma and 2.6Ma for a core that crosses a mineralized interval. The latter shows a decrease in age with increasing depth, recording downward penetration of a weathering front. Surface samples of the Kisenge deposits also record a ≥c.19.2Ma phase, as well as c. 15.7Ma, 14.2Ma and 13.6Ma phases. The obtained ages correspond to distinct periods of paleosurface development and stability during the Mio-Pliocene in Katanga. Because Katanga is a key area bordered to the North by the Congo Basin and to the East by the East African Rift System, these ages also provide constraints for the geodynamic evolution of the entire region. For the Mio-Pliocene, the Kisenge deposits record ages that are not systematically found elsewhere in Africa, although the 10.5–11Ma event corresponds to a roughly simultaneous event in the Kalahari Manganese Field, South Africa. The rest of the Katanga paleosurface record differs somewhat from records for other parts of Africa, for which older, Eocene ages have been obtained. This difference is most probably related to the specific regional geodynamic context: uplift of the East African Plateau, with associated erosion, and the opening of the East African Rift System at c. 25Ma are events whose effects, in the study area, interfere with those of processes responsible for the development of continent-wide paleosurfaces.

Extracellular haem peroxidases mediate Mn(II) oxidation in a marine Roseobacter bacterium via superoxide production.

Manganese (Mn) oxides are among the strongest sorbents and oxidants in environmental systems. A number of biotic and abiotic pathways induce the oxidation of Mn(II) to Mn oxides. Here, we use a combination of proteomic analyses and activity assays, to identify the enzyme(s) responsible for extracellular superoxide-mediated Mn oxide formation by a bacterium within the ubiquitous Roseobacter clade. We show that animal haem peroxidases (AHPs) located on the outer membrane and within the secretome are responsible for Mn(II) oxidation. These novel peroxidases have previously been implicated in direct Mn(II) oxidation by phylogenetically diverse bacteria. Yet, we show that in this Roseobacter species, AHPs mediate Mn(II) oxidation not through a direct reaction but by producing superoxide and likely also by degrading hydrogen peroxide. These findings point to a eukaryotic-like oscillatory oxidative-peroxidative enzymatic cycle by these AHPs that leads to Mn oxide formation by this organism. AHP expression appears unaffected by Mn(II), yet the large energetic investment required to produce and secrete these enzymes points to an as yet unknown physiological function. These findings are further evidence that bacterial peroxidases and secreted enzymes, in general, are unappreciated controls on the cycling of metals and reactive oxygen species (ROS), and by extension carbon, in natural systems.

Microbial community composition of a household sand filter used for arsenic, iron, and manganese removal from groundwater in Vietnam

Household sand filters are used in rural areas of Vietnam to remove As, Fe, and Mn from groundwater for drinking water purposes. Currently, it is unknown what role microbial processes play in mineral oxide formation and As removal during water filtration. We performed most probable number counts to quantify the abundance of physiological groups of microorganisms capable of catalyzing Fe- and Mn-redox transformation processes in a household sand filter. We found up to 104cellsg−1 dry sand of nitrate-reducing Fe(II)-oxidizing bacteria and Fe(III)-reducing bacteria, and no microaerophilic Fe(II)-oxidizing bacteria, but up to 106cellsg−1 dry sand Mn-oxidizing bacteria. 16S rRNA gene amplicon sequencing confirmed MPN counts insofar as only low abundances of known taxa capable of performing Fe- and Mn-redox transformations were detected. Instead the microbial community on the sand filter was dominated by nitrifying microorganisms, e.g. Nitrospira, Nitrosomonadales, and an archaeal OTU affiliated to Candidatus Nitrososphaera. Quantitative PCR for Nitrospira and ammonia monooxygenase genes agreed with DNA sequencing results underlining the numerical importance of nitrifiers in the sand filter. Based on our analysis of the microbial community composition and previous studies on the solid phase chemistry of sand filters we conclude that abiotic Fe(II) oxidation processes prevail over biotic Fe(II) oxidation on the filter. Yet, Mn-oxidizing bacteria play an important role for Mn(II) oxidation and Mn(III/IV) oxide precipitation in a distinct layer of the sand filter. The formation of Mn(III/IV) oxides contributes to abiotic As(III) oxidation and immobilization of As(V) by sorption to Fe(III) (oxyhydr)oxides.

Effects of preparation conditions on Mn-based activated carbon catalysts for desulfurization

Ultrasonic oscillation cannot change the formation of Mn oxides and types of functional groups, but calcination temperatures are key factors.

Zn sorption to biogenic bixbyite-like Mn2O3 produced by Bacillus CUA isolated from soil: XAFS study with constraints on sorption mechanism

Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. Compared to hexagonal birnessites, the sorption characteristics and the underlying mechanism of adsorption of heavy-metal ions to those of the other biogenic Mn oxides are still rarely addressed. A strain of Mn-oxidizing bacteria isolated from Claypani-Udic Argosols was identified as Bacillus with 16S rRNA sequencing analysis. The bacterial Mn(II) oxidation product is a poorly crystallized bixbyite-like Mn2O3 (α-Mn2O3). The maximum adsorption capacities of Zn(II) onto the biogenic Mn oxide at pH6.00 and pH4.00 were 663mmol/kg and 629mmol/kg, respectively. The complex structure of adsorbed Zn2+ was constrained using Zn EXAFS analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO6 octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. At a relatively low Zn2+ loading (100mmol/kg, pH6.00), Zn2+ adsorbed onto the biogenic Mn oxide with two types of tetrahedrally coordinated complexes, i.e. (1) coordinated with one regular/distorted MnO6 octahedron as a monodentate–mononuclear complex and (2) with two MnO6 octahedra (two regular, two distorted or a regular and a distorted) as a bidentate–binuclear complex. While, at a relatively high Zn2+ loading (556mmol/kg, pH4.00; 635mmol/kg, pH6.00), two types of octahedrally coordinated complexes are constrained, i.e. (1) coordinated with one regular/distorted MnO6 octahedron as a monodentate–mononuclear complex and (2) with one regular MnO6 octahedron as a bidentate mononuclear complex. This research extends further understanding on the formation of biogenic Mn oxides in the environment and the adsorption mechanism of heavy metals onto low-valence Mn oxides with distorted structures. The application of low valence biogenic Mn oxides to efficiently remove heavy metals from water is also shown to be promising.

Microbial Communities Promoting Mn(II) Oxidation in Ashumet Pond, a Historically Polluted Freshwater Pond Undergoing Remediation

An extensive culture-dependent and -independent study was conducted to identify microorganisms contributing to the biogeochemical cycling of manganese (Mn) in Ashumet Pond, a freshwater pond in Massachusetts currently undergoing remediation. A variety of bacteria (including Gamma-, Beta-, and Alpha-proteobacteria, Firmicutes, and Bacteroides) and Ascoymete fungi were isolated from the pond that promote Mn(II) oxidation and subsequent formation of Mn(III/IV) oxide minerals. Targeted-amplicon pyrosequencing of the bacterial and fungal communities associated with Mn oxide-encrusted samples show a highly diverse microbial community, of which the cultured phylotypes represent a minor proportion. This suggests a larger community, not identified through culturing, contributes to Mn oxide formation within the Pond.

Identification of Mn(II)-Oxidizing Bacteria from a Low-pH Contaminated Former Uranium Mine

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments.