Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation.

PubMed

Tang, Yuanzhi; Zeiner, Carolyn A; Santelli, Cara M; Hansel, Colleen M

2013-04-01

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by six Mn(II)-oxidizing Ascomycete fungi. All fungal species substantially enhanced rhodochrosite dissolution and surface modification. Mineral-hosted Mn(II) was oxidized resulting in formation of Mn(III/IV) oxides that were all similar to δ-MnO2 but varied in morphology and distribution in relation to cellular structures and the MnCO3 surface. For four fungi, Mn(II) oxidation occurred along hyphae, likely mediated by cell wall-associated proteins. For two species, Mn(II) oxidation occurred via reaction with fungal-derived superoxide produced at hyphal tips. This pathway ultimately resulted in structurally unique Mn oxide clusters formed at substantial distances from any cellular structure. Taken together, findings for these two fungi strongly point to a role for fungal-derived organic molecules in Mn(III) complexation and Mn oxide templation. Overall, this study illustrates the importance of fungi in rhodochrosite dissolution, extends the relevance of biogenic superoxide-based Mn(II) oxidation and highlights the potential role of mycogenic exudates in directing mineral precipitation. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Siderophore-mediated oxidation of Ce and fractionation of HREE by Mn (hydr)oxide-coprecipitation and sorption on MnO2: Experimental evidence for negative Ce-anomalies in abiogenic manganese precipitates

NASA Astrophysics Data System (ADS)

Krämer, Dennis; Tepe, Nathalie; Bau, Michael

2014-05-01

We conducted experiments with Rare Earths and Yttrium (REY), where the REY were sorbed on synthetic manganese dioxide as well as on coprecipitating manganese (hydr)oxide in the presence and absence of the siderophore desferrioxamine-B (DFOB). Siderophores are a group of globally abundant biogenic complexing agents which are excreted by plants and bacteria to enhance the bioavailability of Fe in oxic environments. The model siderophore used in this study, DFOB, is a hydroxamate siderophore occurring in almost all environmental settings with concentrations in the nanomolar to millimolar range and is one of the most thoroughly studied siderophores. In the absence of siderophores and other organic ligands, trivalent Ce is usually surface-oxidized to tetravalent Ce during sorption onto manganese (hydr)oxides. Such Mn precipitates, therefore, often show positive Ce anomalies, whereas the ambient solutions exhibit negative Ce anomalies (Ohta and Kawabe, 2001). In marked contrast, however, REY sorption in the presence of DFOB produces negative Ce anomalies in the Mn precipitates and a distinct and characteristic positive Ce anomaly in the residual siderophore-bearing solution. Furthermore, the heavy REY with ionic radii larger than the radius of Sm are also almost completely prevented from sorption onto the Mn solid phases. Sorption of REY onto Mn (hydr)oxides in the presence of DFOB creates a distinct and pronounced fractionation of Ce and the heavy REY from the light and middle REY. Apart from Ce, which is oxidized in solution by the siderophore, the distribution of the other REY mimics the stability constants for multi-dentate complexes of REY with DFOB, as determined by Christenson & Schijf (2011). Heavier REY are forming stronger complexes (and are hence better "protected" from sorption) than light REY, excluding Ce. Preferential partitioning of Ce into the liquid phase during the precipitation of Mn (hydr)oxides has only rarely been described for natural Mn (hydr)oxides

Oxidative dissolution potential of biogenic and abiogenic TcO 2 in subsurface sediments

NASA Astrophysics Data System (ADS)

Fredrickson, James K.; Zachara, John M.; Plymale, Andrew E.; Heald, Steve M.; McKinley, James P.; Kennedy, David W.; Liu, Chongxuan; Nachimuthu, Ponnusamy

2009-04-01

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O4-] and less mobile in the reduced form [Tc(IV)O 2· nH 2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass

Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

USGS Publications Warehouse

Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

2006-01-01

Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine.

PubMed

Akob, Denise M; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-08-01

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. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

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

PubMed Central

Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

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. PMID:24928873

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine

USGS Publications Warehouse

Akob, Denise M.; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

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.

Enzymatic microbial Mn(II) oxidation and Mn biooxide production in the Guaymas Basin deep-sea hydrothermal plume

NASA Astrophysics Data System (ADS)

Dick, Gregory J.; Clement, Brian G.; Webb, Samuel M.; Fodrie, F. Joel; Bargar, John R.; Tebo, Bradley M.

2009-11-01

Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal "clouds". Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (˜1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (˜40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O 2 concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO 2-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria

Diversity of Mn oxides produced by Mn(II)-oxidizing fungi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santelli, Cara M.; Webb, Samuel M.; Dohnalkova, Alice

Manganese (Mn) oxides are environmentally abundant, highly reactive mineral phases that mediate the biogeochemical cycling of nutrients, contaminants, carbon, and numerous other elements. Despite the belief that microorganisms (specifically bacteria and fungi) are responsible for the majority of Mn oxide formation in the environment, the impact of microbial species, physiology, and growth stage on Mn oxide formation is largely unresolved. Here, we couple microscopic and spectroscopic techniques to characterize the Mn oxides produced by four different species of Mn(II)-oxidizing Ascomycete fungi (Plectosphaerella cucumerina strain DS2psM2a2, Pyrenochaeta sp. DS3sAY3a, Stagonospora sp. SRC1lsM3a, and Acremonium strictum strain DS1bioAY4a) isolated from acid minemore » drainage treatment systems in central Pennsylvania. The site of Mn oxide formation varies greatly among the fungi, including deposition on hyphal surfaces, at the base of reproductive structures (e.g., fruiting bodies), and on envisaged extracellular polymers adjacent to the cell. The primary product of Mn(II) oxidation for all species growing under the same chemical and physical conditions is a nanoparticulate, poorly-crystalline hexagonal birnessite-like phase resembling synthetic d-MnO2. The phylogeny and growth conditions (planktonic versus surface-attached) of the fungi, however, impact the conversion of the initial phyllomanganate to more ordered phases, such as todorokite (A. strictum strain DS1bioAY4a) and triclinic birnessite (Stagonospora sp. SRC1lsM3a). Our findings reveal that the species of Mn(II)-oxidizing fungi impacts the size, morphology, and structure of Mn biooxides, which will likely translate to large differences in the reactivity of the Mn oxide phases.« less

Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-11-01

The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.

Biogenic Manganese-Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi-Copper Oxidase, MnxEFG.

PubMed

Tao, Lizhi; Simonov, Alexandr N; Romano, Christine A; Butterfield, Cristina N; Fekete, Monika; Tebo, Bradley M; Bond, Alan M; Spiccia, Leone; Martin, Lisandra L; Casey, William H

2017-01-26

In a natural geochemical cycle, manganese-oxide minerals (MnO x ) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnO x mineralization. Here, the kinetics of MnO x formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near-neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy-terminated monolayer to be in the range 0.36-0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linking Mn(II)-oxidizing bacteria to natural attenuation at a former U mining site

NASA Astrophysics Data System (ADS)

Akob, D.; Bohu, T.; Beyer, A.; Schäffner, F.; Händel, M.; Johnson, C.; Merten, D.; Büchel, G.; Totsche, K.; Küsel, K.

2012-04-01

Uranium mining near Ronneburg, Germany resulted in widespread environmental contamination with acid mine drainage (AMD) and high concentrations of heavy metals and radionuclides. Despite physical remediation of the area, groundwater is still a source of heavy metal contaminants, e.g., Cd, Ni, Co, Cu and Zn, to nearby ecosystems. However, natural attenuation of heavy metals is occurring in Mn oxide rich soils and sediments ranging in pH from 5 to 7. While microorganisms readily oxidize Mn(II) and precipitate Mn oxides at pH ~7 under oxic conditions, few studies describe Mn(II)-oxidizing bacteria (MOB) at pH ~5 and/or in the presence of heavy metals. In this study we (1) isolated MOB from the contaminated Ronneburg area at pH 5.5 and 7 and (2) evaluated the biological formation of Mn oxides. We isolated nine MOB strains at pH 7 (members of the Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes phyla) and a single isolate at pH 5.5 (Oxalobacteraceae isolate AB_14, within the β-Proteobacteria). LA-ICP-MS showed that all isolates accumulated Mn and Fe in their biomass. However, the Oxalobacteraceae isolate AB_14 oxidizes more Mn without additional Fe in the medium. Preliminary FTIR analysis indicated that all isolates formed precipitates, which showed absorption bands that were characteristic for birnessite. High resolution TEM showed variable morphology of precipitates and EDS confirmed the presence of Mn oxides. Isolate AB_14 was not surrounded with precipitates whereas our Actinobacteria isolate AB_18 was encrusted with Mn oxides. Electron diffraction is currently being used to confirm the presence of birnessite and other Mn oxide phases. This, the first known report of any organism capable of Mn oxidation at low pH, demonstrated that MOB can be involved in the natural attenuation of both moderately acidic and neutral pH soils and sediments via the formation of biogenic Mn oxides. Future work will fully evaluate the minerals formed in this process as well

Manganese (Mn) Oxidation Increases Intracellular Mn in Pseudomonas putida GB-1

PubMed Central

Banh, Andy; Chavez, Valarie; Doi, Julia; Nguyen, Allison; Hernandez, Sophia; Ha, Vu; Jimenez, Peter; Espinoza, Fernanda; Johnson, Hope A.

2013-01-01

Bacterial manganese (Mn) oxidation plays an important role in the global biogeochemical cycling of Mn and other compounds, and the diversity and prevalence of Mn oxidizers have been well established. Despite many hypotheses of why these bacteria may oxidize Mn, the physiological reasons remain elusive. Intracellular Mn levels were determined for Pseudomonas putida GB-1 grown in the presence or absence of Mn by inductively coupled plasma mass spectrometry (ICP-MS). Mn oxidizing wild type P. putida GB-1 had higher intracellular Mn than non Mn oxidizing mutants grown under the same conditions. P. putida GB-1 had a 5 fold increase in intracellular Mn compared to the non Mn oxidizing mutant P. putida GB-1-007 and a 59 fold increase in intracellular Mn compared to P. putida GB-1 ∆2665 ∆2447. The intracellular Mn is primarily associated with the less than 3 kDa fraction, suggesting it is not bound to protein. Protein oxidation levels in Mn oxidizing and non oxidizing cultures were relatively similar, yet Mn oxidation did increase survival of P. putida GB-1 when oxidatively stressed. This study is the first to link Mn oxidation to Mn homeostasis and oxidative stress protection. PMID:24147089

The key role of biogenic manganese oxides in enhanced removal of highly recalcitrant 1,2,4-triazole from bio-treated chemical industrial wastewater.

PubMed

Wu, Ruiqin; Wu, Haobo; Jiang, Xinbai; Shen, Jinyou; Faheem, Muhammad; Sun, Xiuyun; Li, Jiansheng; Han, Weiqing; Wang, Lianjun; Liu, Xiaodong

2017-04-01

The secondary effluent from biological treatment process in chemical industrial plant often contains refractory organic matter, which deserves to be further treated in order to meet the increasingly stringent environmental regulations. In this study, the key role of biogenic manganese oxides (BioMnOx) in enhanced removal of highly recalcitrant 1,2,4-triazole from bio-treated chemical industrial wastewater was investigated. BioMnOx production by acclimated manganese-oxidizing bacterium (MOB) consortium was confirmed through scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) analysis. Pseudomonas and Bacillus were found to be the most predominant species in acclimated MOB consortium. Mn 2+ could be oxidized optimally at neutral pH and initial Mn 2+ concentration below 33 mg L -1 . However, 1,2,4-triazole removal by BioMnOx produced occurred optimally at slightly acidic pH. High dosage of both Mn 2+ and 1,2,4-triazole resulted in decreased 1,2,4-triazole removal. In a biological aerated filter (BAF) coupled with manganese oxidation, 1,2,4-triazole and total organic carbon removal could be significantly enhanced compared to the control system without the participation of manganese oxidation, confirming the key role of BioMnOx in the removal of highly recalcitrant 1,2,4-triazole. This study demonstrated that the biosystem coupled with manganese oxidation had a potential for the removal of various recalcitrant contaminants from bio-treated chemical industrial wastewater.

Removal and Recovery of Toxic Silver Ion Using Deep-Sea Bacterial Generated Biogenic Manganese Oxides

PubMed Central

Pei, Yuanjun; Chen, Xiao; Xiong, Dandan; Liao, Shuijiao; Wang, Gejiao

2013-01-01

Products containing silver ion (Ag+) are widely used, leading to a large amount of Ag+-containing waste. The deep-sea manganese-oxidizing bacterium Marinobacter sp. MnI7-9 efficiently oxidizes Mn2+ to generate biogenic Mn oxide (BMO). The potential of BMO for recovering metal ions by adsorption has been investigated for some ions but not for Ag+. The main aim of this study was to develop effective methods for adsorbing and recovering Ag using BMO produced by Marinobacter sp. MnI7-9. In addition, the adsorption mechanism was determined using X-ray photoelectron spectroscopy analysis, specific surface area analysis, adsorption kinetics and thermodynamics. The results showed that BMO had a higher adsorption capacity for Ag+ compared to the chemical synthesized MnO2 (CMO). The isothermal absorption curves of BMO and CMO both fit the Langmuir model well and the maximum adsorption capacities at 28°C were 8.097 mmol/g and 0.787 mmol/g, for BMO and CMO, respectively. The change in enthalpy (ΔHθ) for BMO was 59.69 kJ/mol indicating that it acts primarily by chemical adsorption. The change in free energy (ΔGθ) for BMO was negative, which suggests that the adsorption occurs spontaneously. Ag+ adsorption by BMO was driven by entropy based on the positive ΔSθ values. The Ag+ adsorption kinetics by BMO fit the pseudo-second order model and the apparent activation energy of Ea is 21.72 kJ/mol. X-ray photoelectron spectroscopy analysis showed that 15.29% Ag+ adsorbed by BMO was transferred to Ag(0) and meant that redox reaction had happened during the adsorption. Desorption using nitric acid and Na2S completely recovered the Ag. The results show that BMO produced by strain MnI7-9 has potential for bioremediation and reutilization of Ag+-containing waste. PMID:24312566

Enhanced biogenic emissions of nitric oxide and nitrous oxide following surface biomass burning

NASA Technical Reports Server (NTRS)

Anderson, Iris C.; Levine, Joel S.; Poth, Mark A.; Riggan, Philip J.

1988-01-01

Recent measurements indicate significantly enhanced biogenic soil emissions of both nitric oxide (NO) and nitrous oxide (N2O) following surface burning. These enhanced fluxes persisted for at least six months following the burn. Simultaneous measurements indicate enhanced levels of exchangeable ammonium in the soil following the burn. Biomass burning is known to be an instantaneous source of NO and N2O resulting from high-temperature combustion. Now it is found that biomass burning also results in significantly enhanced biogenic emissions of these gases, which persist for months following the burn.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.

Constraints on superoxide mediated formation of manganese oxides

PubMed Central

Learman, Deric R.; Voelker, Bettina M.; Madden, Andrew S.; Hansel, Colleen M.

2013-01-01

Manganese (Mn) oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide (O2−) both of biogenic and abiogenic origin as an effective oxidant of Mn(II) leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III) and Mn(III/IV) oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide (H2O2), a product of the reaction of O2− with Mn(II), inhibits the oxidation process presumably through the reduction of Mn(III). Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III)-ligand complexes. While complexing ligands played a role in stabilizing Mn(III), they did not eliminate the inhibition of net Mn(III) formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II) by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II) by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation. PMID:24027565

Enhanced biogenic emissions of nitric oxide and nitrous oxide following surface biomass burning

Treesearch

Iris C. Anderson; Joel S. Levine; Mark A. Poth; Philip J. Riggan

1988-01-01

Recent measurements indicate significantly enhanced biogenic soil emissions of both nitric oxide (NO) and nitrous oxide (N2O) following surface burning. These enhanced fluxes persisted for at least 6 months following the burn. Simultaneous measurements indicate enhanced levels of...

Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

PubMed Central

Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L.; Charnock, John M.; Polya, David A.; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R.

2013-01-01

Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit. PMID:23666325

Multicopper Oxidase Involvement in Both Mn(II) and Mn(III) Oxidation during Bacterial Formation of MnO2

PubMed Central

Soldatova, Alexandra V.; Butterfield, Cristina; Oyerinde, Oyeyemi F.; Tebo, Bradley M.; Spiro, Thomas G.

2013-01-01

Global cycling of environmental manganese requires catalysis by bacteria and fungi for MnO2 formation, since abiotic Mn(II) oxidation is slow under ambient conditions. Genetic evidence from several bacteria implicates multicopper oxidases (MCOs) as being required for MnO2 formation. However, MCOs catalyze one-electron oxidations, whereas conversion of Mn(II) to MnO2 is a two-electron process. Trapping experiments with pyrophosphate (PP), a Mn(III) chelator, have demonstrated that Mn(III) is an intermediate in Mn(II) oxidation when mediated by exosporium from the Mn-oxidizing bacterium Bacillus SG-1. The reaction of Mn(II) depends on O2 and is inhibited by azide, consistent with MCO catalysis. We show that the subsequent conversion of Mn(III) to MnO2 also depends on O2 and is inhibited by azide. Thus, both oxidation steps appear to be MCO-mediated, likely by the same enzyme, indicated by genetic evidence to be the MnxG gene product. We propose a model of how the manganese oxidase active site may be organized to couple successive electron transfers to the formation of polynuclear Mn(IV) complexes as precursors to MnO2 formation. PMID:22892957

Mn(II,III) oxidation and MnO 2 mineralization by an expressed bacterial multicopper oxidase

DOE PAGES

Butterfield, Cristina N.; Soldatova, Alexandra V.; Lee, Sung -Woo; ...

2013-07-01

Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of the spore, encrusting them with Mn(IV) oxides. Molecular studies have identified the mnx (Mn oxidation) genes, including mnxG, encoding a putative multicopper oxidase (MCO), as responsible for this two-electron oxidation, a surprising finding because MCOs only catalyze single-electron transfer reactions. Characterization of themore » enzymatic mechanism has been hindered by the lack of purified protein. By purifying active protein from the mnxDEFG expression construct, we found that the resulting enzyme is a blue (absorption maximum 590 nm) complex containing MnxE, MnxF, and MnxG proteins. Further, by analyzing the Mn(II)- and (III)-oxidizing activity in the presence of a Mn(III) chelator, pyrophosphate, we found that the complex facilitates both electron transfers from Mn(II) to Mn(III) and from Mn(III) to Mn(IV). X-ray absorption spectroscopy of the Mn mineral product confirmed its similarity to Mn(IV) oxides generated by whole spores. Our results demonstrate that Mn oxidation from soluble Mn(II) to Mn(IV) oxides is a two-step reaction catalyzed by an MCO-containing complex. Lastly, with the purification of active Mn oxidase, we will be able to uncover its mechanism, broadening our understanding of Mn mineral formation and the bioinorganic capabilities of MCOs.« less

Mn(II,III) oxidation and MnO2 mineralization by an expressed bacterial multicopper oxidase

PubMed Central

Butterfield, Cristina N.; Soldatova, Alexandra V.; Lee, Sung-Woo; Spiro, Thomas G.; Tebo, Bradley M.

2013-01-01

Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of the spore, encrusting them with Mn(IV) oxides. Molecular studies have identified the mnx (Mn oxidation) genes, including mnxG, encoding a putative multicopper oxidase (MCO), as responsible for this two-electron oxidation, a surprising finding because MCOs only catalyze single-electron transfer reactions. Characterization of the enzymatic mechanism has been hindered by the lack of purified protein. By purifying active protein from the mnxDEFG expression construct, we found that the resulting enzyme is a blue (absorption maximum 590 nm) complex containing MnxE, MnxF, and MnxG proteins. Further, by analyzing the Mn(II)- and (III)-oxidizing activity in the presence of a Mn(III) chelator, pyrophosphate, we found that the complex facilitates both electron transfers from Mn(II) to Mn(III) and from Mn(III) to Mn(IV). X-ray absorption spectroscopy of the Mn mineral product confirmed its similarity to Mn(IV) oxides generated by whole spores. Our results demonstrate that Mn oxidation from soluble Mn(II) to Mn(IV) oxides is a two-step reaction catalyzed by an MCO-containing complex. With the purification of active Mn oxidase, we will be able to uncover its mechanism, broadening our understanding of Mn mineral formation and the bioinorganic capabilities of MCOs. PMID:23818588

Mn(II,III) oxidation and MnO2 mineralization by an expressed bacterial multicopper oxidase

NASA Astrophysics Data System (ADS)

Butterfield, Cristina N.; Soldatova, Alexandra V.; Lee, Sung-Woo; Spiro, Thomas G.; Tebo, Bradley M.

2013-07-01

Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of the spore, encrusting them with Mn(IV) oxides. Molecular studies have identified the mnx (Mn oxidation) genes, including mnxG, encoding a putative multicopper oxidase (MCO), as responsible for this two-electron oxidation, a surprising finding because MCOs only catalyze single-electron transfer reactions. Characterization of the enzymatic mechanism has been hindered by the lack of purified protein. By purifying active protein from the mnxDEFG expression construct, we found that the resulting enzyme is a blue (absorption maximum 590 nm) complex containing MnxE, MnxF, and MnxG proteins. Further, by analyzing the Mn(II)- and (III)-oxidizing activity in the presence of a Mn(III) chelator, pyrophosphate, we found that the complex facilitates both electron transfers from Mn(II) to Mn(III) and from Mn(III) to Mn(IV). X-ray absorption spectroscopy of the Mn mineral product confirmed its similarity to Mn(IV) oxides generated by whole spores. Our results demonstrate that Mn oxidation from soluble Mn(II) to Mn(IV) oxides is a two-step reaction catalyzed by an MCO-containing complex. With the purification of active Mn oxidase, we will be able to uncover its mechanism, broadening our understanding of Mn mineral formation and the bioinorganic capabilities of MCOs.

Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities.

PubMed

Najafpour, Mohammad Mahdi; Mostafalu, Ramin; Hołyńska, Małgorzata; Ebrahimi, Foad; Kaboudin, Babak

2015-11-01

Nano-sized Mn oxides contain Mn3O4, β-MnOOH and Mn2O3 have been prepared by a previously reported method using thermal decomposition of β-cyclodextrin-Mn complexes. In the next step, the water-oxidizing activities of these Mn oxides using cerium(IV) ammonium nitrate as a chemical oxidant are studied. The turnover frequencies for β-MnO(OH) and Mn3O4 are 0.24 and 0.01-0.17 (mmol O2/mol Mns), respectively. Subsequently, water-oxidizing activities of these compounds are compared to the other previously reported Mn oxides. Important factors affecting water oxidation by these Mn oxides are also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

PubMed

Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

2011-11-01

Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Impact of environmental chemistry on mycogenic Mn oxide minerals

NASA Astrophysics Data System (ADS)

Santelli, C. M.; Farfan, G. A.; Post, A.; Post, J. E.

2012-12-01

Manganese (Mn) oxide minerals are ubiquitous in aquatic and terrestrial environments and their presence can have broad environmental consequences. In particular, Mn oxides scavenge nutrients and metals, degrade complex organics, and oxidize a variety of inorganic contaminants. The "reactivity" of Mn oxides, however, is highly dependent upon crystallite size, composition, and structure, which are largely determined by environmental factors such as solution chemistry. It is has been suggested that most Mn oxides in terrestrial and aquatic environments are formed by microbial activity; indeed, a diversity of Mn(II)-oxidizing bacteria and fungi have been isolated and their mineral byproducts are consistent with those observed in natural systems. Previous studies showed that Mn(II)-oxidizing Ascomycete fungi produce highly-disordered, nanocrystalline Mn oxides that are structurally similar to synthetic δ-MnO2 or natural vernadite. Unlike related studies with Mn-oxidizing bacteria, Mn oxides produced by these fungi did not "age" or transform to more crystalline mineral phases with time. We hypothesize that fungal growth conditions, in particular the low concentration of cations, are inhibiting secondary mineral formation. The overall goal of this research is to examine the structure and speciation of fungally-precipitated Mn oxides with respect to fungal species, time, and concentration of soluble Mn(II), Na, and Ca - three environmentally relevant cations that promote the transformation of δ-MnO2 to more crystalline mineral phases such as feitknechtite, birnessite, or ranciéite. For this study, we examined the Mn oxides formed by different species of Mn(II)-oxidizing fungi (Pyrenochaeta sp., Stagonospora sp., Plectosphaerella cucumerina., and Acremonium strictum). Isolates were grown for 8 or 16 days in a nutrient lean media consisting of yeast extract, trace elements and 0.2 mM MnCl2 supplemented with varying concentrations of Na, Ca, or Mn(II) compounds. The

Oxidation of MnO(100) and NaMnO2 formation: Characterization of Mn2+ and Mn3+ surfaces via XPS and water TPD

NASA Astrophysics Data System (ADS)

Feng, Xu; Cox, David F.

2018-09-01

The oxidation of clean and Na precovered MnO(100) has been investigated by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD) of adsorbed water. XPS results indicate that Mn3O4-like and Mn2O3-like surfaces can be formed by various oxidation treatments of clean and nearly-stoichiometric MnO(100), while a NaMnO2-like surface can be produced by the oxidation of MnO(100) pre-covered with multilayers of metallic Na. Water TPD results indicate that water adsorption/desorption is sensitive to the available oxidation states of surface Mn cations, and can be used to distinguish between surfaces exposing Mn2+and Mn3+ cations, or a combination of these oxidation states. Carbon dioxide and water TPD results from the NaMnO2-like surface indicate that pre-adsorbed water blocks the uptake of CO2, while water displaces pre-adsorbed CO2. No indication of a strong reactive interaction is observed between CO2, water and the NaMnO2-like surface under the conditions of our study.

Microbe–microbe interactions trigger Mn(II)-oxidizing gene expression

PubMed Central

Liang, Jinsong; Bai, Yaohui; Men, Yujie; Qu, Jiuhui

2017-01-01

Manganese (Mn) is an important metal in geochemical cycles. Some microorganisms can oxidize Mn(II) to Mn oxides, which can, in turn, affect the global cycles of other elements by strong sorption and oxidation effects. Microbe–microbe interactions have important roles in a number of biological processes. However, how microbial interactions affect Mn(II) oxidation still remains unknown. Here, we investigated the interactions between two bacteria (Arthrobacter sp. and Sphingopyxis sp.) in a co-culture, which exhibited Mn(II)-oxidizing activity, although neither were able to oxidize Mn(II) in isolation. We demonstrated that the Mn(II)-oxidizing activity in co-culture was most likely induced via contact-dependent interactions. The expressed Mn(II)-oxidizing protein in the co-culture was purified and identified as a bilirubin oxidase belonging to strain Arthrobacter. Full sequencing of the bilirubin oxidase-encoding gene (boxA) was performed. The Mn(II)-oxidizing protein and the transcripts of boxA were detected in the co-culture, but not in either of the isolated cultures. This indicate that boxA was silent in Arthrobacter monoculture, and was activated in response to presence of Sphingopyxis in the co-culture. Further, transcriptomic analysis by RNA-Seq, extracellular superoxide detection and cell density quantification by flow cytometry indicate induction of boxA gene expression in Arthrobacter was co-incident with a stress response triggered by co-cultivation with Sphingopyxis. Our findings suggest the potential roles of microbial physiological responses to stress induced by other microbes in Mn(II) oxidation and extracellular superoxide production. PMID:27518809

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

PubMed

Jung, Haesung; Jun, Young-Shin

2016-01-05

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.

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

NASA Astrophysics Data System (ADS)

Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

2017-08-01

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 4 mM, 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 6-24 mM, 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

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: influence of Mn/Fe ratio, pH, Ca2+, and humic acid.

PubMed

Zhang, Gaosheng; Liu, Huijuan; Qu, Jiuhui; Jefferson, William

2012-01-15

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater. Copyright © 2011 Elsevier Inc. All rights reserved.

Mn(II) Oxidation by the Multicopper Oxidase Complex Mnx: A Coordinated Two-Stage Mn(II)/(III) and Mn(III)/(IV) Mechanism.

PubMed

Soldatova, Alexandra V; Romano, Christine A; Tao, Lizhi; Stich, Troy A; Casey, William H; Britt, R David; Tebo, Bradley M; Spiro, Thomas G

2017-08-23

The bacterial manganese oxidase MnxG of the Mnx protein complex is unique among multicopper oxidases (MCOs) in carrying out a two-electron metal oxidation, converting Mn(II) to MnO 2 nanoparticles. The reaction occurs in two stages: Mn(II) → Mn(III) and Mn(III) → MnO 2 . In a companion study , we show that the electron transfer from Mn(II) to the low-potential type 1 Cu of MnxG requires an activation step, likely forming a hydroxide bridge at a dinuclear Mn(II) site. Here we study the second oxidation step, using pyrophosphate (PP) as a Mn(III) trap. PP chelates Mn(III) produced by the enzyme and subsequently allows it to become a substrate for the second stage of the reaction. EPR spectroscopy confirms the presence of Mn(III) bound to the enzyme. The Mn(III) oxidation step does not involve direct electron transfer to the enzyme from Mn(III), which is shown by kinetic measurements to be excluded from the Mn(II) binding site. Instead, Mn(III) is proposed to disproportionate at an adjacent polynuclear site, thereby allowing indirect oxidation to Mn(IV) and recycling of Mn(II). PP plays a multifaceted role, slowing the reaction by complexing both Mn(II) and Mn(III) in solution, and also inhibiting catalysis, likely through binding at or near the active site. An overall mechanism for Mnx-catalyzed MnO 2 production from Mn(II) is presented.

Oxidative Formation and Removal of Complexed Mn(III) by Pseudomonas Species

PubMed Central

Wright, Mitchell H.; Geszvain, Kati; Oldham, Véronique E.; Luther, George W.; Tebo, Bradley M.

2018-01-01

The observation of significant concentrations of soluble Mn(III) complexes in oxic, suboxic, and some anoxic waters has triggered a re-evaluation of the previous Mn paradigm which focused on the cycling between soluble Mn(II) and insoluble Mn(III,IV) species as operationally defined by filtration. Though Mn(II) oxidation in aquatic environments is primarily bacterially-mediated, little is known about the effect of Mn(III)-binding ligands on Mn(II) oxidation nor on the formation and removal of Mn(III). Pseudomonas putida GB-1 is one of the most extensively investigated of all Mn(II) oxidizing bacteria, encoding genes for three Mn oxidases (McoA, MnxG, and MopA). P. putida GB-1 and associated Mn oxidase mutants were tested alongside environmental isolates Pseudomonas hunanensis GSL-007 and Pseudomonas sp. GSL-010 for their ability to both directly oxidize weakly and strongly bound Mn(III), and to form these complexes through the oxidation of Mn(II). Using Mn(III)-citrate (weak complex) and Mn(III)-DFOB (strong complex), it was observed that P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 and mutants expressing only MnxG and McoA were able to directly oxidize both species at varying levels; however, no oxidation was detected in cultures of a P. putida mutant expressing only MopA. During cultivation in the presence of Mn(II) and citrate or DFOB, P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 formed Mn(III) complexes transiently as an intermediate before forming Mn(III/IV) oxides with the overall rates and extents of Mn(III,IV) oxide formation being greater for Mn(III)-citrate than for Mn(III)-DFOB. These data highlight the role of bacteria in the oxidative portion of the Mn cycle and suggest that the oxidation of strong Mn(III) complexes can occur through enzymatic mechanisms involving multicopper oxidases. The results support the observations from field studies and further emphasize the complexity of the geochemical cycling of

Oxidative Formation and Removal of Complexed Mn(III) by Pseudomonas Species.

PubMed

Wright, Mitchell H; Geszvain, Kati; Oldham, Véronique E; Luther, George W; Tebo, Bradley M

2018-01-01

The observation of significant concentrations of soluble Mn(III) complexes in oxic, suboxic, and some anoxic waters has triggered a re-evaluation of the previous Mn paradigm which focused on the cycling between soluble Mn(II) and insoluble Mn(III,IV) species as operationally defined by filtration. Though Mn(II) oxidation in aquatic environments is primarily bacterially-mediated, little is known about the effect of Mn(III)-binding ligands on Mn(II) oxidation nor on the formation and removal of Mn(III). Pseudomonas putida GB-1 is one of the most extensively investigated of all Mn(II) oxidizing bacteria, encoding genes for three Mn oxidases (McoA, MnxG, and MopA). P. putida GB-1 and associated Mn oxidase mutants were tested alongside environmental isolates Pseudomonas hunanensis GSL-007 and Pseudomonas sp. GSL-010 for their ability to both directly oxidize weakly and strongly bound Mn(III), and to form these complexes through the oxidation of Mn(II). Using Mn(III)-citrate (weak complex) and Mn(III)-DFOB (strong complex), it was observed that P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 and mutants expressing only MnxG and McoA were able to directly oxidize both species at varying levels; however, no oxidation was detected in cultures of a P. putida mutant expressing only MopA. During cultivation in the presence of Mn(II) and citrate or DFOB, P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 formed Mn(III) complexes transiently as an intermediate before forming Mn(III/IV) oxides with the overall rates and extents of Mn(III,IV) oxide formation being greater for Mn(III)-citrate than for Mn(III)-DFOB. These data highlight the role of bacteria in the oxidative portion of the Mn cycle and suggest that the oxidation of strong Mn(III) complexes can occur through enzymatic mechanisms involving multicopper oxidases. The results support the observations from field studies and further emphasize the complexity of the geochemical cycling of

Theoretical investigation of the reaction of Mn+ with ethylene oxide.

PubMed

Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

2012-01-12

The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

Mn 4+ emission in pyrochlore oxides

DOE PAGES

Du, Mao-Hua

2014-08-27

For the existing Mn 4+ activated red phosphors have relatively low emission energies (or long emission wavelengths) and are therefore inefficient for general lighting. Density functional calculations are performed to study Mn 4+ emission in rare-earth hafnate, zirconate, and stannate pyrochlore oxides (RE 2Hf 2O 7, RE 2Zr 2O 7, and RE 2Sn 2O 7). We show how the different sizes of the RE 3+ cation in these pyrochlores affect the local structure of the distorted MnO 6 octahedron, the Mn–O hybridization, and the Mn 4+ emission energy. The Mn 4+ emission energies of many pyrochlores are found to bemore » higher than those currently known for Mn 4+ doped oxides and should be closer to that of Y 2O 3:Eu 3+ (the current commercial red phosphor for fluorescent lighting). The O–Mn–O bond angle distortion in a MnO6 octahedron is shown to play an important role in weakening Mn–O hybridization and consequently increasing the Mn 4+ emission energy. Our result shows that searching for materials that allow significant O–Mn–O bond angle distortion in a MnO 6 octahedron is an effective approach to find new Mn 4+ activated red phosphors with potential to replace the relatively expensive Y 2O 3:Eu 3+ phosphor.« less

As(III) oxidation by MnO2 during groundwater treatment.

PubMed

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

PubMed

Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

2015-04-01

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

Comparison of nano-sized Mn oxides with the Mn cluster of photosystem II as catalysts for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Haghighi, Behzad; Tomo, Tatsuya; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2015-02-01

"Back to Nature" is a promising way to solve the problems that we face today, such as air pollution and shortage of energy supply based on conventional fossil fuels. A Mn cluster inside photosystem II catalyzes light-induced water-splitting leading to the generation of protons, electrons and oxygen in photosynthetic organisms, and has been considered as a good model for the synthesis of new artificial water-oxidizing catalysts. Herein, we surveyed the structural and functional details of this cluster and its surrounding environment. Then, we review the mechanistic findings concerning the cluster and compare this biological catalyst with nano-sized Mn oxides, which are among the best artificial Mn-based water-oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

Negative cerium anomalies in manganese (hydr)oxide precipitates due to cerium oxidation in the presence of dissolved siderophores

NASA Astrophysics Data System (ADS)

Kraemer, Dennis; Tepe, Nathalie; Pourret, Olivier; Bau, Michael

2017-01-01

We present experimental results on the sorption behavior of rare earth elements and yttrium (REY) on precipitating manganese (hydr)oxide in the presence of the biogenic siderophore desferrioxamine B (DFOB). In marked contrast to inorganic systems, where preferential adsorption of HREY and depletion of LREY is commonly observed in manganese (hydr)oxide precipitates, sorption of REY in presence of the DFOB siderophore leads to HREY-depleted and LREY-enriched patterns in the precipitates. Moreover, our data indicate that surface oxidation of Ce(III) to Ce(IV) during sorption onto manganese (hydr)oxides and the resulting development of a positive Ce anomaly, which are commonly observed in inorganic experiments, are prevented in the presence of DFOB. Instead, Ce(III) is oxidized to Ce(IV) but associated with the dissolved desferrioxamine B which forms complexes with Ce(IV), that are at least twenty orders of magnitude more stable than those with Ce(III) and REY(III). The overall result is the formation of a positive Ce anomaly in the solution and a negative Ce anomaly in the Mn (hydr)oxides. The distribution of the strictly trivalent REY and Eu(III) between the manganese (hydr)oxide phase and the remaining ambient solution mimics the distribution of published stability constants for complexes of REY(III) with DFOB, i.e. the heavy REY form more stable complexes with the ligand and hence are better shielded from sorption than the LREY. Surface complexation modeling corroborates our experimental results. Negative Ce anomalies in Mn precipitates have been described from biogenic Mn oxides. Our results provide experimental evidence for the development of negative Ce anomalies in abiogenic Mn (hydr)oxide precipitates and show that the presence of the widespread siderophore desferrioxamine B during mineral precipitation results in HREY-depleted Mn (hydr)oxides with negative Ce anomalies.

Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those ofmore » the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.« less

Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romano, Christine A.; Zhou, Mowei; Song, Yang

Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase, Mnx, in Bacillus sp. PL-12 is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. However, MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant tomore » crystallization, so its structure is unknown. In this study, native mass spectrometry defines the subunit topology and copper binding of the Mnx complex, while high resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for conceptualizing how Mnx produces nanoparticulate Mn oxides.« less

Unraveling the role of animal heme peroxidases in superoxide mediated Mn oxide formation

NASA Astrophysics Data System (ADS)

Learman, D. R.; Hansel, C. M.

2013-12-01

Manganese(III,IV) oxides are important in the environment as they can impact the fate of a broad range of nutrients (e.g. carbon and phosphate) and contaminates (e.g. lead and chromium). Bacteria play a valuable role in the production of Mn oxides, yet the mechanisms and physiological reasons remain unclear. Roseobacter sp. AzwK-3b, an organism within the abundant and ubiquitous Roseobacter clade, has recently been shown to oxidize Mn(II) via a novel pathway that involves enzymatic extracellular superoxide production. However, in reactions with only Mn(II) and abiotically generated superoxide, we find superoxide alone is not enough to produce Mn(III,IV) oxides. Scavenging of the byproduct hydrogen peroxide (via the addition of catalase) is required to generate Mn oxides via abiotic reaction of Mn(II) with superoxide. Thus, R. AzwK-3b must produce superoxide and also scavenge hydrogen peroxide to form Mn oxides. Further, in-gel Mn(II) oxidation assay revealed a protein band that could generate Mn oxides in the presence of soluble Mn(II). This Mn(II)-oxidizing protein band was excised from the gel and the peptides identified via mass spectrometry. An animal heme peroxidase (AHP) was the predominant protein found in this band. This protein is homologous to the AHPs previously implicated as a Mn(II)-oxidizing enzyme within the Alphaproteobacteria, Erythrobacter SD-21 and Aurantimonas manganoxydans strain SI85-9A1. Currently, protein expression of the AHPs in R. AzwK-3b is being examined to determine if expression is correlated with Mn(II) concentration or oxidative stress. Our data suggests that AHPs do not directly oxidize Mn(II) but rather plays a role in scavenging hydrogen peroxide and/or producing an organic Mn(III) ligand that complexes Mn(III) and likely aids in Mn oxide precipitation.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

EPA Science Inventory

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 d...

Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

PubMed

Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

2015-11-01

Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxidation of anthracene using waste Mn oxide minerals: the importance of wetting and drying sequences.

PubMed

Clarke, Catherine; Tourney, Janette; Johnson, Karen

2012-02-29

PAHs are a common problem in contaminated urban soils due to their recalcitrance. This study presents results on the oxidation of anthracene on synthetic and natural Mn oxide surfaces. Evaporation of anthracene spiked Mn oxide slurries in air results in the oxidation of 30% of the anthracene to anthraquinone. Control minerals, quartz and calcite, also oxidised a small but significant proportion of the anthracene (4.5% and 14% conversion, respectively) when spiked mineral slurries were evaporated in air. However, only Mn oxide minerals showed significant anthracene oxidation (5-10%) when evaporation took place in the absence of oxygen (N2 atmosphere). In the fully hydrated systems where no drying took place, natural Mn oxides showed an increase in anthracene oxidation with decreasing pH, with a conversion of 75% anthracene at pH 4. These results show both acidification and drying favor the oxidation of anthracene on Mn oxide mineral surfaces. It has also been demonstrated that non-redox active mineral surfaces, such as calcite, may play a role in contaminant breakdown during wetting and drying sequences. Given that climate changes suggest that wetting and drying sequences are likely to become more significant these results have important implications for contaminated land remediation technologies. Copyright © 2012 Elsevier B.V. All rights reserved.

Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

USGS Publications Warehouse

Wang, Bronwen; Burau, Richard G.

1995-01-01

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

Graphene oxide-MnO2 nanocomposite for supercapacitor application

NASA Astrophysics Data System (ADS)

Muhammed Shafi, P.; Vishal, Jose K.; Chandra Bose, A.

2016-09-01

Increased depletion of fossil fuels along with global warming and climate change made the society to think about alternate green and sustainable energy sources and better energy storage devices. Extensive research has been performed on the development of solar cells, fuel cells, Lithium- ion battery and supercapacitors to combat the green house effect and its consequences, and to meet the increased energy crisis. Supercapacitors, also known as electrochemical capacitors are gained a great attention because of their pulse power supply, long cycle life (>100,000), simple principle and high dynamic of charge propagation. Its greater power density than lithium- ion battery and much larger energy density than conventional capacitors brought super capacitors to a promising energy storage device to meet the increased energy demands. Here we demonstrate supercapacitor electrode materials with graphene oxide (electric double layer capacitor) and α-MnO2 nanomaterial (pseudo-capacitor), as well as composite of these materials, which means that the bulk of the material undergoes a fast redox reaction to provide the capacitive response and they exhibit superior specific energies in addition to the carbon-based supercapacitors (double-layer capacitors). A simple soft chemical route is utilized to synthesize graphene oxide, α-MnO2 and graphene oxide-MnO2 composite. The phase and the structure of the synthesized materials are studied using X-ray diffractometry (XRD). The functional group and the presence of impurities are understood from Fourier transform infrared (FTIR) spectra. The capacitive properties of the graphene oxide, graphene oxide - MnO2 nanocomposite and α-MnO2 are tested with the help of cyclic voltammetry (CV) and galvanostatic charge - discharge techniques using 1 M Na2SO4 in aqueous solution as electrolyte. It was found that graphene oxide - MnO2 nanocomposite shows better electrochemical behaviour compared to individual graphene oxide and α-MnO2 nanomaterial.

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

PubMed

Marcus, Daniel N; Pinto, Ameet; Anantharaman, Karthik; Ruberg, Steven A; Kramer, Eva L; Raskin, Lutgarde; Dick, Gregory J

2017-04-01

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. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation.

PubMed

Zhu, Mengqiang; Paul, Kristian W; Kubicki, James D; Sparks, Donald L

2009-09-01

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals

PubMed Central

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-01-01

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals.

PubMed

Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

2015-06-03

In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV).

O-H bond oxidation by a monomeric Mn(III)-OMe complex.

PubMed

Wijeratne, Gayan B; Day, Victor W; Jackson, Timothy A

2015-02-21

Manganese-containing, mid-valent oxidants (Mn(III)-OR) that mediate proton-coupled electron-transfer (PCET) reactions are central to a variety of crucial enzymatic processes. The Mn-dependent enzyme lipoxygenase is such an example, where a Mn(III)-OH unit activates fatty acid substrates for peroxidation by an initial PCET. This present work describes the quantitative generation of the Mn(III)-OMe complex, [Mn(III)(OMe)(dpaq)](+) (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) via dioxygen activation by [Mn(II)(dpaq)](+) in methanol at 25 °C. The X-ray diffraction structure of [Mn(III)(OMe)(dpaq)](+) exhibits a Mn-OMe group, with a Mn-O distance of 1.825(4) Å, that is trans to the amide functionality of the dpaq ligand. The [Mn(III)(OMe)(dpaq)](+) complex is quite stable in solution, with a half-life of 26 days in MeCN at 25 °C. [Mn(III)(OMe)(dpaq)](+) can activate phenolic O-H bonds with bond dissociation free energies (BDFEs) of less than 79 kcal mol(-1) and reacts with the weak O-H bond of TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol) with a hydrogen/deuterium kinetic isotope effect (H/D KIE) of 1.8 in MeCN at 25 °C. This isotope effect, together with other experimental evidence, is suggestive of a concerted proton-electron transfer (CPET) mechanism for O-H bond oxidation by [Mn(III)(OMe)(dpaq)](+). A kinetic and thermodynamic comparison of the O-H bond oxidation reactivity of [Mn(III)(OMe)(dpaq)](+) to other M(III)-OR oxidants is presented as an aid to gain more insight into the PCET reactivity of mid-valent oxidants. In contrast to high-valent counterparts, the limited examples of M(III)-OR oxidants exhibit smaller H/D KIEs and show weaker dependence of their oxidation rates on the driving force of the PCET reaction with O-H bonds.

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2011 CFR

2011-07-01

... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Barium manganese oxide (BaMnO3). 721...

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2010 CFR

2010-07-01

... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721...

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00...

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00...

40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00...

Graphene oxide--MnO2 nanocomposites for supercapacitors.

PubMed

Chen, Sheng; Zhu, Junwu; Wu, Xiaodong; Han, Qiaofeng; Wang, Xin

2010-05-25

A composite of graphene oxide supported by needle-like MnO(2) nanocrystals (GO-MnO(2) nanocomposites) has been fabricated through a simple soft chemical route in a water-isopropyl alcohol system. The formation mechanism of these intriguing nanocomposites investigated by transmission electron microscopy and Raman and ultraviolet-visible absorption spectroscopy is proposed as intercalation and adsorption of manganese ions onto the GO sheets, followed by the nucleation and growth of the crystal species in a double solvent system via dissolution-crystallization and oriented attachment mechanisms, which in turn results in the exfoliation of GO sheets. Interestingly, it was found that the electrochemical performance of as-prepared nanocomposites could be enhanced by the chemical interaction between GO and MnO(2). This method provides a facile and straightforward approach to deposit MnO(2) nanoparticles onto the graphene oxide sheets (single layer of graphite oxide) and may be readily extended to the preparation of other classes of hybrids based on GO sheets for technological applications.

Nano-sized layered Mn oxides as promising and biomimetic water oxidizing catalysts for water splitting in artificial photosynthetic systems.

PubMed

Najafpour, Mohammad Mahdi; Heidari, Sima; Amini, Emad; Khatamian, Masoumeh; Carpentier, Robert; Allakhverdiev, Suleyman I

2014-04-05

One challenge in artificial photosynthetic systems is the development of artificial model compounds to oxidize water. The water-oxidizing complex of Photosystem II which is responsible for biological water oxidation contains a cluster of four Mn ions bridged by five oxygen atoms. Layered Mn oxides as efficient, stable, low cost, environmentally friendly and easy to use, synthesize, and manufacture compounds could be considered as functional and structural models for the site. Because of the related structure of these Mn oxides and the catalytic centre of the active site of the water oxidizing complex of Photosystem II, the study of layered Mn oxides may also help to understand more about the mechanism of water oxidation by the natural site. This review provides an overview of the current status of layered Mn oxides in artificial photosynthesis and discuss the sophisticated design strategies for Mn oxides as water oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

Mn accumulation in a submerged plant Egeria densa (Hydrocharitaceae) is mediated by epiphytic bacteria.

PubMed

Tsuji, Kousuke; Asayama, Takuma; Shiraki, Nozomi; Inoue, Shota; Okuda, Erina; Hayashi, Chizuru; Nishida, Kazuma; Hasegawa, Hiroshi; Harada, Emiko

2017-07-01

Many aquatic plants act as biosorbents, removing and recovering metals from the environment. To assess the biosorbent activity of Egeria densa, a submerged freshwater macrophyte, plants were collected monthly from a circular drainage area in Lake Biwa basin and the Mn concentrations of the plants were analysed. Mn concentrations in these plants were generally above those of terrestrial hyperaccumulators, and were markedly higher in spring and summer than in autumn. Mn concentrations were much lower in plants incubated in hydroponic medium at various pH levels with and without Mn supplementation than in field-collected plants. The precipitation of Mn oxides on the leaves was determined by variable pressure scanning electron microscopy-energy dispersive X-ray analysis and Leucoberbelin blue staining. Several strains of epiphytic bacteria were isolated from the field-collected E. densa plants, with many of these strains, including those of the genera Acidovorax, Comamonas, Pseudomonas and Rhizobium, found to have Mn-oxidizing activity. High Mn concentrations in E. densa were mediated by the production of biogenic Mn oxide in biofilms on leaf surfaces. These findings provide new insights into plant epidermal bacterial flora that affect metal accumulation in plants and suggest that these aquatic plants may have use in Mn phytomining. © 2017 John Wiley & Sons Ltd.

Biogenic Emission Inventories: Scaling Local Biogenic Measurements to Regions

NASA Astrophysics Data System (ADS)

Lamb, B.; Pressley, S.; Westberg, H.; Guenther, A.

2002-12-01

Biogenic Hydrocarbons, such as isoprene, are important trace gas species that are naturally emitted by vegetation and that affect the oxidative capacity of the atmosphere. Biogenic emissions are regulated by many environmental variables; the most important variables are thought to be temperature and light. Long-term isoprene flux measurements are useful for verifying existing canopy models and exploring other correlations between isoprene fluxes and environmental parameters. Biogenic Emission Models, such as BEIS (Biogenic Emission Inventory System) rely on above canopy environmental parameters and below canopy scaling factors to estimate canopy scale biogenic hydrocarbon fluxes. Other models, which are more complex, are coupled micrometeorological and physiological modules that provide feedback mechanisms present in a canopy environment. These types of models can predict biogenic emissions well, however, the required input is extensive, and for regional applications, they can be cumbersome. This paper presents analyses based on long-term isoprene flux measurements that have been collected since 1999 at the AmeriFlux site located at the University of Michigan Biological Station (UMBS) as part of the Program for Research on Oxidants: PHotochemistry, Emissions, and Transport (PROPHET). The goals of this research were to explore a potential relationship between the surface energy budget (primarily sensible heat flux) and isoprene emissions. Our hypothesis is that the surface energy flux is a better model parameter for isoprene emissions at the canopy scale than temperature and light levels, and the link to the surface energy budget will provide a significant improvement in isoprene emission models. Preliminary results indicate a significant correlation between daily isoprene emissions and sensible heat fluxes for a predominantly aspen/oak stand located in northern Michigan. Since surface energy budgets are an integral part of mesoscale meteorological models, this

Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx.

PubMed

Romano, Christine A; Zhou, Mowei; Song, Yang; Wysocki, Vicki H; Dohnalkova, Alice C; Kovarik, Libor; Paša-Tolić, Ljiljana; Tebo, Bradley M

2017-09-29

Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase in Bacillus sp. PL-12, Mnx, is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins, MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant to crystallization, so its structure is unknown. Here, we show that native mass spectrometry defines the subunit topology and copper binding of Mnx, while high-resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for understanding Mn biomineralization by such unexplored enzymes.Significant challenges exist for structural characterization of enzymes responsible for biomineralization. Here the authors show that native mass spectrometry and high resolution electron microscopy can define the subunit topology and copper binding of a manganese oxidizing complex, and describe early stage formation of its mineral products.

Ferromagnetic phase in partially oxidized FeMn films

NASA Astrophysics Data System (ADS)

Svalov, A. V.; Savin, P. A.; Lepalovskij, V. N.; Vas'kovskiy, V. O.; Larrañaga, A.; Kurlyandskaya, G. V.

2018-04-01

The structure, magnetic and magnetoresistive properties of ferromagnetic phase in partially oxidized FeMn films was studied. The oxidation was performed by annealing of the samples under atmospheric pressure in a gas mixture (nitrogen with 0.5% oxygen) at the temperature of 300 °C. The resulting ferromagnetic phase was isotropic in the film plane. The value of the anisotropic magnetoresistance was similar to the value of the anisotropic magnetoresistance usually observed in films of pure iron. The oxidation of antiferromagnetic FeMn films resulted in the appearance of an exchange bias.

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for the...

Importance of trivalency and the eg1 configuration in the photocatalytic oxidation of water by Mn and Co oxides

PubMed Central

Maitra, Urmimala; Naidu, B. S.; Govindaraj, A.; Rao, C. N. R.

2013-01-01

Prompted by the early results on the catalytic activity of LiMn2O4 and related oxides in the photochemical oxidation of water, our detailed study of several manganese oxides has shown that trivalency of Mn is an important factor in determining the catalytic activity. Thus, Mn2O3, LaMnO3, and MgMn2O4 are found to be very good catalysts with turnover frequencies of 5 × 10−4 s−1, 4.8 × 10−4 s−1, and 0.8 ×10−4 s−1, respectively. Among the cobalt oxides, Li2Co2O4 and LaCoO3—especially the latter—exhibit excellent catalytic activity, with the turnover frequencies being 9 × 10−4 s−1 and 1.4 × 10−3 s−1, respectively. The common feature among the catalytic Mn and Co oxides is not only that Mn and Co are in the trivalent state, but Co3+ in the Co oxides is in the intermediate t2g5eg1 state whereas Mn3+ is in the t2g3eg1 state. The presence of the eg1 electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides. PMID:23818589

Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene.

PubMed

Friedman, Beth; Brophy, Patrick; Brune, William H; Farmer, Delphine K

2016-02-02

In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.

Kineococcus radiotolerans Dps forms a heteronuclear Mn-Fe ferroxidase center that may explain the Mn-dependent protection against oxidative stress.

PubMed

Ardini, Matteo; Fiorillo, Annarita; Fittipaldi, Maria; Stefanini, Simonetta; Gatteschi, Dante; Ilari, Andrea; Chiancone, Emilia

2013-06-01

The ferroxidase center of DNA-binding protein from starved cells (Dps) is a major player in the iron oxidation/detoxification process that leads to a decreased reactive oxygen species production. The possible Mn(II) participation in this process has been studied in Dps from Kineococcus radiotolerans, a radiation-resistant bacterium with a high cytosolic Mn/Fe ratio and a high capacity to survive ionizing and stress conditions. The X-ray structure of recombinant K. radiotolerans Dps loaded with Mn(II) has been solved at 2.0Å resolution. Mn(II) binding to K. radiotolerans Dps and its effect on Fe(II) oxidation have been characterized in spectroscopic measurements. In K. radiotolerans Dps, the Fe-Fe ferroxidase center can have a Mn-Fe composition. Mn(II) binds only at the high affinity, so-called A site, whereas Fe(II) binds also at the low affinity, so-called B site. The Mn-Fe and Fe-Fe centers behave distinctly upon iron oxidation by O2. A site-bound Mn(II) or Fe(II) plays a catalytic role, while B site-bound Fe(II) behaves like a substrate and can be replaced by another Fe(II) after oxidation. When H2O2 is the Fe(II) oxidant, single electrons are transferred to aromatic residues near the ferroxidase center and give rise to intra-protein radicals thereby limiting OH release in solution. The presence of the Mn-Fe center results in significant differences in the development of such intra-protein radicals. Mn(II) bound at the Dps ferroxidase center A site undergoes redox cycling provided the B site contains Fe. The results provide a likely molecular mechanism for the protective role of Mn(II) under oxidative stress conditions as it participates in redox cycling in the hetero-binuclear ferroxidase center. Copyright © 2013 Elsevier B.V. All rights reserved.

First Principles Study on the CO Oxidation on Mn-Embedded Divacancy Graphene

PubMed Central

Jiang, Quanguo; Zhang, Jianfeng; Ao, Zhimin; Huang, Huajie; He, Haiyan; Wu, Yuping

2018-01-01

The CO oxidation mechanism on graphene with divacancy (DG) embedded with transition metal from Sc to Zn has been studied by using first principles calculations. The results indicate that O2 molecule is preferentially adsorbed on Sc, Ti, V, Cr, Mn, and Fe-DG, which can avoid the CO poisoning problem that many catalysts facing and is beneficial to the CO oxidation progress. Further study indicates that Mn-DG shows the best catalytic properties for CO oxidation with consideration of both Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) oxidation mechanisms. Along the ER mechanism, the reaction energy barrier for the first step (CO free + O2 pre-adsorbed → OOCO) is 0.96 eV. Along the LH mechanism, the energy barrier for the rate limiting step (CO adsorbed + O2 adsorbed → OOCO) is only 0.41 eV, indicating that the CO oxidation on Mn-DG will occur along LH mechanism. The Hirshfeld charge distributions of O2 and CO molecules is tuned by the embedded Mn atom, and the charge transfer from the embedded Mn atom to the adsorbed molecules plays an important role for the CO oxidation. The result shows that the Mn-embedded divacancy graphene is a noble-metal free and efficient catalyst for CO oxidation at low temperature.

Importance of trivalency and the e(g)(1) configuration in the photocatalytic oxidation of water by Mn and Co oxides.

PubMed

Maitra, Urmimala; Naidu, B S; Govindaraj, A; Rao, C N R

2013-07-16

Prompted by the early results on the catalytic activity of LiMn2O4 and related oxides in the photochemical oxidation of water, our detailed study of several manganese oxides has shown that trivalency of Mn is an important factor in determining the catalytic activity. Thus, Mn2O3, LaMnO3, and MgMn2O4 are found to be very good catalysts with turnover frequencies of 5 × 10(-4) s(-1), 4.8 × 10(-4) s(-1), and 0.8 × 10(-4) s(-1), respectively. Among the cobalt oxides, Li2Co2O4 and LaCoO3--especially the latter--exhibit excellent catalytic activity, with the turnover frequencies being 9 × 10(-4) s(-1) and 1.4 × 10(-3) s(-1), respectively. The common feature among the catalytic Mn and Co oxides is not only that Mn and Co are in the trivalent state, but Co(3+) in the Co oxides is in the intermediate t2g(5)e(g)(1) state whereas Mn(3+) is in the t2g(3e(g)(1) state. The presence of the e(g)(1) electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides.

Stability of βMnOOH and manganese oxide deposition from springwater

USGS Publications Warehouse

Hem, J.D.; Roberson, C.E.; Fournier, Reba B.

1982-01-01

Beta MnOOH is precipitated preferentially (with respect to Mn3O4) at temperatures near O°C when Mn2+ is oxidized in aerated aqueous solutions. Upon aging in solutions open to the atmosphere a slurry of βMnOOH tends to disproportionate to form MnO2 and Mn2+. In such aged solutions, Mn2+ and H+ activities can be constant, and both the oxidation reaction Mn2++¼O2(aq) + 3/2H2O → βMnOOH (c) + 2H+ and the disproportionate reaction 2βMnOOH (c) + 2H+ → MnO2(c) + Mn2+ + 2H2O can have positive reaction affinities. It is not possible for both reactions to be in thermodynamic equilibrium in the same system unless oxygen is almost completely absent. A value for ΔGf0 of −129.8±0.6 kcal/mol was obtained for βMnOOH from experimental data by assuming that the reaction affinity for the oxidation reaction is equal to that for the disproportionation. A value for ΔGf0 for βMnOOH of −129.8±0.5 kcal/mol was determined by measuring the redox potentials for the postulated half-reaction MnO2 (c) + H+ + e− → βMnOOH (c) at 0°, 5°, and 15°C and extrapolating to 25°C. Both these values are consistent with laboratory observations that βMnOOH is less stable than γMnOOH or Mn3O4 at 25°C. Analytical data for manganese-depositing springwater samples are consistent with a nonequilibrium model involving disproportionation of either βMnOOH or Mn3O4.

40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium oxide...

40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium oxide...

40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium oxide...

40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium oxide...

40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium oxide...

High-temperature oxidation of aluminum electroplated Fe-Mn alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernabai, U.; Felli, F.; Capuano, G.A.

1990-04-01

Austenitic Mn-Al alloys (20-32 W/O Mn, 7-10 Al, 2-3 Si, 1C) were found to have satisfactory oxidation resistance up to 950{degree}C under isothermal conditions in air. Surface enrichment of aluminum is a necessary condition for obtaining an almost pure alumina scale for uses at higher temperatures. Four different Mn-steels were Al-coated by the Capuano electroplating process. In all the steels there was an increase in the hot-oxidation resistance. The best results were obtained with steels containing both Al and Si, and this for temperatures up to 1,100{degree}C.

Tuning electronic and magnetic properties of Mn-mullite oxide sub-nanoclusters via MnOn polyhedron units.

PubMed

Li, Hui; Cho, Kyeongjae; Li, Shunfang; Wang, Weichao

2018-06-13

Ternary oxide nano-clusters compared to unary metallic and binary ones potentially exhibit more remarkable properties due to their higher stoichiometric flexibility in addition to cluster size variations. Herein, by combining with the structural searching scheme CALYPSO, we have built a series of Mn-mullite oxide clusters (SmxMnyOz)n {(xyz) = (125); (115); n = 1-4, 8} prior to investigation of their geometric and electronic structures via first-principles calculations. In small size regime (n < 4), (SmxMnyOz)n prefer nonstoichiometric (Sm1Mn1O5)n phases composed of nonmagnetic MnO4 tetrahedrons. When n ≧ 4, the clusters tend to develop as stoichiometric (Sm1Mn2O5)n species, including magnetic MnOn polyhedrons and Mn-Mn dimers, which contribute 3d-orbitals (dz2 and/or dx2-y2) around the Fermi levels. The different magnetic behaviors of nonstoichiometric and stoichiometric species originate from the distinct couplings of MnOn polyhedronal units, wherein Mn atoms experience different ligand fields and thus display different spin states. Such findings enable the tuning of electronic properties and potential applications in heterogeneous catalysis, electrochemical catalysis, and the related fields via engineering cluster size and stoichiometry.

Metal Inhibition of Growth and Manganese Oxidation in Pseudomonas putida GB-1

NASA Astrophysics Data System (ADS)

Pena, J.; Sposito, G.

2009-12-01

Biogenic manganese oxides (MnO2) are ubiquitous nanoparticulate minerals that contribute to the adsorption of nutrient and toxicant metals, the oxidative degradation of various organic compounds, and the respiration of metal-reducing bacteria in aquatic and terrestrial environments. The formation of these minerals is catalyzed by a diverse and widely-distributed group of bacteria and fungi, often through the enzymatic oxidation of aqueous Mn(II) to Mn(IV). In metal-impacted ecosystems, toxicant metals may alter the viability and metabolic activity of Mn-oxidizing organisms, thereby limiting the conditions under which biogenic MnO2 can form and diminishing their potential as adsorbent materials. Pseudomonas putida GB-1 (P. putida GB-1) is a model Mn-oxidizing laboratory culture representative of freshwater and soil biofilm-forming bacteria. Manganese oxidation in P. putida GB-1 occurs via two single-electron-transfer reactions, involving a multicopper oxidase enzyme found on the bacterial outer membrane surface. Near the onset of the stationary phase of growth, dark brown MnO2 particles are deposited in a matrix of bacterial cells and extracellular polymeric substances, thus forming heterogeneous biomineral assemblages. In this study, we assessed the influence of various transition metals on microbial growth and manganese oxidation capacity in a P. putida GB-1 culture propagated in a nutrient-rich growth medium. The concentration-response behavior of actively growing P. putida GB-1 cells was investigated for Fe, Co, Ni, Cu and Zn at pH ≈ 6 in the presence and absence of 1 mM Mn. Toxicity parameters such as EC0, EC50 and Hillslope, and EC100 were obtained from the sigmoidal concentration-response curves. The extent of MnO2 formation in the presence of the various metal cations was documented 24, 50, 74 and 104 h after the metal-amended medium was inoculated. Toxicity values were compared to twelve physicochemical properties of the metals tested. Significant

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction.

PubMed

Hansel, Colleen M; Zeiner, Carolyn A; Santelli, Cara M; Webb, Samuel M

2012-07-31

Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems.

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction

PubMed Central

Hansel, Colleen M.; Zeiner, Carolyn A.; Santelli, Cara M.; Webb, Samuel M.

2012-01-01

Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems. PMID:22802654

Novel Solar Energy Conversion Materials by Design of Mn(II) Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lany, S.; Peng, H.; Ndione, P.

2013-01-01

Solar energy conversion materials need to fulfill simultaneously a number of requirements in regard of their band-structure, optical properties, carrier transport, and doping. Despite their desirable chemical properties, e.g., for photo-electrocatalysis, transition-metal oxides usually do not have desirable semiconducting properties. Instead, oxides with open cation d-shells are typically Mott or charge-transfer insulators with notoriously poor transport properties, resulting from large effective electron/hole masses or from carrier self-trapping. Based on the notion that the electronic structure features (p-d interaction) supporting the p-type conductivity in d10 oxides like Cu2O and CuAlO2 occurs in a similar fashion also in the d5 (high-spin) oxides,more » we recently studied theoretically the band-structure and transport properties of the prototypical binary d5 oxides MnO and Fe2O3 [PRB 85, 201202(R)]. We found that MnO tends to self-trap holes by forming Mn+III, whereas Fe2O3 self-traps electrons by forming Fe+II. However, the self-trapping of holes is suppressed by when Mn is tetrahedrally coordinated, which suggests specific routes to design novel solar conversion materials by considering ternary Mn(II) oxides or oxide alloys. We are presenting theory, synthesis, and initial characterization for these novel energy materials.« less

Mn-Ce-Co complex oxide nanoparticles: hydrothermal synthesis and their catalytic subcritical oxidation of 4,4'-Dibromobiphenyl.

PubMed

Chen, Jinyang; Xu, Tianjiao; Ding, Junying; Ji, Yimei; Ni, Pei; Li, Zhilian

2012-10-15

In situ transformation of 4,4'-Dibromobiphenyl (4,4'-DBB) in water was observed with hydrothermal diamond anvil cell (HDAC) up to 633 K. It shows that 4,4'-DBB dissolves in water to form a homogenous phase at the temperature of 588 K and thus subcritical water oxidation of 4,4'-DBB higher than the temperature can be a homogenous phase. To accelerate the oxidative degradation, some Mn-Ce-Co complex oxide nanoparticles of about 100 nm were prepared by co-precipitation hydrothermal method. The nanoparticles show enough stability and catalytic activity for oxidative degradation of 4,4'-DBB in subcritical water. The catalytic activation increases with some Co doping and as for the complex oxides of Mn(1)Ce(1), Mn(0.9)Ce(1)Co(0.1), Mn(0.5)Ce(1)Co(0.5), Mn(0.1)Ce(1)Co(0.9), and Co(1)Ce(1), the Mn(0.9)Ce(1)Co(0.1) presents the best activation. The main intermediate products of degradation are benzoic acid and phenol. The apparent activation energy (E(a)) is 35.92 with 5% Mn(0.9)Ce(1)Co(0.1) as catalyst and 46.69 kJ/mol with no catalyst about the chemical oxygen demand (COD). Copyright © 2012 Elsevier B.V. All rights reserved.

Biological Low-pH Mn(II) Oxidation in a Manganese Deposit Influenced by Metal-Rich Groundwater

PubMed Central

Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.

2016-01-01

ABSTRACT The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems. IMPORTANCE This study provides multiple lines of evidence to show that microbes are the main drivers of Mn(II) oxidation even at acidic pH, offering new insights into Mn biogeochemical cycling. A distinct, highly adapted microbial community inhabits acidic, oligotrophic Mn deposits and mediates biological Mn oxidation. These data highlight the importance of biological processes for Mn biogeochemical cycling

Virus Removal by Biogenic Cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Gusseme, B.; Du Laing, G; Hennebel, T

2010-01-01

The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups ofmore » the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L{sup -1} bio-Ce. Given the fact that virus removal with 50 mg L{sup -1} Ce(III) as CeNO{sub 3} was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.« less

The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean

PubMed Central

Emerson, David

2016-01-01

Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157

Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

NASA Astrophysics Data System (ADS)

Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

2017-12-01

Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

The effect of coal bed dewatering and partial oxidation on biogenic methane potential

USGS Publications Warehouse

Jones, Elizabeth J.P.; Harris, Steve H.; Barnhart, Elliott P.; Orem, William H.; Clark, Arthur C.; Corum, Margo D.; Kirshtein, Julie D.; Varonka, Matthew S.; Voytek, Mary A.

2013-01-01

Coal formation dewatering at a site in the Powder River Basin was associated with enhanced potential for secondary biogenic methane determined by using a bioassay. We hypothesized that dewatering can stimulate microbial activity and increase the bioavailability of coal. We analyzed one dewatered and two water-saturated coals to examine possible ways in which dewatering influences coal bed natural gas biogenesis by looking at differences with respect to the native coal microbial community, coal-methane organic intermediates, and residual coal oxidation potential. Microbial biomass did not increase in response to dewatering. Small Subunit rRNA sequences retrieved from all coals sampled represented members from genera known to be aerobic, anaerobic and facultatively anaerobic. A Bray Curtis similarity analysis indicated that the microbial communities in water-saturated coals were more similar to each other than to the dewatered coal, suggesting an effect of dewatering. There was a higher incidence of long chain and volatile fatty acid intermediates in incubations of the dewatered coal compared to the water-saturated coals, and this could either be due to differences in microbial enzymatic activities or to chemical oxidation of the coal associated with O2 exposure. Dilute H2O2 treatment of two fractions of structural coal (kerogen and bitumen + kerogen) was used as a proxy for chemical oxidation by O2. The dewatered coal had a low residual oxidation potential compared to the water-saturated coals. Oxidation with 5% H2O2 did increase the bioavailability of structural coal, and the increase in residual oxidation potential in the water saturated coals was approximately equivalent to the higher methanogenic potential measured in the dewatered coal. Evidence from this study supports the idea that coal bed dewatering could stimulate biogenic methanogenesis through partial oxidation of the structural organics in coal once anaerobic conditions are restored.

Manganese(IV) Oxide Production by Acremonium sp. Strain KR21-2 and Extracellular Mn(II) Oxidase Activity

PubMed Central

Miyata, Naoyuki; Tani, Yukinori; Maruo, Kanako; Tsuno, Hiroshi; Sakata, Masahiro; Iwahori, Keisuke

2006-01-01

Ascomycetes that can deposit Mn(III, IV) oxides are widespread in aquatic and soil environments, yet the mechanism(s) involved in Mn oxide deposition remains unclear. A Mn(II)-oxidizing ascomycete, Acremonium sp. strain KR21-2, produced a Mn oxide phase with filamentous nanostructures. X-ray absorption near-edge structure (XANES) spectroscopy showed that the Mn phase was primarily Mn(IV). We purified to homogeneity a laccase-like enzyme with Mn(II) oxidase activity from cultures of strain KR21-2. The purified enzyme oxidized Mn(II) to yield suspended Mn particles; XANES spectra indicated that Mn(II) had been converted to Mn(IV). The pH optimum for Mn(II) oxidation was 7.0, and the apparent half-saturation constant was 0.20 mM. The enzyme oxidized ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)] (pH optimum, 5.5; Km, 1.2 mM) and contained two copper atoms per molecule. Moreover, the N-terminal amino acid sequence (residues 3 to 25) was 61% identical with the corresponding sequence of an Acremonium polyphenol oxidase and 57% identical with that of a Myrothecium bilirubin oxidase. These results provide the first evidence that a fungal multicopper oxidase can convert Mn(II) to Mn(IV) oxide. The present study reinforces the notion of the contribution of multicopper oxidase to microbially mediated precipitation of Mn oxides and suggests that Acremonium sp. strain KR21-2 is a good model for understanding the oxidation of Mn in diverse ascomycetes. PMID:17021194

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

PubMed

Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

2017-01-03

The design of a high-performance catalyst for Hg 0 oxidation and predicting the extent of Hg 0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg 0 oxidation, and the reaction mechanism and the reaction kinetics of Hg 0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg 0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg 0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg 0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg 0 with adsorbed HCl), and the rate of Hg 0 oxidation mainly depended on Cl • concentration on the surface. As H 2 O, SO 2 , and NO not only inhibited Cl • formation on the surface but also interfered with the interface reaction between gaseous Hg 0 and Cl • on the surface, Hg 0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H 2 O, SO 2 , and NO. Furthermore, the extent of Hg 0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter k E-R , and the predicted result was consistent with the experimental result.

Biological low pH Mn(II) oxidation in a manganese deposit influenced by metal-rich groundwater

USGS Publications Warehouse

Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.; Küsel, Kirsten

2016-01-01

The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems.

Water oxidation catalyzed by the tetranuclear Mn complex [Mn(IV)4O5(terpy)4(H2O)2](ClO4)6.

PubMed

Gao, Yunlong; Crabtree, Robert H; Brudvig, Gary W

2012-04-02

The tetranuclear manganese complex [Mn(IV)(4)O(5)(terpy)(4)(H(2)O)(2)](ClO(4))(6) (1; terpy = 2,2':6',2″-terpyridine) gives catalytic water oxidation in aqueous solution, as determined by electrochemistry and GC-MS. Complex 1 also exhibits catalytic water oxidation when adsorbed on kaolin clay, with Ce(IV) as the primary oxidant. The redox intermediates of complex 1 adsorbed on kaolin clay upon addition of Ce(IV) have been characterized by using diffuse reflectance UV/visible and EPR spectroscopy. One of the products in the reaction on kaolin clay is Mn(III), as determined by parallel-mode EPR spectroscopic studies. When 1 is oxidized in aqueous solution with Ce(IV), the reaction intermediates are unstable and decompose to form Mn(II), detected by EPR spectroscopy, and MnO(2). DFT calculations show that the oxygen in the mono-μ-oxo bridge, rather than Mn(IV), is oxidized after an electron is removed from the Mn(IV,IV,IV,IV) tetramer. On the basis of the calculations, the formation of O(2) is proposed to occur by reaction of water with an electrophilic manganese-bound oxyl radical species, (•)O-Mn(2)(IV/IV), produced during the oxidation of the tetramer. This study demonstrates that [Mn(IV)(4)O(5)(terpy)(4)(H(2)O)(2)](ClO(4))(6) may be relevant for understanding the role of the Mn tetramer in photosystem II.

In situ arsenic oxidation and sorption by a Fe-Mn binary oxide waste in soil.

PubMed

McCann, Clare M; Peacock, Caroline L; Hudson-Edwards, Karen A; Shrimpton, Thomas; Gray, Neil D; Johnson, Karen L

2018-01-15

The ability of a Fe-Mn binary oxide waste to adsorb arsenic (As) in a historically contaminated soil was investigated. Initial laboratory sorption experiments indicated that arsenite [As(III)] was oxidized to arsenate [As(V)] by the Mn oxide component, with concurrent As(V) sorption to the Fe oxide. The binary oxide waste had As(III) and As(V) adsorption capacities of 70mgg -1 and 32mgg -1 respectively. X-ray Absorption Near-Edge Structure and Extended X-ray Absorption Fine Structure at the As K-edge confirmed that all binary oxide waste surface complexes were As(V) sorbed by mononuclear bidentate corner-sharing, with 2 Fe at ∼3.27Ǻ. The ability of the waste to perform this coupled oxidation-sorption reaction in real soils was investigated with a 10% by weight addition of the waste to an industrially As contaminated soil. Electron probe microanalysis showed As accumulation onto the Fe oxide component of the binary oxide waste, which had no As innately. The bioaccessibility of As was also significantly reduced by 7.80% (p<0.01) with binary oxide waste addition. The results indicate that Fe-Mn binary oxide wastes could provide a potential in situ remediation strategy for As and Pb immobilization in contaminated soils. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Removal of thallium from aqueous solutions using Fe-Mn binary oxides.

PubMed

Li, Huosheng; Chen, Yongheng; Long, Jianyou; Li, Xiuwan; Jiang, Daqian; Zhang, Ping; Qi, Jianying; Huang, Xuexia; Liu, Juan; Xu, Ruibing; Gong, Jian

2017-09-15

In this study, Fe-Mn binary oxides, which harbor the strong oxidative power of manganese dioxide and the high adsorption capacity of iron oxides, were synthesized for Tl(I) removal using a concurrent chemical oxidation and precipitation method. The adsorption of Tl onto the Fe-Mn adsorbent was fast, effective, and selective, with equilibrium sorption reaching over 95% under a broad operating pH (3-12), and high ionic strength (0.1-0.5mol/L). The adsorption can be well fitted with both Langmuir and Freundlich isotherms, and the kinetics can be well described by the pseudo-second-order model. Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) spectra suggest that surface complexation, oxidation and precipitation were the main mechanisms for the removal of Tl. This study shows that the Fe-Mn binary oxides could be a promising adsorbent for Tl removal. Copyright © 2017 Elsevier B.V. All rights reserved.

Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

PubMed

Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

2016-12-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

NASA Astrophysics Data System (ADS)

Hamilton, J. F.; Alfarra, M. R.; Robinson, N.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Coe, H.; Allan, J. D.

2013-11-01

Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding these transformation processes has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a Southeast Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high-resolution aerosol mass spectrometry and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyl tetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

NASA Astrophysics Data System (ADS)

Hamilton, J. F.; Alfarra, M. R.; Robinson, N.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Coe, H.; Allan, J. D.

2013-07-01

Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding the process of these transformations has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a South East Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high resolution aerosol mass spectrometry and fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyltetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

Mycogenic Mn(II) oxidation promotes remediation of acid mine drainage and other anthropogenically impacted environments

NASA Astrophysics Data System (ADS)

Santelli, C. M.; Chaput, D.; Hansel, C. M.; Burgos, W. D.

2014-12-01

Manganese is a pollutant in worldwide environments contaminated with metals and organics, such as acid mine drainage (AMD), freshwater ponds, and agricultural waste storage sites. Microorganisms contribute to the removal of dissolved Mn compounds in the environment by promoting Mn(II) oxidation reactions. The oxidation of Mn(II) results in the precipitation of sparingly soluble Mn(IV) oxide minerals, effectively removing the metal from the aqueous milieu (e.g., groundwater or wastewater streams). In recent years, our research has identified a diversity of Mn(II)-oxidizing fungi inhabiting these polluted environments, however their overall contribution to the remediation process in situ remains poorly understood. Here we present results of culture-based and Next Generation Sequencing (NGS) studies in AMD treatment systems actively remediating Mn and other metals where we profile the bacterial, fungal, algal and archaeal communities to determine the overall community diversity and to establish the relative abundance of known Mn(II) oxidizers. A variety of treatment systems with varying Mn-removal efficiencies were sampled to understand the relationship between remediation efficiency and microbial community composition and activity. Targeted-amplicon sequencing of DNA and RNA of the 16S rRNA genes (bacteria and archaea), 23S rRNA genes (algae) and ITS region (fungi) was performed using both 454 pyrosequencing and Illumina platforms. Results showed that only the fungal taxonomic profiles significantly differed between sites that removed the majority of influent Mn and those that did not. Specifically, Ascomycota (which include known Mn(II) oxidizers isolated from these treatment systems) dominated greater efficiency systems whereas less efficient systems were dominated by Basidiomycota. Furthermore, known Mn(II) oxidizers accounted for only a minor proportion of bacterial sequences but a far greater proportion of fungal sequences. These culture-independent studies lend

Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

NASA Astrophysics Data System (ADS)

Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

2013-05-01

Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

Efficient catalytic As(III) oxidation on the surface of ferrihydrite in the presence of aqueous Mn(II).

PubMed

Lan, Shuai; Ying, Hong; Wang, Xiaoming; Liu, Fan; Tan, Wenfeng; Huang, Qiaoyun; Zhang, Jing; Feng, Xionghan

2018-01-01

Arsenic is a carcinogenic element that exists primarily as arsenate [As(V)] and arsenite [As(III)] in the nature environment, with As(III) being more toxic and mobile of the two species. In addition, ferrihydrite, which is widely distributed in soils and aquatic environments, can catalyze the oxidation of Mn(II) and accelerate the formation of high-valence Mn, which can significantly influence the speciation, toxicity, and mobility of As when these species co-exist. In this context, we herein explored the mechanism of As(III) oxidation in the presence of ferrihydrite and Mn(II) using a kinetic approach combined with multiple spectroscopic techniques, including X-ray absorption near edge spectroscopy, in situ horizontal attenuated total-reflectance Fourier transform infrared spectroscopy, and in situ quick scanning X-ray absorption spectroscopy. Our results indicate that efficient As(III) oxidation by dissolved O 2 occurs on the surface of ferrihydrite in the presence of aqueous Mn(II). Compared with As(III) oxidation in the presence of ferrihydrite and Mn oxides (i.e., Mn oxides/hydroxides), the degree of As(III) oxidation in the ferrihydrite-Mn(II) system was significantly higher, and the majority of generated As(V) was adsorbed on the mineral (i.e., ferrihydrite) surface. Furthermore, As(III) oxidation was enhanced upon increasing both the molar ratio of Mn(II)/As(III) and the solution pH. The greater As(III) oxidation by O 2 in the ferrihydrite-Mn(II) system was mainly attributed to the formation of a strong oxidant of the instantaneous intermediate Mn(III) species via Mn(II) oxidation under catalysis by the ferrihydrite surface. Moreover, As(III) oxidation occurred mainly on the ferrihydrite surface and was accompanied by the regeneration of Mn(II), thereby rendering it recyclable. These results therefore provide new insights into the mechanism of As(III) oxidation on the surfaces of Fe oxides (i.e., Fe oxides/hydroxides) in the presence of aqueous Mn(II) as

Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

2018-05-01

Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors.

PubMed

Nam, Inho; Kim, Nam Dong; Kim, Gil-Pyo; Park, Junsu; Yi, Jongheop

2012-07-01

A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth.

PubMed

Catling, D C; Zahnle, K J; McKay, C

2001-08-03

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.

Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal.

PubMed

Ma, Zichuan; Zhao, Dongyuan; Chang, Yongfang; Xing, Shengtao; Wu, Yinsu; Gao, Yuanzhe

2013-10-21

Magnetic nanomaterials that can be easily separated and recycled due to their magnetic properties have received considerable attention in the field of water treatment. However, these nanomaterials usually tend to aggregate and alter their properties. Herein, we report an economical and environmentally friendly method for the synthesis of magnetic nanoparticles with core-shell structure. MnFe2O4 nanoparticles have been successfully coated with amorphous Mn-Co oxide shells. The synthesized MnFe2O4@Mn-Co oxide nanoparticles have highly negatively charged surface in aqueous solution over a wide pH range, thus preventing their aggregation and enhancing their performance for heavy metal cation removal. The adsorption isotherms are well fitted to a Langmuir adsorption model, and the maximal adsorption capacities of Pb(II), Cu(II) and Cd(II) on MnFe2O4@Mn-Co oxide are 481.2, 386.2 and 345.5 mg g(-1), respectively. All the metal ions can be completely removed from the mixed metal ion solutions in a short time. Desorption studies confirm that the adsorbent can be effectively regenerated and reused.

Diffusion Behavior of Mn and Si Between Liquid Oxide Inclusions and Solid Iron-Based Alloy at 1473 K

NASA Astrophysics Data System (ADS)

Kim, Sun-Joong; Tago, Hanae; Kim, Kyung-Ho; Kitamura, Shin-ya; Shibata, Hiroyuki

2018-06-01

In order to clarify the changes in the composition of oxide inclusions in steel, the effect of the metal and oxide composition on the reaction between solid Fe-based alloys and liquid multi-component oxides was investigated using the diffusion couple method at 1473 K. The measured concentration gradients of Mn and Si in the metal indicated that Mn diffused into the metal from the oxide, while the diffusion of Si occurred in the opposite direction. In addition, the MnO content in the oxide decreased with heat treatment time, while the SiO2 content increased. The compositional changes in both phases indicated that the Mn content in the metal near the interface increased with heat treatment with decreasing MnO content in the oxide. Assuming local equilibrium at the interface, the calculated [Mn]2/[Si] ratio at the interface in equilibrium with the oxide increased with increases in the MnO/SiO2 ratio in the oxide. The difference in the [Mn]2/[Si] ratios between the interface and the metal matrix increased, which caused the diffusion of Mn and Si between the multi-component oxide and metal. By measuring the diffusion lengths of Mn and Si in the metal, the chemical diffusion coefficients of Mn and Si were obtained to calculate the composition changes in Mn and Si in the metal. The calculated changes in Mn and Si in the metal agreed with the experimental results.

Mn-Oxide Minerals from a Terrestrial Cave Environment: Biomarkers for the Search for Life on Mars?

NASA Technical Reports Server (NTRS)

Spilde, M. N.; Brearley, A. J.; Papike, J. J.

2001-01-01

Mn-oxides are promising biomarkers because microbes greatly accelerate Mn-oxide formation rates and produce distinctive oxidation states. Mn minerals in terrestrial caves form subaerially and could conceivably be present in the subsurface of Mars. Additional information is contained in the original extended abstract.

Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface

NASA Astrophysics Data System (ADS)

Sung, Windsor; Morgan, James J.

1981-12-01

A laboratory study was undertaken to ascertain the role of surface catalysis in Mn(II) oxidative removal. γ-FeOOH, a ferric oxyhydroxide formed by O2 oxidation of ferrous iron in solution, was studied in the following ways: surface charge characteristics by acid base titration, adsorption of Mn(II) and surface oxidation of Mn(II). A rate law was formulated to account for the effects of pH and the amount of surface on the surface oxidation rate of Mn(II). The presence of milli-molar levels of γ-FeOOH was shown to reduce significantly the half-life of Mn(II) in 0.7 M NaCl from hundreds of hours to hours. The numerical values of the surface rate constants for the γ-FeOOH and that reported for colloidal MnO2 are comparable in order of magnitude.

Formation of Deep Sea Umber Deposits Linked to Microbial Metal Oxidation at the South Atlantic Ridge

NASA Astrophysics Data System (ADS)

Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

2015-04-01

Umber deposits are important metalliferous deposits, which occur in off-axis half-graben structures at ancient and modern ocean floor. The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biochemical mechanisms involved to the precipitation of Mn oxides and co-precipitation of Fe oxyhydroxides and Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data suggest that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic Fe(II)-oxidizing bacteria, which constitute a trophic base that may support the activities of heterotrophic Mn(II)-oxidizing bacteria. The biological origin of umber deposits underscore the importance of geomicrobiologcial interaction in triggering the formation of deep-sea deposits, with important implications for the generation of submarine Mn deposits and crusts.

Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer: aircraft vertical profiles in Houston, TX

NASA Astrophysics Data System (ADS)

Brown, S. S.; Dubé, W. P.; Bahreini, R.; Middlebrook, A. M.; Brock, C. A.; Warneke, C.; de Gouw, J. A.; Washenfelder, R. A.; Atlas, E.; Peischl, J.; Ryerson, T. B.; Holloway, J. S.; Schwarz, J. P.; Spackman, R.; Trainer, M.; Parrish, D. D.; Fehshenfeld, F. C.; Ravishankara, A. R.

2013-11-01

Organic compounds are a large component of aerosol mass, but organic aerosol (OA) sources remain poorly characterized. Recent model studies have suggested nighttime oxidation of biogenic hydrocarbons as a potentially large OA source, but analysis of field measurements to test these predictions is sparse. We present nighttime vertical profiles of nitrogen oxides, ozone, VOCs and aerosol composition measured during low approaches of the NOAA P-3 aircraft to airfields in Houston, TX. This region has large emissions of both biogenic hydrocarbons and nitrogen oxides. The latter category serves as a source of the nitrate radical, NO3, a key nighttime oxidant. Biogenic VOCs (BVOC) and urban pollutants were concentrated within the nocturnal boundary layer (NBL), which varied in depth from 100-400 m. Despite concentrated NOx at low altitude, ozone was never titrated to zero, resulting in rapid NO3 radical production rates of 0.2-2.7 ppbv h-1 within the NBL. Monoterpenes and isoprene were frequently present within the NBL and underwent rapid oxidation (up to 1 ppbv h-1), mainly by NO3 and to a lesser extent O3. Concurrent enhancement in organic and nitrate aerosol on several profiles was consistent with primary emissions and with secondary production from nighttime BVOC oxidation, with the latter equivalent to or slightly larger than the former. Some profiles may have been influenced by biomass burning sources as well, making quantitative attribution of organic aerosol sources difficult. Ratios of organic aerosol to CO within the NBL ranged from 14 to 38 μg m-3 OA/ppmv CO. A box model simulation incorporating monoterpene emissions, oxidant formation rates and monoterpene SOA yields suggested overnight OA production of 0.5 to 9 μg m-3.

Effects of dew point on selective oxidation of TRIP steels containing Si, Mn, and B

NASA Astrophysics Data System (ADS)

Lee, Suk-Kyu; Kim, Jong-Sang; Choi, Jin-Won; Kang, Namhyun; Cho, Kyung-Mox

2011-04-01

The selective oxidation of Si, Mn, and B on TRIP steel surfaces is a widely known phenomenon that occurs during heat treatment. However, the relationship between oxide formation and the annealing factors is not completely understood. This study examines the effect of the annealing conditions (dew point and annealing temperature) on oxide formation. A low dew point of -40 °C leads to the formation of Si-based oxides on the surface. A high dew point of -20 °C changes the oxide type to Mn-based oxides because the formation of Si oxides on the surface is suppressed by internal oxidation. Mn-based oxides exhibit superior wettability due to aluminothermic reduction during galvanizing.

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope

Consequences of MnSOD interactions with nitric oxide: nitric oxide dismutation and the generation of peroxynitrite and hydrogen peroxide.

PubMed

Filipović, Milos R; Stanić, Dragana; Raicević, Smiljana; Spasić, Mihajlo; Niketić, Vesna

2007-01-01

The present study demonstrates that manganese superoxide dismutase (MnSOD) (Escherichia coli), binds nitric oxide (*NO) and stimulates its decay under both anaerobic and aerobic conditions. The results indicate that previously observed MnSOD-catalyzed *NO disproportionation (dismutation) into nitrosonium (NO+) and nitroxyl (NO-) species under anaerobic conditions is also operative in the presence of molecular oxygen. Upon sustained aerobic exposure to *NO, MnSOD-derived NO- species initiate the formation of peroxynitrite (ONOO-) leading to enzyme tyrosine nitration, oxidation and (partial) inactivation. The results suggest that both ONOO- decomposition and ONOO(-)-dependent tyrosine residue nitration and oxidation are enhanced by metal centre-mediated catalysis. We show that the generation of ONOO- is accompanied by the formation of substantial amounts of H2O2. MnSOD is a critical mitochondrial antioxidant enzyme, which has been found to undergo tyrosine nitration and inactivation in various pathologies associated with the overproduction of *NO. The results of the present study can account for the molecular specificity of MnSOD nitration in vivo. The interaction of *NO with MnSOD may represent a novel mechanism by which MnSOD protects the cell from deleterious effects associated with overproduction of *NO.

Mn(II) Oxidation by the Multicopper Oxidase Complex Mnx: A Binuclear Activation Mechanism.

PubMed

Soldatova, Alexandra V; Tao, Lizhi; Romano, Christine A; Stich, Troy A; Casey, William H; Britt, R David; Tebo, Bradley M; Spiro, Thomas G

2017-08-23

The bacterial protein complex Mnx contains a multicopper oxidase (MCO) MnxG that, unusually, catalyzes the two-electron oxidation of Mn(II) to MnO 2 biomineral, via a Mn(III) intermediate. Although Mn(III)/Mn(II) and Mn(IV)/Mn(III) reduction potentials are expected to be high, we find a low reduction potential, 0.38 V (vs Normal Hydrogen Electrode, pH 7.8), for the MnxG type 1 Cu 2+ , the electron acceptor. Indeed the type 1 Cu 2+ is not reduced by Mn(II) in the absence of molecular oxygen, indicating that substrate oxidation requires an activation step. We have investigated the enzyme mechanism via electronic absorption spectroscopy, using chemometric analysis to separate enzyme-catalyzed MnO 2 formation from MnO 2 nanoparticle aging. The nanoparticle aging time course is characteristic of nucleation and particle growth; rates for these processes followed expected dependencies on Mn(II) concentration and temperature, but exhibited different pH optima. The enzymatic time course is sigmoidal, signaling an activation step, prior to turnover. The Mn(II) concentration and pH dependence of a preceding lag phase indicates weak Mn(II) binding. The activation step is enabled by a pK a > 8.6 deprotonation, which is assigned to Mn(II)-bound H 2 O; it induces a conformation change (consistent with a high activation energy, 106 kJ/mol) that increases Mn(II) affinity. Mnx activation is proposed to decrease the Mn(III/II) reduction potential below that of type 1 Cu(II/I) by formation of a hydroxide-bridged binuclear complex, Mn(II)(μ-OH)Mn(II), at the substrate site. Turnover is found to depend cooperatively on two Mn(II) and is enabled by a pK a 7.6 double deprotonation. It is proposed that turnover produces a Mn(III)(μ-OH) 2 Mn(III) intermediate that proceeds to the enzyme product, likely Mn(IV)(μ-O) 2 Mn(IV) or an oligomer, which subsequently nucleates MnO 2 nanoparticles. We conclude that Mnx exploits manganese polynuclear chemistry in order to facilitate an otherwise

Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals.

PubMed

Feng, Xiong Han; Zhai, Li Mei; Tan, Wen Feng; Liu, Fan; He, Ji Zheng

2007-05-01

Several Mn oxide minerals commonly occurring in soils were synthesized by modified or optimized methods. The morphologies, structures, compositions and surface properties of the synthesized Mn oxide minerals were characterized. Adsorption and redox reactions of heavy metals on these minerals in relation to the mineral structures and surface properties were also investigated. The synthesized birnessite, todorokite, cryptomelane, and hausmannite were single-phased minerals and had the typical morphologies from analyses of XRD and TEM/ED. The PZCs of the synthesized birnessite, todorokite and cryptomelane were 1.75, 3.50 and 2.10, respectively. The magnitude order of their surface variable negative charge was: birnessite> or =cryptomelane>todorokite. The hausmannite had a much higher PZC than others with the least surface variable negative charge. Birnessite exhibited the largest adsorption capacity on heavy metals Pb(2+), Cu(2+), Co(2+), Cd(2+) and Zn(2+), while hausmannite the smallest one. Birnessite, cryptomelane and todorokite showed the greatest adsorption capacity on Pb(2+) among the tested heavy metals. Hydration tendency (pK(1)) of the heavy metals and the surface variable charge of the Mn minerals had significant impacts on the adsorption. The ability in Cr(III) oxidation and concomitant release of Mn(2+) varied greatly depending on the structure, composition, surface properties and crystallinity of the minerals. The maximum amounts of Cr(III) oxidized by the Mn oxide minerals in order were (mmol/kg): birnessite (1330.0)>cryptomelane (422.6)>todorokite (59.7)>hausmannite (36.6).

Enzymatic Manganese(II) Oxidation by Metabolically Dormant Spores of Diverse Bacillus Species

PubMed Central

Francis, Chris A.; Tebo, Bradley M.

2002-01-01

Bacterial spores are renowned for their longevity, ubiquity, and resistance to environmental insults, but virtually nothing is known regarding whether these metabolically dormant structures impact their surrounding chemical environments. In the present study, a number of spore-forming bacteria that produce dormant spores which enzymatically oxidize soluble Mn(II) to insoluble Mn(IV) oxides were isolated from coastal marine sediments. The highly charged and reactive surfaces of biogenic metal oxides dramatically influence the oxidation and sorption of both trace metals and organics in the environment. Prior to this study, the only known Mn(II)-oxidizing sporeformer was the marine Bacillus sp. strain SG-1, an extensively studied bacterium in which Mn(II) oxidation is believed to be catalyzed by a multicopper oxidase, MnxG. Phylogenetic analysis based on 16S rRNA and mnxG sequences obtained from 15 different Mn(II)-oxidizing sporeformers (including SG-1) revealed extensive diversity within the genus Bacillus, with organisms falling into several distinct clusters and lineages. In addition, active Mn(II)-oxidizing proteins of various sizes, as observed in sodium dodecyl sulfate-polyacrylamide electrophoresis gels, were recovered from the outer layers of purified dormant spores of the isolates. These are the first active Mn(II)-oxidizing enzymes identified in spores or gram-positive bacteria. Although extremely resistant to denaturation, the activities of these enzymes were inhibited by azide and o-phenanthroline, consistent with the involvement of multicopper oxidases. Overall, these studies suggest that the commonly held view that bacterial spores are merely inactive structures in the environment should be revised. PMID:11823231

Oxidative dissolution of biogenic uraninite in groundwater at Old Rifle, CO

USGS Publications Warehouse

Campbell, Kate M.; Veeramani, Harish; Ulrich, Kai-Uwe; Blue, Lisa Y.; Giammar, Dianiel E.; Bernier-Latmani, Rizlan; Stubbs, Joanne E.; Suvorova, Elena; Yabusaki, Steve; Lezama-Pacheco, Juan S.; Mehta, Apurva; Long, Philip E.; Bargar, John R.

2011-01-01

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50–100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Biogenic Emission Inventory System (BEIS)

EPA Pesticide Factsheets

Biogenic Emission Inventory System (BEIS) estimates volatile organic compound (VOC) emissions from vegetation and nitric oxide (NO) emission from soils. Recent BEIS development has been restricted to the SMOKE system

Nanostructured Mn-Fe Binary Mixed Oxide: Synthesis, Characterization and Evaluation for Arsenic Removal.

PubMed

Pillewan, Pradnya; Mukherjee, Shrabanti; Bansiwal, Amit; Rayalu, Sadhana

2014-07-01

Adsorption of arsenic on bimetallic Mn and Fe mixed oxide was carried out using both field as well as simulated water. The material was synthesized using hydrothermal method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Langmuir and Freundlich adsorption isotherms were computed using batch adsorption studies to determine the adsorption capacity of Mn-Fe binary mixed oxide for arsenic. Adsorption capacity for MFBMO obtained from Freundlich model was found to be 2.048 mg/g for simulated water and 1.084 mg/g for field water. Mn-Fe binary mixed oxide was found to be effective adsorbent for removal of arsenic from water.

Surface Selective Oxide Reduction During the Intercritical Annealing of Medium Mn Steel

NASA Astrophysics Data System (ADS)

Jo, Kyoung Rae; Cho, Lawrence; Oh, Jong Han; Kim, Myoung Soo; Kang, Ki Cheol; De Cooman, Bruno C.

2017-08-01

Third generation advanced high-strength steels achieve an excellent strength-ductility balance using a cost-effective alloy composition. During the continuous annealing of medium Mn steel, the formation of an external selective oxide layer of MnO has a negative impact on the coating quality after galvanizing. A procedure to reduce the selective oxide was therefore developed. It involves annealing in the temperature range of 1073 K to 1323 K (800 °C to 1050 °C) in a HNx gas atmosphere. Annealing at higher temperatures and the use of larger H2 volume fractions are shown to make the gas atmosphere reducing with respect to MnO. The reduction of the surface MnO layer was observed by SEM, GDOES, and cross-sectional TEM analysis.

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

NASA Astrophysics Data System (ADS)

Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

2002-12-01

There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

Anaerobic oxidation of [1,2-14C]Dichloroethene under Mn(IV)-reducing conditions

USGS Publications Warehouse

Bradley, Paul M.; Landmeyer, James E.; Dinicola, Richard S.

1998-01-01

Anaerobic oxidation of [1,2-14C]dichloroethene to14CO2 under Mn(IV)-reducing conditions was demonstrated. The results indicate that oxidative degradation of partially chlorinated solvents like dichloroethene can be significant even under anoxic conditions and demonstrate the potential importance of Mn(IV) reduction for remediation of chlorinated groundwater contaminants.

Microwave synthesis and electrochemical characterization of Mn/Ni mixed oxide for supercapacitor application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasankumar, T.; Jose, Sujin P., E-mail: sujamystica@yahoo.com; Ilangovan, R.

Nanostructured Mn/Ni mixed metal oxide was synthesized at ambient temperature by facile microwave irradiation technique. The crystal structure and surface morphology were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. X-ray diffraction analysis confirmed the formation of Mn/Ni mixed oxide in rhombohedral phase and the grain size calculated was found to be 87 nm. The irregular spherical morphology of the prepared sample was exhibited by the SEM images. The characteristic peaks of FTIR at about 630 cm{sup −1} and 749 cm{sup −1} were attributed to the Mn-O and Ni-O stretching vibrations respectively. The presence of both Mn and Ni inmore » the prepared sample was validated by the EDS spectra which in turn confirmed the formation of mixed oxide. Cyclic voltammetry and galvanostatic chargedischarge measurements were employed to investigate the electrochemical performance of the mixed oxide. The cyclic voltammetry curves demonstrated good capacitive performance of the sample in the potential window −0.2V to 0.9V. The charge discharge study revealed the suitability of the prepared mixed oxide for the fabrication of supercapacitor electrode.« less

A novel solution for hydroxylated PAHs removal by oxidative coupling reaction using Mn oxide.

PubMed

Kang, Ki-Hoon; Lim, Dong-Min; Shin, Hyun-Sang

2008-01-01

In this study, removals of 1-naphthol by oxidative-coupling reaction using birnessite, one of the natural Mn oxides present in soil, was investigated in various experimental conditions (reaction time, Mn oxide loadings, pH). The removal efficiency of 1-naphthol by birnessite was high in all the experimental conditions, and UV-visible and mass spectrometric analyses on the supernatant after reaction confirmed that the reaction products were oligomers formed by oxidative-coupling reaction. Pseudo-first order rate constants, k, for the oxidative transformation of 1-naphthol by birnessite was derived from the kinetic experiments under various amounts of birnessite loadings, and using the observed pseudo-first order rate constants with respect to birnessite loadings, the surface area normalised specific rate constant, k(surf), was also determined to be 9.3 x 10(-4) (L/m(2).min) for 1-naphthol. In addition, the oxidative transformation of 1-naphthol was found to be dependent on solution pH, and the pseudo-first order rate constants were increased from 0.129 at pH 10 to 0.187 at pH 4. (c) IWA Publishing 2008.

Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach

NASA Astrophysics Data System (ADS)

Du, Jinpeng; Qu, Zhenping; Dong, Cui; Song, Lixin; Qin, Yuan; Huang, Na

2018-03-01

Mn-Ce oxides catalysts were synthesized by a novel method combining redox-precipitation and hydrothermal approach. The results indicate that the ratio between manganese and cerium plays a crucial role in the formation of catalysts, and the textual properties as well as catalytic activity are remarked affected. Mn0.6Ce0.4O2 possesses a predominant catalytic activity in the oxidation of toluene, over 70% of toluene is converted at 200 °C, and the complete conversion temperature is 210 °C. The formation of Mn-Ce solid solution markedly improves the surface area as well as pore volume of Mn-Ce oxide catalyst, and Mn0.6Ce0.4O2 possesses the largest surface area of 298.5 m2/g. The abundant Ce3+ and Mn3+ on Mn0.6Ce0.4O2 catalyst facilitate the formation of oxygen vacancies, and improve the transfer of oxygen in the catalysts. Meanwhile, it is found that cerium in Mn-Ce oxide plays a key role in the adsorption of toluene, while manganese is proved to be crucial in the oxidation of toluene, the cooperation between manganese and cerium improves the catalytic reaction process. In addition, the reaction process is investigated by in situ DRIFT measurement, and it is found that the adsorbed toluene could be oxidized to benzyl alcohol as temperature rises around 80-120 °C that can be further be oxidized to benzoic acid. Then benzoic acid could be decomposed to formate and/or carbonate species as temperature rises to form CO2 and H2O. In addition, the formed by-product phenol could be further oxidized into CO2 and H2O when the temperature is high enough.

MnO2-Graphene Oxide-PEDOT:PSS Nanocomposite for an Electrochemical Supercapacitor

NASA Astrophysics Data System (ADS)

Patil, Dipali S.; Pawar, Sachin A.; Shin, Jae Cheol; Kim, Hyo Jin

2018-04-01

A ternary nanocomposite with poly (3,4 ethylene dioxythiophene:poly(styrene sulfonate) (PEDOT:PSS)-MnO2 nanowires-graphene oxide (PMn-GO) was synthesized by using simple chemical route. The formation of the nanocomposite was analyzed by using X-ray diffraction and X-ray photoelectron spectroscopy. Field-emission scanning microscopy (FESEM) revealed the formation of MnO2 nanowires and graphene oxide nanosheets. The highest specific capacitance (areal capacitance) of 841 Fg -1 (177 mFcm -2) at 10 mVs -1 and energy density of 0.593 kWhkg -1 at 0.5 mA were observed for PMn-GO, indicating a constructive synergistic effect of PEDOT:PSS, MnO2 nanowires and graphene oxide. The achieved promising electrochemical characteristics showed that this ternary nanocomposite is a good alternative as an electrode material for supercapacitor.

Secondary Fe- and Mn-Oxides Associated with Faults Near Moab, Utah: Records of Past Fluid Flow

NASA Astrophysics Data System (ADS)

Garcia, V. H.; Reiners, P. W.

2015-12-01

Secondary Fe- and Mn-oxides are locally common near faults and fractures, and as cements within sandstones of the Colorado Plateau, and provide evidence of past fluid-flow. Here we describe textural, mineralogic, and geochronologic observations from fault-zone Fe- and Mn-oxide mineralization in Flat Iron Mesa, near Moab, Utah. Several hypotheses have been proposed for their origin, including reactions associated with the mixing of deep reduced and near-surface oxygenated waters. We integrate field observations, detailed SEM and petrographic observations, geochemical models, (U-Th)/He and Ar/Ar dating, and other data to develop interpretations of the formation of these deposits. SEM imaging shows that sandstone matrix cement adjacent to the faults follows two precipitation sequences: Fe-oxide followed by barite and Fe-oxide followed by Mn-oxide. Dense oxide layers also accumulated in cm-scale fractures near faults, and show the following precipitation sequence: Fe-oxide, barite, Ba rich Mn-oxide, and pure Mn-oxide. The latter sequence is observed at larger scale across faults in one site in Flat Iron Mesa. Our new He dates for Mn-oxides are 1.7-2.9 Ma while Fe-oxide dates are 2.7-3.0 Ma. If these dates represent formation ages, they are consistent with the interpreted precipitation sequence but would require protracted mineralization over Ma-timescales. Alternatively, they may represent varying degrees of He retentivity in earlier formed deposits. Previous Ar/Ar dates have been interpreted as a 20-25 Ma formation age. Ongoing Ar/Ar and He diffusion studies will resolve this discordance. Assuming the previous Ar dates do not reflect contamination by detrital K-bearing phases and do reflect oxide formation, potential interpretations for the younger He ages include recent U-Th addition, recrystallization, later oxide growth, or large diffusive He loss at low temperatures.

Role of flue gas components in mercury oxidation over TiO2 supported MnOx-CeO2 mixed-oxide at low temperature.

PubMed

Li, Hailong; Wu, Chang-Yu; Li, Ying; Li, Liqing; Zhao, Yongchun; Zhang, Junying

2012-12-01

MnO(x)-CeO(2) mixed-oxide supported on TiO(2) (Mn-Ce/Ti) was synthesized by an ultrasound-assisted impregnation method and employed to oxidize elemental mercury (Hg(0)) at 200°C in simulated coal combustion flue gas. Over 90% of Hg(0) oxidation was achieved on the Mn-Ce/Ti catalyst at 200°C under simulated flue gas representing those from burning low-rank coals with a high gas hourly space velocity of 60,000 h(-1). Gas-phase O(2) regenerated the lattice oxygen and replenished the chemisorbed oxygen, which facilitated Hg(0) oxidation. HCl was the most effective flue gas component responsible for Hg(0) oxidation. 10 ppm HCl plus 4% O(2) resulted in 100% Hg(0) oxidation under the experimental conditions. SO(2) competed with Hg(0) for active sites, thus deactivating the catalyst's capability in oxidizing Hg(0). NO covered the active sites and consumed surface oxygen active for Hg(0) oxidation, hence limiting Hg(0) oxidation. Water vapor showed prohibitive effect on Hg(0) oxidation due to its competition with HCl and Hg(0) for active adsorption sites. This study provides information about the promotional or inhibitory effects of individual flue gas components on Hg(0) oxidation over a highly effective Mn-Ce/Ti catalyst. Such knowledge is of fundamental importance for industrial applications of the Mn-Ce/Ti catalyst in coal-fired power plants. Copyright © 2012 Elsevier B.V. All rights reserved.

Hollow spiny shell of porous Ni-Mn oxides: A facile synthesis route and their application as electrode in supercapacitors

NASA Astrophysics Data System (ADS)

Wan, Houzhao; Lv, Lin; Peng, Lu; Ruan, Yunjun; Liu, Jia; Ji, Xiao; Miao, Ling; Jiang, Jianjun

2015-07-01

Hollow spiny shell Ni-Mn precursors composed of one-dimensional nanoneedles were synthesized via a simple hydrothermal method without any template. The hollow Spiny shell Ni-Mn oxides are obtained under thermal treatment at different temperatures. The BET surface areas of Ni-Mn oxides reach up to 112 and 133 m2 g-1 when calcination temperatures occur at 300 and 400 °C, respectively. The electrochemical performances of as-synthesized hollow spiny shell Ni-Mn oxides gradually die down with annealing temperatures increasing. The porous hollow spiny shell Ni-Mn oxide obtained at 300 °C delivers a maximum capacitance of 1140 F g-1 at a high current density of 1 A g-1 after 1000th cycles and the specific capacitance of Ni-Mn oxide will increase with cycling times increasing. So, porous hollow spiny shell Ni-Mn oxide obtained at low annealing temperature can form a competitive electrode material for supercapacitors.

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

NASA Astrophysics Data System (ADS)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

PubMed

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

PubMed

Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

2015-02-07

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

Evaluation of biogenic emission flux and its impact on oxidants and inorganic aerosols in East Asia

NASA Astrophysics Data System (ADS)

Han, K. M.; Song, C. H.; Park, R. S.; Woo, J.; Kim, H.

2010-12-01

As a major precursor during the summer season, biogenic species are of primary importance in the ozone and SOAs (secondary organic aerosols) formations. Isoprene and mono-terpene also influence the level of inorganic aerosols (i.e. sulfate and nitrate) by controlling OH radicals. However, biogenic emission fluxes are highly uncertain in East Asia. While isoprene emission fluxes from the GEIA (Global Emissions Inventory Activity) and POET (Precursors of Ozone and their Effects in the Troposphere) inventories estimate approximately 20 Tg yr-1 in East Asia, those from the MEGAN (Model of Emissions of Gases and Aerosols from Nature) and MOHYCAN (MOdel for Hydrocarbon emissions by the CANopy) estimate approximately 10 Tg yr-1 and 5 Tg yr-1, respectively. In order to evaluate and/or quantify the magnitude of biogenic emission fluxes over East Asia, the tropospheric HCHO columns obtained from the GOME (Global Ozone Monitoring Experiment) observations were compared with the HCHO columns from the CMAQ (Community Multi-scale Air Quality) simulations over East Asia. In this study, US EPA Models-3/CMAQ v4.5.1 model simulation using the ACE-ASIA (Asia Pacific Regional Aerosol Characterization Experiment) emission inventory for anthropogenic pollutants and GEIA, POET, MEGAN, and MOHYCAN emission inventories for biogenic species was carried out in conjunction with the Meteorological fields generated from the PSU/NCAR MM5 (Pennsylvania state University/National Center for Atmospheric Research Meso-scale Model 5) model for the summer episodes of the year 2002. In addition to an evaluation of the biogenic emission flux, we investigated the impact of the uncertainty in biogenic emission inventory on inorganic aerosol formations and variations of oxidants (OH, O3, and H2O2) in East Asia. In this study, when the GEIA and POET emission inventories are used, the CMAQ-derived HCHO columns are highly overestimated over East Asia, particularly South China compared with GOME-derived HCHO

BOREAS TGB-5 Biogenic Soil Emissions of NO and N2O

NASA Technical Reports Server (NTRS)

Levine, J. S.; Winstead, E. L.; Parsons, D. A. B.; Scholes, M. C.; Cofer, W. R.; Cahoon, D. R.; Sebacher, D. I.; Scholes, R. J.; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

2000-01-01

The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB)-5 team made several measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains biogenic soil emissions of nitric oxide and nitrous oxide that were measured over a wide range of spatial and temporal site parameters. Since very little is known about biogenic soil emissions of nitric oxide and nitrous oxide from the boreal forest, the goal of the measurements was to characterize the biogenic soil fluxes of nitric oxide and nitrous oxide from black spruce and jack pine areas in the boreal forest. The diurnal variation and monthly variation of the emissions was examined as well as the impact of wetting through natural or artificial means. Temporally, the data cover mid-August 1993, June to August 1994, and mid-July 1995. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884).

Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon

This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn 2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO 2) nanosheets.

Study of electrochemical reduced graphene oxide and MnO2 heterostructure for supercapacitor application

NASA Astrophysics Data System (ADS)

Jana, S. K.; Rao, V. P.; Banerjee, S.

2013-02-01

In this paper we have shown enhanced supercapacitive property of electrochemically reduced graphene oxide (ERGO) and manganese dioxide (MnO2) based heterostructure over single MnO2 thin film grown by electrochemical deposition on indium tin oxide (ITO). ERGO improves the electrical conduction leading to decrease of the internal resistance of the heterostructure.

The effects of fire on biogenic soil emissions of nitric oxide and nitrous oxide

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Cofer, Wesley R., III; Sebacher, Daniel I.; Boston, Penelope J.; Winstead, Edward L.; Sebacher, Shirley

1988-01-01

Measurements of biogenic soil emissions of nitric oxide (NO) and nitrous oxide (N2O) before and after a controlled burn conducted in a chaparral ecosystem on June 22, 1987, showed significantly enhanced emissions of both gases after the burn. Mean NO emissions from heavily burned and wetted (to simulate rainfall) sites exceeded 40 ng N/sq m s, and increase of 2 to 3 compared to preburn wetted site measurements. N2O emissions from burned and wetted sites ranged from 9 to 22 ng N/sq m s. Preburn N2O emissions from these wetted sites were all below the detection level of the instrumentation, indicating a flux below 2 ng N/sq m s. The flux of NO exceeded the N2O flux from burned wetted sites by factors ranging from 2.7 to 3.4. These measurements, coupled with preburn and postburn measurements of ammonium and nitrate in the soil of this chaparral ecosystem and measurements of NO and N2O emissions obtained under controlled laboratory conditions, suggest that the postfire enhancement of NO and N2O emissions is due to production of these gases by nitrifying bacteria.

Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation.

PubMed

Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

2010-07-01

Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH 2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH 2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn-O bond upon oxidation from Mn(II)OH 2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand.

Dissolution of Biogenic and Synthetic UO2 under Varied Reducing Conditions

PubMed Central

ULRICH, KAI – UWE; SINGH, ABHAS; SCHOFIELD, ELEANOR J.; BARGAR, JOHN R.; VEERAMANI, HARISH; SHARP, JONATHAN O.; LATMANI, RIZLAN BERNIER -; GIAMMAR, DANIEL E.

2008-01-01

The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles’ surface free energy, structural defects, and compositional variability in analogy to abiotic UO2+x (0 ≤ x ≤ 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00. Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases. PMID:18754482

Observations on the oxidation of Mn-modified Ni-base Haynes 230 alloy under SOFC exposure conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Z Gary; Xia, Gordon; Stevenson, Jeffry W.

2005-07-01

The commercial Ni-base Haynes 230 alloy (Ni-Cr-Mo-W-Mn) was modified with two increased levels of Mn (1 and 2 wt per cent) and evaluated for its oxidation resistance under simulated SOFC interconnect exposure conditions. Oxidation rate, oxide morphology, oxide conductivity and thermal expansion were measured and compared with commercial Haynes 230. It was observed that additions of higher levels of Mn to the bulk alloy facilitated the formation of a bi-layered oxide scale that was comprised of an outer M3O4 (M=Mn, Cr, Ni) spinel-rich layer at the oxide – gas interface over a Cr2O3-rich sub-layer at the metal – oxide interface.more » The modified alloys showed higher oxidation rates and the formation of thicker oxide scales compared to the base alloy. The formation of a spinel-rich top layer improved the scale conductivity, especially during the early stages of the oxidation, but the higher scale growth rate resulted in an increase in the area-specific electrical resistance over time. Due to their face-centered cubic crystal structure, both commercial and modified alloys demonstrated a coefficient of thermal expansion that was higher than that of typical anode-supported and electrolyte-supported SOFCs.« less

The effect of Ca2+ ions and ionic strength on Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

PubMed Central

Tebo, Bradley M.

2017-01-01

Manganese(IV) oxides, believed to form primarily through microbial activities, are extremely important mineral phases in marine environments where they scavenge a variety of trace elements and thereby control their distributions. The presence of various ions common in seawater are known to influence Mn oxide mineralogy yet little is known about the effect of these ions on the kinetics of bacterial Mn(II) oxidation and Mn oxide formation. We examined factors affecting bacterial Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1 in natural and artificial seawater of varying ionic conditions. Ca2+ concentration dramatically affected Mn(II) oxidation, while Mg2+, Sr2+, K+, Na+ and NO3− ions had no effect. The rate of Mn(II) oxidation at 10mM Ca2+ (seawater composition) was four or five times that without Ca2+. The relationship between Ca2+ content and oxidation rate demonstrates that the equilibrium constant is small (on the order of 0.1) and the binding coefficient is 0.5. The pH optimum for Mn(II) oxidation changed depending on the amount of Ca2+ present, suggesting that Ca2+ exerts a direct effect on the enzyme perhaps as a stabilizing bridge between polypeptide components. We also examined the effect of varying concentrations of NaCl or KNO3 (0 mM – 2000 mM) on the kinetics of Mn(II) oxidation in solutions containing 10 mM Ca2+. Mn(II) oxidation was unaffected by changes in ionic strength (I) below 0.2, but it was inhibited by increasing salt concentrations above this value. Our results suggest that the critical coagulation concentration is around 200 mM of salt (I = ca. 0.2), and that the ionic strength of seawater (I > 0.2) accelerates the precipitation of Mn oxides around the spores. Under these conditions, the aggregation of Mn oxides reduces the supply of dissolved O2 and/or Mn2+ and inhibits the Mn(II) -> Mn(III) step controlling the enzymatic oxidation of Mn(II). Our results suggest that the hardness and ionic strength of the aquatic

Epitaxial Growth of Intermetallic MnPt Films on Oxides and Large Exchange Bias

DOE PAGES

Liu, Zhiqi; Biegalski, Michael D; Hsu, Mr. S. L.; ...

2015-11-05

We achieved a high-quality epitaxial growth of inter­metallic MnPt films on oxides, with potential for multiferroic heterostructure applications. Also, antisite-stabilized spin-flipping induces ferromagnetism in MnPt films, although it is robustly antiferromagnetic in bulk. Moreover, highly ordered antiferromagnetic MnPt films exhibit superiorly large exchange coupling with a ferromagnetic layer.

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

PubMed

Pettong, Tanut; Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Sukha, Phansiri; Sirisinudomkit, Pichamon; Seubsai, Anusorn; Chareonpanich, Metta; Kongkachuichay, Paisan; Limtrakul, Jumras; Sawangphruk, Montree

2016-12-14

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo 2 O 4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGO AE ) was fabricated in this work. The MnCo 2 O 4 NFs at the positive electrode store the negative charges, i.e., solvated OH - , while the N-rGO AE at the negative electrode stores the positive charges, i.e., solvated K + . An as-fabricated aqueous-based MnCo 2 O 4 //N-rGO AE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg -1 and 9851 W kg -1 , respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo 2 O 4 , the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo 2 O 4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo 2 O 4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation†

PubMed Central

Lassalle-Kaiser, Benedikt; Hureau, Christelle; Pantazis, Dimitrios A.; Pushkar, Yulia; Guillot, Régis; Yachandra, Vittal K.; Yano, Junko; Neese, Frank; Anxolabéhère-Mallart, Elodie

2014-01-01

Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 × 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH2 complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH2 and Mn(III)OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn–O bond upon oxidation from Mn(II)OH2 to Mn(III)OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand. PMID:24772190

Biogenic magnetite as a paleomagnetic recorder of the ferromanganese crust in the West Pacific

NASA Astrophysics Data System (ADS)

Kim, W.; Shin, J. Y.; Kim, J.

2017-12-01

Various magnetic measurements were carried out to diagnose magnetic mineralogy of the ferromanganese crust obtained in the Magellan Seamounts, the West Pacific ( 20°N). Thermal demagnetization revealed a Curie temperature of 560oC, corresponding to (titano)magnetite. Component analysis of isothermal remanent magnetization identified a presence of two types of magnetite. Measurements of first order reverse curve showed a dominance of non-interacting single-domain magnetite, which is one of the intrinsic feature of biogenic magnetite. Although most of the magnetic particles on transmitted electron microscopy are covered by amorphous Fe-Mn minerals, some are observed as a prototype of biogenic magnetite showing a chain of 10 nm sized cubes. However, a magnetite signal (i.e., Verway transition at -120 oC) was not detected in low-temperature treatment probably due to surface oxidation of magnetite. Contribution of interacting magnetite of detrital origin is <30% throughout a crust. Interestingly, contribution of detrital magnetite is almost three times higher since 10 Ma. At this boundary, a growth rate of the crust is double up and flux of other detrital signals, including Al, Mg, Ti and Zr, are also increased.

Effect of Heat-Treatment Temperature on the Interfacial Reaction Between Oxide Inclusions and Si-Mn Killed Steel

NASA Astrophysics Data System (ADS)

Zhang, Xueliang; Yang, Shufeng; Liu, Chengsong; Li, Jingshe; Hao, Weixing

2018-06-01

The effect of heat-treatment temperature on the interfacial reaction between MnO-SiO2-FeO oxide and Fe-Mn-Si alloy was investigated by the diffusion couple method in the temperature range of 1173-1573 K. The reaction at the interface between the alloy and oxide was not obvious during treatment at 1173 K, but, with increasing heat-treatment temperature, the interfacial reaction was strengthened and the proportion of the MnO·SiO2 phase in the oxide increased. The width of the particle-precipitation zone in the alloy increased with increasing temperature from 1173 K to 1473 K but decreased at 1573 K owing to coarsening of the precipitated particles. In addition, Mn2+ and Si4+ in the oxide significantly diffused into the alloy at 1573 K, resulting in an obvious increase of the Mn and Si contents in the alloy near the interface.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

PubMed

Lorenz, Volker; Ehle, Sophie; Liebing, Phil; Engelhardt, Felix; Hashemi-Haeri, Haleh; Oehler, Florian; Hinderberger, Dariush; Busse, Sabine; Urbaschok, Jens; Edelmann, Frank T

2017-12-19

A unique trivalent manganese siloxide complex, blue-violet Mn III Li 2 Cl[(Ph 2 SiO) 2 O] 2 (THF) 4 ·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph 2 SiOH) 2 O (1) followed by reaction with MnCl 2 (THF) 2 gave the structurally remarkable Mn(ii) precursor Mn II Li 4 Cl 2 [(Ph 2 SiO) 2 O] 2 (THF) 5 ·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO 4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

The oxidative transformation of sodium arsenite at the interface of alpha-MnO2 and water.

PubMed

Li, Xiu-juan; Liu, Cheng-shuai; Li, Fang-bai; Li, Yong-tao; Zhang, Li-jia; Liu, Chuan-ping; Zhou, Yong-zhang

2010-01-15

Arsenite is acute contaminant to human health in soil and water environment. In this study, Pyrolusite (alpha-MnO(2)) was used to investigate the oxidative transformation of arsenite into arsenate with batch experiments under different reaction conditions. The results showed that arsenite transformation occurred and was accompanied by the adsorption and fixation of both As(III) and As(V) on alpha-MnO(2). About 90% of sodium arsenite (10mg/L) were transformed by alpha-MnO(2) under the conditions of 25 degrees C and pH 6.0, 36.6% of which was adsorbed and 28.9% fixed by alpha-MnO(2). Increased alpha-MnO(2) dosages promoted As (III) transformation rate and adsorption of arsenic species. The transformation rate and adsorption of arsenic species raised with increasing pH values of reaction solution from 4.7 to 8.0. The oxidation rate decreased and adsorbed As(III) and As(V) increased with increasing initial arsenite concentration. The enhancement on oxidative transformation of sodium arsenite may result from abundant active sites of alpha-MnO(2). Along with adsorption and fixation of arsenic species during the reaction, the crystal structure of alpha-MnO(2) did not change, but the surface turned petty and loosen. Our results demonstrated that alpha-MnO(2) has important potential in arsenic transformation and removal as the environmentally friendly natural oxidant in soil and surface water.

Oxidized Mn:Ge magnetic semiconductor: Observation of anomalous Hall effect and large magnetoresistance

NASA Astrophysics Data System (ADS)

Duc Dung, Dang; Choi, Jiyoun; Feng, Wuwei; Cao Khang, Nguyen; Cho, Sunglae

2018-03-01

We report on the structural and magneto-transport properties of the as-grown and oxidized Mn:Ge magnetic semiconductors. Based on X-ray diffraction and X-ray photoelectron spectroscopy results, the samples annealed at 650 and 700 °C became fully oxidized and the chemical binding energies of Mn was found to be Mn3O4. Thus, the system became Mn3O4 clusters embedded in Ge1-yOy. The as-grown sample showed positive linear Hall effect and negligible negative magnetoresistance (MR), which trend remained for the sample annealed up to 550 °C. Interestingly, for the samples annealed at above 650 °C, we observed the anomalous Hall effect around 45 K and the giant positive MR, which are respectively 59.2% and 78.5% at 7 kOe annealed at 650 °C and 700 °C.

Microwave assisted synthesis of graphene oxide - MnO2 nanocomposites for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Vimuna, V. M.; Athira, A. R.; Xavier, T. S.

2018-05-01

Grapheneoxide-MnO2 nanocomposite was successfully synthesized through the self-limiting deposition of nano scale MnO2 on the surface of graphene oxide under microwave- irradiation in a water- isopropyl alcohol system. The structural and morphological properties of as synthesized samples have been studied. These nanostructured graphene oxide-MnO2 (GMC) hybrid materials are used for investigation of electrochemical behaviours. It was found that the electrochemical performance of as prepared nanocomposite could be enhanced by chemical interaction between GO and MnO2. Cyclic voltammetry is employed to assess the properties of these nanocomposites for use in supercapacitors. The specific capacitance of the synthesized sample corresponding to scan rate of 20mV/s is calculated to be 280 Fg-1. Furthermore, we emphasize the fabrication challenges and future perspectives of such materials for energy storage.

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

NASA Astrophysics Data System (ADS)

Postma, D.; Appelo, C. A. J.

2000-04-01

The reduction of Mn-oxide by Fe2+ was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement of adsorbed Ca2+ with Mg2+. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the FeCl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe2+ reacts with MnO2 producing Fe(OH)3, Mn2+ and H+. The protons are transported downstream and cause the disproportionation of MnOOH at a separate reaction front. Between the two Mn reaction fronts, the dissolution and precipitation of Fe(OH)3 and Al(OH)3 act as proton buffers. Reactive transport modeling, using the code PHREEQC 2.0, was done to quantify and analyze the reaction controls and the coupling between transport and chemical processes. A model containing only mineral equilibria constraints for birnessite, manganite, gibbsite, and ferrihydrite, was able to explain the overall reaction pattern with the sequential appearance of Mn2+, Al3+, Fe3+, and Fe2+ in the column outlet solution. However, the initial breakthrough of a peak of Ca2+ and the observed pH buffering indicated that exchange processes were of importance as well. The amount of potential exchangers, such as birnessite and ferrihydrite, did vary in the course of the experiment. A model containing surface complexation coupled to varying concentrations of birnessite and ferrihydrite and a constant charge exchanger in addition to mineral equilibria

Self-trapping of holes in p-type oxides: Theory for small polarons in MnO

NASA Astrophysics Data System (ADS)

Peng, Haowei; Lany, Stephan

2012-02-01

Employing the p-d repulsion to increase the valence band dispersion and the energy of the VBM is an important design principle for p-type oxides, as manifested in prototypical p-type oxides like Cu2O or CuAlO2 which show a strong Cu-d/O-p interaction. An alternative opportunity to realize this design principle occurs for Mn(+II) compounds, where the p-d orbital interaction occurs dominantly in the fully occupied d^5 majority spin direction of Mn. However, the ability of Mn to change the oxidation state from +II to +III can lead to a small polaron mechanism for hole transport which hinders p-type conductivity. This work addresses the trends of hole self-trapping for MnO between octahedral (rock-salt structure) and tetrahedral coordination (zinc-blende structure). We employ an on-site hole-state potential so to satisfy the generalized Koopmans condition. This approach avoids the well-known difficulty of density-functional calculations to describe correctly the localization of polaronic states, and allows to quantitatively predict the self-trapping energies. We find that the tetrahedrally coordinated Mn is less susceptible to hole self-trapping than the octahedrally coordinated Mn.

Oscillatory oxidation of Mn(II) ions by hexacyanoferrates(III) and bistability in the reductions of MnO 2 by hexacyanoferrates(II) in a CSTR

NASA Astrophysics Data System (ADS)

Olexová, Anna; Melicherčík, Milan; Treindl, L'udovít

1997-04-01

A new transition metal oscillator based on the oxidation of Mn 2+ ions by Fe(CN) 3-6 ions in a CSTR has been found. As well as the oscillations of the absorbance of the Mn(IV) species, pH-oscillations have been observed. In the reduction of manganese dioxide by Fe(CN) 4-6 ions a kinetic bistability has been described. A skeleton mechanism described recently for Mn(II)H 2O 2 and Mn(II)Br 2 oscillators has been applied here and further developed by the idea of the catalytic activity of colloidal particles and of the assistance of the pH-value change of both main processes, i.e. of the Mn(II) oxidation by Fe(CN) 3-6 ions and of the Mn(IV) reduction by Fe(CN) 4-6 ions. This appears to be the first case where both sides of a reversible reaction are autocatalytic.

Bioleaching of zinc and manganese from spent Zn-Mn batteries and mechanism exploration.

PubMed

Xin, Baoping; Jiang, Wenfeng; Aslam, Hina; Zhang, Kai; Liu, Changhao; Wang, Renqing; Wang, Yutao

2012-02-01

In this work, bioleaching was used to extract valuable Zn and Mn from spent Zn-Mn batteries. The results showed that 96% of Zn extraction was achieved within 24h regardless of energy source types and bioleaching bacteria species. However, initial pH had a remarkable influence on Zn release, extraction dose sharply decreased from 2200 to 500mg/l when the initial pH value increased from 1.5 to 3.0 or higher. In contrast to Zn, all the tested factors evidently affected Mn extraction; the maximum released dose of 3020mg/l was obtained under the optimum conditions. The acidic dissolution by biogenic H(2)SO(4) by the non-contact mechanism was responsible for Zn extraction, while Mn extraction was owed to both contact/biological and non-contact mechanisms. The combined action of acidic dissolution of soluble Mn(2+) by biogenic H(2)SO(4) and reductive dissolution of insoluble Mn(4+) by Fe(2+) resulted in 60% of Mn extraction, while contact of microbial cells with the spent battery material and incubation for more than 7days was required to achieve the maximum extraction of Mn. Copyright © 2011 Elsevier Ltd. All rights reserved.

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

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

PubMed Central

Bohu, Tsing; Santelli, Cara M.; Akob, Denise M.; Neu, Thomas R.; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

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. PMID:26236307

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

USGS Publications Warehouse

Bohu, Tsing; Santelli, Cara M; Akob, Denise M.; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

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.

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

PubMed

Bohu, Tsing; Santelli, Cara M; Akob, Denise M; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

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 ABAG biogenic emissions inventory project

NASA Technical Reports Server (NTRS)

Carson-Henry, C. (Editor)

1982-01-01

The ability to identify the role of biogenic hydrocarbon emissions in contributing to overall ozone production in the Bay Area, and to identify the significance of that role, were investigated in a joint project of the Association of Bay Area Governments (ABAG) and NASA/Ames Research Center. Ozone, which is produced when nitrogen oxides and hydrocarbons combine in the presence of sunlight, is a primary factor in air quality planning. In investigating the role of biogenic emissions, this project employed a pre-existing land cover classification to define areal extent of land cover types. Emission factors were then derived for those cover types. The land cover data and emission factors were integrated into an existing geographic information system, where they were combined to form a Biogenic Hydrocarbon Emissions Inventory. The emissions inventory information was then integrated into an existing photochemical dispersion model.

MnO2 Nanorods Intercalating Graphene Oxide/Polyaniline Ternary Composites for Robust High-Performance Supercapacitors

NASA Astrophysics Data System (ADS)

Han, Guangqiang; Liu, Yun; Zhang, Lingling; Kan, Erjun; Zhang, Shaopeng; Tang, Jian; Tang, Weihua

2014-04-01

New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ~20 nm are conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance reaching 512 F/g and outstanding cycling performance, with ~97% capacitance retained over 5000 cycles. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications.

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

PubMed

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

The Effects of Bismuth Oxide on Microstructures and Magnetic Properties of Mn-Mg-Al Ferrites

NASA Astrophysics Data System (ADS)

Nekouee, Kh. A.; Rahimi, A. H.; Haghighi, M. Alineghad; Ehsani, N.

2018-04-01

In the present paper, the effects of bismuth oxide as an additive on microstructure and magnetic properties of Mg0.9Mn0.1Al0.4Fe1.6O4 were investigated. Mg-Mn-Al ferrite powders were prepared by the conventional solid state synthesis method. Two different amounts of bismuth oxide (2.5 wt.% and 5 wt.%) were utilized as the sintering aid and their microstructure and physical properties were compared to those of the sample without additives. X-ray diffraction (XRD) analysis indicated that crystal lattice distortion due to the microstructural constraints as the result from incorporation of bismuth oxide into the microstructure was developed by adding bismuth oxide. XRD Rietveld refinement was used to define the cation distribution and to refine the lattice parameter and oxygen parameter for the sample without bismuth oxide as (Mg0.16Mn0.02Al0.15Fe0.77)A(Mg0.74Mn0.08Al0.25Fe0.83)BO4 and 8.3308 Å and 0.2542, respectively. Microstructure studies show that a bismuth rich liquid phase forms during the sintering at 1250°C, which enhances the densification of sintered bodies up to 13% (a relative density of 93%). Magnetization of sintered samples were increased from 21.1 emu/g to 26.2 emu/g upon addition of 2.5 wt.% bismuth oxide and then decreased to 24.9 emu/g when 5 wt.% bismuth oxide was added.

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

DOE PAGES

Perry, Albert; Kabir, Sadia; Matanovic, Ivana; ...

2017-06-16

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perry, Albert; Kabir, Sadia; Matanovic, Ivana

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

Novel Montmorillonite/TiO₂/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

PubMed

Napruszewska, Bogna D; Michalik-Zym, Alicja; Rogowska, Melania; Bielańska, Elżbieta; Rojek, Wojciech; Gaweł, Adam; Wójcik-Bania, Monika; Bahranowski, Krzysztof; Serwicka, Ewa M

2017-11-19

A novel design of combustion catalysts is proposed, in which clay/TiO₂/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N₂ adsorption/desorption at -196 °C, and H₂ TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO₂ component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH₃ (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO₂/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO₂/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.

Combination of microbial oxidation and biogenic schwertmannite immobilization: A potential remediation for highly arsenic-contaminated soil.

PubMed

Yang, Zhihui; Wu, Zijian; Liao, Yingping; Liao, Qi; Yang, Weichun; Chai, Liyuan

2017-08-01

Here, a novel strategy that combines microbial oxidation by As(III)-oxidizing bacterium and biogenic schwertmannite (Bio-SCH) immobilization was first proposed and applied for treating the highly arsenic-contaminated soil. Brevibacterium sp. YZ-1 isolated from a highly As-contaminated soil was used to oxidize As(III) in contaminated soils. Under optimum culture condition for microbial oxidation, 92.3% of water-soluble As(III) and 84.4% of NaHCO 3 -extractable As(III) in soils were removed. Bio-SCH synthesized through the oxidation of ferrous sulfate by Acidithiobacillus ferrooxidans immobilize As(V) in the contaminated soil effectively. Consequently, the combination of microbial oxidation and Bio-SCH immobilization performed better in treating the highly As-contaminated soil with immobilization efficiencies of 99.3% and 82.6% for water-soluble and NaHCO 3 -extractable total As, respectively. Thus, the combination can be considered as a green remediation strategy for developing a novel and valuable solution for As-contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influences of graphene oxide support on the electrochemical performances of graphene oxide-MnO2 nanocomposites

PubMed Central

2011-01-01

MnO2 supported on graphene oxide (GO) made from different graphite materials has been synthesized and further investigated as electrode materials for supercapacitors. The structure and morphology of MnO2-GO nanocomposites are characterized by X-ray diffraction, X-ray photoemission spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and Nitrogen adsorption-desorption. As demonstrated, the GO fabricated from commercial expanded graphite (denoted as GO(1)) possesses more functional groups and larger interplane gap compared to the GO from commercial graphite powder (denoted as GO(2)). The surface area and functionalities of GO have significant effects on the morphology and electrochemical activity of MnO2, which lead to the fact that the loading amount of MnO2 on GO(1) is much higher than that on GO(2). Elemental analysis performed via inductively coupled plasma optical emission spectroscopy confirmed higher amounts of MnO2 loading on GO(1). As the electrode of supercapacitor, MnO2-GO(1) nanocomposites show larger capacitance (307.7 F g-1) and better electrochemical activity than MnO2-GO(2) possibly due to the high loading, good uniformity, and homogeneous distribution of MnO2 on GO(1) support. PMID:21951643

Biogenic VOC Oxidation is Modulated by Anthropogenic Pollution in the South East US

NASA Astrophysics Data System (ADS)

Misztal, P. K.; Romer, P.; Duffey, K.; Cohen, R. C.; Kaser, L.; Seco, R.; Park, J.; Kim, S.; Guenther, A. B.; Goldstein, A. H.

2013-12-01

Biogenic volatile organic compounds (VOC) are known to play important roles for atmospheric chemistry, formation of secondary organic aerosol (SOA), and thus climate. However, the impacts of anthropogenic emissions on the BVOC oxidation mechanisms and SOA formation processes are not yet well understood. The SOAS summer 2013 campaign goals include looking holistically at physicochemical processes of BVOC emission, oxidation, and subsequent SOA formation and the role of anthropogenic emissions in those processes. Gas-phase composition changes of the broad range of VOCs were measured by PTR-ToF-MS at the Centreville SEARCH site located in a mixed deciduous forest near Brent, Alabama. The instrument sampled from the top of the tower at a high acquisition rate (10 Hz) using an inlet collocated with other measurements (wind, radicals, nitrogen oxides, etc.). Isoprene concentrations were extremely high, peaking at up to approximately 10 ppb during the hottest and sunniest days. Isoprene oxidation chemistry was clearly affected by anthropogenic influences. The rate of isoprene oxidation and the abundance of the first (MVK, MAC, etc.) and second (hydroxyacetone, etc.) order products were significantly different under cleaner conditions than under more polluted conditions. Isoprene oxidation likely is more dominated by the hydroperoxyl pathway under clean conditions while the NO pathway is more important under pollution conditions. Observations of the full range of detected isoprene oxidation products will be discussed and examined under relatively clean and polluted conditions. Both daytime and nighttime oxidation pathways will be examined, and comparison with airborne measurements will be shown to relate our ground based observations to more regional photochemical VOC processing.

MnO2 Nanorods Intercalating Graphene Oxide/Polyaniline Ternary Composites for Robust High-Performance Supercapacitors

PubMed Central

Han, Guangqiang; Liu, Yun; Zhang, Lingling; Kan, Erjun; Zhang, Shaopeng; Tang, Jian; Tang, Weihua

2014-01-01

New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ~20 nm are conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance reaching 512 F/g and outstanding cycling performance, with ~97% capacitance retained over 5000 cycles. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications. PMID:24769835

Biogenic copper oxide nanoparticles synthesis using Tabernaemontana divaricate leaf extract and its antibacterial activity against urinary tract pathogen

NASA Astrophysics Data System (ADS)

Sivaraj, Rajeshwari; Rahman, Pattanathu K. S. M.; Rajiv, P.; Salam, Hasna Abdul; Venckatesh, R.

2014-12-01

This investigation explains the biosynthesis and characterization of copper oxide nanoparticles from an Indian medicinal plant by an eco-friendly method. The main objective of this study is to synthesize copper oxide nanoparticles from Tabernaemontana divaricate leaves through a green chemistry approach. Highly stable, spherical copper oxide nanoparticles were synthesized by using 50% concentration of Tabernaemontana leaf extract. Formation of copper oxide nanoparticles have been characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM) analysis. All the analyses revealed that copper oxide nanoparticles were 48 ± 4 nm in size. Functional groups and chemical composition of copper oxide were also confirmed. Antimicrobial activity of biogenic copper oxide nanoparticles were investigated and maximum zone of inhibition was found in 50 μg/ml copper oxide nanoparticles against urinary tract pathogen (Escherichia coli).

Fe-Mn binary oxide incorporated into diatomite as an adsorbent for arsenite removal: preparation and evaluation.

PubMed

Chang, Fangfang; Qu, Jiuhui; Liu, Huijuan; Liu, Ruiping; Zhao, Xu

2009-10-15

Fe-Mn binary oxide incorporated into diatomite (FMBO-diatomite) was prepared by a simple coating method, and exhibited high oxidation and adsorption ability for arsenite [As(III)]. After being incorporated by Fe-Mn binary oxide, the surface area of diatomite increased 36%, and the pore volume increased five times. The pHzpc of FMBO-diatomite was determined to be 8.1. These characteristics are responsible for the increased As(III) adsorption efficiency. The adsorption equilibria of As(III) on FMBO-diatomite were described well by a Langmuir isotherm model due to the homogeneous distribution of Fe-Mn binary oxide on a diatomite surface. As(III) was oxidized into As(V), and then adsorbed by FMBO-diatomite. The oxidation and adsorption efficiencies for As(III) depended deeply on the pH of solution. When the pH was raised to 8.1, the As(III) adsorption efficiency of FMBO-diatomite was almost equal to the As(III) oxidation efficiency. Silicate and phosphate had negative effects on As(III) adsorption. Also the influence of silicate and phosphate with the pH variation was different.

Magnetically retrievable nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) spinel nanocatalyst for alcohol oxidation

NASA Astrophysics Data System (ADS)

Bhat, Pooja B.; Bhat, Badekai Ramachandra

2016-03-01

Ultrasmall nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) nanocatalyst was synthesized by traditional co-precipitation method and was examined for oxidation of aromatic alcohols to carbonyls using hydrogen peroxide as terminal oxidant. A very high surface area of 104.55 m2 g-1 was achieved for ferromagnetic MnFe2O4 and 100.50 m2 g-1 for superparamagnetic NiFe2O4, respectively. Efficient oxidation was observed due to the synergized effect of nickel hydroxide (bronsted base) on Lewis center (Fe) of the nanocatalyst. Catalyst recycling experiments revealed that the ultrasmall nanocatalyst can be easily recovered by external magnet and applied for nearly complete oxidation of alcohols for at least five successive cycles. Furthermore, the nickel hydroxide functionalised ultrasmall nanocatalyst exhibited higher efficiency for benzyl alcohol oxidation compared to Ni(OH)2, bare MnFe2O4 and NiFe2O4. Higher conversion rate was observed for nickel hydroxide functionalised NiFe2O4 compared to MnFe2O4. Ultrasmall magnetic nickel hydroxide functionalised nanocatalyst showed environmental friendly, greener route for the oxidation of alcohols without significant loss in activity and selectivity within successive runs.

HOMOGENEOUS AIR OXIDATION OF HYDROCARBONS UTILIZING MN AND CO CATALYSTS

EPA Science Inventory

Homogeneous Air Oxidation of Hydrocarbons Utilizing Mn and Co Catalysts

Thomas M. Becker and Michael A. Gonzalez*, Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Martin Luther King Drive, Mail Sto...

Anaerobic nitrification-denitrification mediated by Mn-oxides in meso-tidal sediments: Implications for N2 and N2O production

NASA Astrophysics Data System (ADS)

Fernandes, Sheryl Oliveira; Javanaud, Cedric; Aigle, Axel; Michotey, Valérie D.; Guasco, Sophie; Deborde, Jonathan; Deflandre, Bruno; Anschutz, Pierre; Bonin, Patricia C.

2015-04-01

Field measurements in the Arcachon Bay (southwest France) indicated anaerobic production of NOx via nitrification, which was coupled to the reduction of Mn-oxides. To prove the occurrence of this process, laboratory microcosm experiments were set up. A 15N tracer-based approach was used to track if NOx produced through Mn-oxide-mediated anaerobic nitrification would be reduced to N2 via denitrification or anammox. We also hypothesized the generation of the potent greenhouse gas nitrous oxide (N2O) during nitrification-denitrification in the presence of Mn-oxides. The microcosms were prepared using sediment sectioned at varying depths (0-2.5, 2.5-4.5, 4.5-8.5, 8.5-12 and 12-17 cm) during two sampling campaigns in October (fall) and January (winter). Labeling with 15NO3- revealed low N2 production originating from NO3- in the water column (Pw), which did not increase significantly on amendment with Mn-oxides during both sampling periods. However, for both seasons, a significant increase of N2 produced via nitrification (Pn) was observed upon addition of Mn-oxides reaching 76-fold enhancement at ≤ 2.5 cm. To support these results, sediment slurries of October were subjected to amendment of 15NH4+, 14NO3- with or without addition of Mn-oxides. A substantial production of P15 (N2 production from 15NH4+) within 0-17 cm provided further evidence on nitrification-denitrification mediated by Mn-oxides probably with minimal intervention of anammox. In organically rich sediments, anaerobic nitrification-denitrification mediated by Mn-oxides could play an important role in lowering re-mineralized NH4+ levels in the benthic system. As hypothesized, significant production of N2O through the pathway was observed revealing newer mechanisms leading to the generation of the radiative gas.

Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

PubMed

Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-05-07

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

Nanotubular MnO2/graphene oxide composites for the application of open air-breathing cathode microbial fuel cells.

PubMed

Gnana Kumar, G; Awan, Zahoor; Suk Nahm, Kee; Xavier, J Stanley

2014-03-15

Nanotubular shaped α-MnO2/graphene oxide nanocomposites were synthesized via a simple, cost and time efficient hydrothermal method. The growth of hollow structured MnO2 nanotubes preferentially occurred along the [001] direction as evidenced from the morphological and structural characterizations. The tunnels of α-MnO2 nanotubes easily accommodated the molecular oxygen and exhibited excellent catalytic activity towards the oxygen reduction reaction over the rod structure and was further enhanced with the effective carbon support graphene oxide. The MnO2 nanotubes/graphene oxide nanocomposite modified electrode exhibited a maximum power density of 3359 mW m(-2) which is 7.8 fold higher than that of unmodified electrode and comparable with the Pt/C modified electrode. The microbial fuel cell equipped with MnO2 nanotubes/graphene oxide nanocomposite modified cathode exhibited quick start up and excellent durability over the studied electrodes and is attributed to the high surface area and number of active sites. These findings not only provide the fundamental studies on carbon supported low-dimensional transition-metal oxides but also open up the new possibilities of their applications in green energy devices. © 2013 Elsevier B.V. All rights reserved.

Ultrasmall PdmMn1-mOx binary alloyed nanoparticles on graphene catalysts for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Ahmed, Mohammad Shamsuddin; Park, Dongchul; Jeon, Seungwon

2016-03-01

A rare combination of graphene (G)-supported palladium and manganese in mixed-oxides binary alloyed catalysts (BACs) have been synthesized with the addition of Pd and Mn metals in various ratios (G/PdmMn1-mOx) through a facile wet-chemical method and employed as an efficient anode catalyst for ethanol oxidation reaction (EOR) in alkaline fuel cells. The as prepared G/PdmMn1-mOx BACs have been characterized by several instrumental techniques; the transmission electron microscopy images show that the ultrafine alloyed nanoparticles (NPs) are excellently monodispersed onto the G. The Pd and Mn in G/PdmMn1-mOx BACs have been alloyed homogeneously, and Mn presents in mixed-oxidized form that resulted by X-ray diffraction. The electrochemical performances, kinetics and stability of these catalysts toward EOR have been evaluated using cyclic voltammetry in 1 M KOH electrolyte. Among all G/PdmMn1-mOx BACs, the G/Pd0.5Mn0.5Ox catalyst has shown much superior mass activity and incredible stability than that of pure Pd catalysts (G/Pd1Mn0Ox, Pd/C and Pt/C). The well dispersion, ultrafine size of NPs and higher degree of alloying are the key factor for enhanced and stable EOR electrocatalysis on G/Pd0.5Mn0.5Ox.

A Salt-Inducible Mn-Catalase (KatB) Protects Cyanobacterium from Oxidative Stress.

PubMed

Chakravarty, Dhiman; Banerjee, Manisha; Bihani, Subhash C; Ballal, Anand

2016-02-01

Catalases, enzymes that detoxify H2O2, are widely distributed in all phyla, including cyanobacteria. Unlike the heme-containing catalases, the physiological roles of Mn-catalases remain inadequately characterized. In the cyanobacterium Anabaena, pretreatment of cells with NaCl resulted in unusually enhanced tolerance to oxidative stress. On exposure to H2O2, the NaCl-treated Anabaena showed reduced formation of reactive oxygen species, peroxides, and oxidized proteins than the control cells (i.e. not treated with NaCl) exposed to H2O2. This protective effect correlated well with the substantial increase in production of KatB, a Mn-catalase. Addition of NaCl did not safeguard the katB mutant from H2O2, suggesting that KatB was indeed responsible for detoxifying the externally added H2O2. Moreover, Anabaena deficient in KatB was susceptible to oxidative effects of salinity stress. The katB gene was strongly induced in response to osmotic stress or desiccation. Promoter-gfp analysis showed katB to be expressed only in the vegetative cells but not in heterocysts. Biochemically, KatB was an efficient, robust catalase that remained active in the presence of high concentrations of NaCl. Our findings unravel the role of Mn-catalase in acclimatization to salt/oxidative stress and demonstrate that the oxidative stress resistance of an organism can be enhanced by a simple compound such as NaCl. © 2016 American Society of Plant Biologists. All Rights Reserved.

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3.

PubMed

Lee, Sang Moon; Park, Kwang Hee; Kim, Sung Su; Kwon, Dong Wook; Hong, Sung Chang

2012-09-01

TiO2-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH3 with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn4+ displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO2 catalysts were important for the low-temperature SCR at 80-160 and 200-350 degrees C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO2 oxidation at low temperatures. Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO(x)). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO2 catalysts.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

NASA Astrophysics Data System (ADS)

Zhen, Shuying; Sun, Wang; Li, Peiqian; Tang, Guangze; Rooney, David; Sun, Kening; Ma, Xinxin

2016-05-01

In this work Cu1.4Mn1.6O4 (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu+/Cu2+ and Mn3+/Mn4+ couples exist in the CMO sample, and a maximum conductivity of 78 S cm-1 is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc2O3 stabilized ZrO2 (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm2 at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm-2 at 800 °C under H2 (3% H2O) as the fuel and ambient air as the oxidant. These results indicate that Cu1.4Mn1.6O4 is a superior and promising cathode material for IT-SOFCs.

High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-09-01

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

Preparation of Reduced Graphene Oxide/MnO Composite and Its Electromagnetic Wave Absorption Performance

NASA Astrophysics Data System (ADS)

Yuan, Jiangtao; Li, Kunzhen; Liu, Zhongfei; Jin, Shaowei; Li, Shikuo; Zhang, Hui

2018-02-01

The composite containing reduced graphene oxide and MnO nanoparticles (RGO/MnO) has been prepared via a one step pyrolysis method. The MnO nanoparticles were uniformly dispersed on the surface of RGO nanosheets forming MnO/RGO composite. The composite displays a maximum absorption of ‒38.9 dB at 13.5 GHz and the bandwidth of reflection loss corresponding to -10 dB can reach 4.9 GHz (from 11.5 to 16.4 GHz) with a coating layer thickness of only 2 mm. Therefore, the obtained RGO/MnO composite a perfect lightweight and high-performance electromagnetic wave absorbent.

Superexchange Effects on Oxygen Reduction Activity of Edge-Sharing [Cox Mn1-x O6 ] Octahedra in Spinel Oxide.

PubMed

Zhou, Ye; Sun, Shengnan; Xi, Shibo; Duan, Yan; Sritharan, Thirumany; Du, Yonghua; Xu, Zhichuan J

2018-03-01

Mn-Co containing spinel oxides are promising, low-cost electrocatalysts for the oxygen reduction reaction (ORR). Most studies are devoted to the design of porous Mn-Co spinels or to strongly coupled hybrids (e.g., MnCo 2 O 4 /N-doped-rmGO) to maximize the mass efficiency. The lack of analyses by metal oxide intrinsic activity (activity normalized to catalysts' surface area) hinders the development of fundamental understanding of the physicochemical principles behind the catalytic activities. A systematic study on the composition dependence of ORR in ZnCo x Mn 2- x O 4 (x = 0.0-2.0) spinel is presented here with special attention to the role of edge sharing [Co x Mn 1- x O 6 ] octahedra in the spinel structure. The ORR specific activity of ZnCo x Mn 2- x O 4 spans across a potential window of 200 mV, indicating an activity difference of ≈3 orders of magnitude. The curve of composition-dependent ORR specific activity as a function of Co substitution exhibits a volcano shape with an optimum Mn/Co ratio of 0.43. It is revealed that the modulated e g occupancy of active Mn cations (0.3-0.9), as a consequence of the superexchange effect between edge sharing [CoO 6 ] and [MnO 6 ], reflects the ORR activity of edge sharing [Co x Mn 1- x O 6 ] octahedra in the ZnCo x Mn 2- x O 4 spinel oxide. These findings offer crucial insights in designing spinel oxide catalysts with fine-tuned e g occupancy for efficient catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of Benzoin to Benzil Using Alumina-Supported Active MnO2

NASA Astrophysics Data System (ADS)

Crouch, R. David; Holden, Michael S.; Burger, Jennifer S.

2001-07-01

The use of alumina-supported active MnO2 to oxidize benzoin to benzil is described. The advantages of this reagent include ease of handling and separation from the product and lower toxicity than previously reported supported oxidizing agents. The product is purified by elution through a simple chromatography column consisting of a silica gel-packed Pasteur pipet. Students' yields are comparable to yields from other reported oxidation methods.

XPS and EELS characterization of Mn2SiO4, MnSiO3 and MnAl2O4

NASA Astrophysics Data System (ADS)

Grosvenor, A. P.; Bellhouse, E. M.; Korinek, A.; Bugnet, M.; McDermid, J. R.

2016-08-01

X-ray Photoelectron Spectroscopy (XPS) and Electron Energy Loss Spectroscopy (EELS) are strong candidate techniques for characterizing steel surfaces and substrate-coating interfaces when investigating the selective oxidation and reactive wetting of advanced high strength steels (AHSS) during the continuous galvanizing process. However, unambiguous identification of ternary oxides such as Mn2SiO4, MnSiO3, and MnAl2O4 by XPS or EELS, which can play a significant role in substrate reactive wetting, is difficult due to the lack of fully characterized standards in the literature. To resolve this issue, samples of Mn2SiO4, MnSiO3 and MnAl2O4 were synthesized and characterized by XPS and EELS. The unique features of the XPS and EELS spectra for the Mn2SiO4, MnSiO3 and MnAl2O4 standards were successfully derived, thereby allowing investigators to fully differentiate and identify these oxides at the surface and subsurface of Mn, Si and Al alloyed AHSS using these techniques.

Photocatalytic oxidation of aromatic amines using MnO2@g ...

EPA Pesticide Factsheets

An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of energy at room temperature Prepared for submission to the journal, Advanced Materials Letters.

Multireversible redox processes in pentanuclear bis(triple-helical) manganese complexes featuring an oxo-centered triangular {Mn(II)2Mn(III)(μ3-O)}5+ or {Mn(II)Mn(III)2(μ3-O)}6+ core wrapped by two {Mn(II)2(bpp)3}-.

PubMed

Romain, Sophie; Rich, Jordi; Sens, Cristina; Stoll, Thibaut; Benet-Buchholz, Jordi; Llobet, Antoni; Rodriguez, Montserrat; Romero, Isabel; Clérac, Rodolphe; Mathonière, Corine; Duboc, Carole; Deronzier, Alain; Collomb, Marie-Noëlle

2011-09-05

A new pentanuclear bis(triple-helical) manganese complex has been isolated and characterized by X-ray diffraction in two oxidation states: [{Mn(II)(μ-bpp)(3)}(2)Mn(II)(2)Mn(III)(μ-O)](3+) (1(3+)) and [{Mn(II)(μ-bpp)(3)}(2)Mn(II)Mn(III)(2)(μ-O)](4+) (1(4+)). The structure consists of a central {Mn(3)(μ(3)-O)} core of Mn(II)(2)Mn(III) (1(3+)) or Mn(II)Mn(III)(2) ions (1(4+)) which is connected to two apical Mn(II) ions through six bpp(-) ligands. Both cations have a triple-stranded helicate configuration, and a pair of enantiomers is present in each crystal. The redox properties of 1(3+) have been investigated in CH(3)CN. A series of five distinct and reversible one-electron waves is observed in the -1.0 and +1.50 V potential range, assigned to the Mn(II)(4)Mn(III)/Mn(II)(5), Mn(II)(3)Mn(III)(2)/Mn(II)(4)Mn(III), Mn(II)(2)Mn(III)(3)/Mn(II)(3)Mn(III)(2), Mn(II)Mn(III)(4)/Mn(II)(2)Mn(III)(3), and Mn(III)(5)/Mn(II)Mn(III)(4) redox couples. The two first oxidation processes leading to Mn(II)(3)Mn(III)(2) (1(4+)) and Mn(II)(2)Mn(III)(3) (1(5+)) are related to the oxidation of the Mn(II) ions of the central core and the two higher oxidation waves, close in potential, are thus assigned to the oxidation of the two apical Mn(II) ions. The 1(4+) and 1(5+) oxidized species and the reduced Mn(4)(II) (1(2+)) species are quantitatively generated by bulk electrolyses demonstrating the high stability of the pentanuclear structure in four oxidation states (1(2+) to 1(5+)). The spectroscopic characteristics (X-band electron paramagnetic resonance, EPR, and UV-visible) of these species are also described as well as the magnetic properties of 1(3+) and 1(4+) in solid state. The powder X- and Q-band EPR signature of 1(3+) corresponds to an S = 5/2 spin state characterized by a small zero-field splitting parameter (|D| = 0.071 cm(-1)) attributed to the two apical Mn(II) ions. At 40 K, the magnetic behavior is consistent for 1(3+) with two apical S = 5/2 {Mn(II)(bpp)(3)}(-) and one S

Long-term in situ oxidation of biogenic uraninite in an alluvial aquifer: impact of dissolved oxygen and calcium.

PubMed

Lezama-Pacheco, Juan S; Cerrato, José M; Veeramani, Harish; Alessi, Daniel S; Suvorova, Elena; Bernier-Latmani, Rizlan; Giammar, Daniel E; Long, Philip E; Williams, Kenneth H; Bargar, John R

2015-06-16

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

NASA Astrophysics Data System (ADS)

Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu.; Rogov, V. A.; Sadykov, V. A.

2018-03-01

Mixed NaWMn/SiO2 oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na-W, Na-Mn, W-Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO2 mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575‒900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700-900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction ( 443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow ( 56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.

Morphology and phase identification of micron to nanosized manganese oxide (MnO) with variations in sintering time

NASA Astrophysics Data System (ADS)

Sasongko, Muhammad Ilman Nur; Puspitasari, Poppy; Yazirin, Cepi; Tsamroh, Dewi Izzatus; Risdanareni, Puput

2017-09-01

Manganese oxide (MnO) occurs in many rock types and may take the form of minerals. MnO has its drawbacks, namely highly reactive oxidizing species classified as dangerous and explosive at temperatures above 55 °C. Despite this,MnO has excellent magnetic, electrochemical, and conductivity properties, which should be reduced to nano-size to maximize their use and improve the properties of MnO. Phase and morphology characterization of powder this research aims to reduce the grain size of the MnO from micro to nano using the sol-gel method with various sintering times. Sol-gel is a simple synthesis method that has been proven capable of synthesizing a wide variety of micro-sized oxide materials into nano. Sintering time is a technique performed in the synthesis process to dry the material to a temperature above the normal temperature. The temperature used for sintering starting from 600 °C to 1000 °C. Characterizations were done using XRD, SEM, EDX, and FTIR machines. The sintering processes in this study used a temperature of 600 °C with different sintering periods of 30, 60 and 90 minutes. The XRD characterization with a 30-minute sintering time resulted in the smallest MnO in the form crystalline powder of 47.3 nm. The highest intensity (degree of crystallinity) found in MnO sintered for 90 minutes. The results of the morphological characterization of SEM showed a morphological change in MnO from micro-sized triangular to nano-sized spherical shape. The EDX characterization results indicated that the 30-minute sintering caused the lowest change in Mn and the highest change in O. The results of FTIR characterization showed a shift in C-H and Mn-O followed by an increase in the group of N-H, C=O and Mn-O.

Production of Manganese Oxide Nanoparticles by Shewanella Species

PubMed Central

Farooqui, Saad M.; White, Alan R.

2016-01-01

ABSTRACT Several species of the bacterial genus Shewanella are well-known dissimilatory reducers of manganese under anaerobic conditions. In fact, Shewanella oneidensis is one of the most well studied of all metal-reducing bacteria. In the current study, a number of Shewanella strains were tested for manganese-oxidizing capacity under aerobic conditions. All were able to oxidize Mn(II) and to produce solid dark brown manganese oxides. Shewanella loihica strain PV-4 was the strongest oxidizer, producing oxides at a rate of 20.3 mg/liter/day and oxidizing Mn(II) concentrations of up to 9 mM. In contrast, S. oneidensis MR-1 was the weakest oxidizer tested, producing oxides at 4.4 mg/liter/day and oxidizing up to 4 mM Mn(II). Analysis of products from the strongest oxidizers, i.e., S. loihica PV-4 and Shewanella putrefaciens CN-32, revealed finely grained, nanosize, poorly crystalline oxide particles with identical Mn oxidation states of 3.86. The biogenic manganese oxide products could be subsequently reduced within 2 days by all of the Shewanella strains when culture conditions were made anoxic and an appropriate nutrient (lactate) was added. While Shewanella species were detected previously as part of manganese-oxidizing consortia in natural environments, the current study has clearly shown manganese-reducing Shewanella species bacteria that are able to oxidize manganese in aerobic cultures. IMPORTANCE Members of the genus Shewanella are well known as dissimilatory manganese-reducing bacteria. This study shows that a number of species from Shewanella are also capable of manganese oxidation under aerobic conditions. Characterization of the products of the two most efficient oxidizers, S. loihica and S. putrefaciens, revealed finely grained, nanosize oxide particles. With a change in culture conditions, the manganese oxide products could be subsequently reduced by the same bacteria. The ability of Shewanella species both to oxidize and to reduce manganese indicates

Microwave-assisted synthesis of Mn{sub 3}O{sub 4} nanoparticles@reduced graphene oxide nanocomposites for high performance supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

She, Xiao; Zhang, Xinmin; Liu, Jingya

2015-10-15

Highlights: • Mn{sub 3}O{sub 4}@rGO nanocomposites were prepared by one-step microwave-assisted method. • The growth of Mn{sub 3}O{sub 4} and the reduction of graphene oxide occurred simultaneously. • Specific capacitance of the nanocomposite is higher than those of rGO and Mn{sub 3}O{sub 4}. • The nanocomposites have good rate capability and cycling stability. - ABSTRACT: One-step microwave-assisted synthetic route for the fabrication of Mn{sub 3}O{sub 4} nanoparticles@reduced graphene oxide (Mn{sub 3}O{sub 4}@rGO) nanocomposites has been demonstrated. The morphological structures of the nanocomposites are characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analyses (TGA), and scanningmore » electron microscopy (SEM), respectively. All of the results indicate that the microwave-assisted synthesis results in the growth of Mn{sub 3}O{sub 4} and the reduction of graphene oxide simultaneously in ethylene glycol-water system. The specific capacitance of the as-prepared Mn{sub 3}O{sub 4}@rGO nanocomposite is higher than those of rGO and pure Mn{sub 3}O{sub 4}, which indicates the synergetic interaction between rGO and Mn{sub 3}O{sub 4}. The nanocomposites also have good rate capability and cycling stability in electrochemical experiments. This facile technique may be extended to the large scale and cost effective production of other composites based on graphene and metal oxide for many applications.« less

Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

PubMed Central

Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-01-01

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

PubMed

Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

2014-11-18

Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

PubMed Central

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

2015-01-01

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface. PMID:26469151

Synthesis and characterization of MnS2/reduced graphene oxide nanohybrids for with photocatalytic and antibacterial activity.

PubMed

Fakhri, Ali; Kahi, Delaram Salehpour

2017-01-01

A facile one-step hydrothermal route was developed here to prepare MnS 2 /reduced graphene oxide nanohybrids. The crystal morphologies could be controlled by adjusting the solvent, surfactant, and pH of the precursor solution. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-Vis absorption spectra, and photoluminescence spectra (PL), were used to characterize the structures of the samples were used to characterize the structures of the samples, and the specific surface area was determined using the Brunauer-Emmett-Teller (BET) method. The thickness of the MnS 2 nanoparticles and MnS 2 /reduced graphene oxide nanohybrids were measured to be about 20 and 5nm, respectively. The total pore volume and specific surface area were 0.540 and 1.173cm 3 g -1 and 45.91 and 98.23m 2 g -1 for pure MnS 2 and MnS 2 /r-GO hybrids, respectively. Carbophenothion as an insecticide photodegradation was used to estimate the photocatalytic activity of the MnS 2 /reduced graphene oxide nanohybrids morphologies under UV light. The Carbophenothion hardly decomposed during photolysis over a period of 45min. The rate constant, k value, for the photocatalysis of Carbophenothion by MnS 2 /reduced graphene oxide nanohybrids under UV light radiation is 0.134min -1 . The antibacterial properties of the nanohybrids were evaluated by determining their minimum inhibitory and bactericidal concentrations (MIC and MBC), using a broth microdilution assay for Escherichia coli (E. coli) bacteria. The MIC and MBC values are 4.0 and 32.0μg/mL. Copyright © 2016 Elsevier B.V. All rights reserved.

Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons.

PubMed

Ng, Nga L; Kroll, Jesse H; Keywood, Melita D; Bahreini, Roya; Varutbangkul, Varuntida; Flagan, Richard C; Seinfeld, John H; Lee, Anita; Goldstein, Allen H

2006-04-01

Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase concentrations (monitored by a Proton Transfer Reaction Mass Spectrometer, PTR-MS), we study the general mechanisms of SOA formation. Aerosol growth data are presented in terms of a "growth curve", a plot of aerosol mass formed versus the amount of hydrocarbon reacted. From the shapes of the growth curves, it is found that all the hydrocarbons studied can be classified into two groups based entirely on the number of double bonds of the hydrocarbon, regardless of the reaction systems (ozonolysis or photooxidation) and the types of hydrocarbons studied: compounds with only one double bond and compounds with more than one double bond. For compounds with only one double bond, the first oxidation step is rate-limiting, and aerosols are formed mainly from low volatility first-generation oxidation products; whereas for compounds with more than one double bond, the second oxidation step may also be rate-limiting and second-generation products contribute substantially to SOA growth. This behavior is characterized by a vertical section in the growth curve, in which continued aerosol growth is observed even after all the parent hydrocarbon is consumed.

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

NASA Astrophysics Data System (ADS)

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. Electronic supplementary information (ESI) available: Fig. S1, AFM image (5 μm × 5 μm) of graphene nanoplate-MnO2 composite obtained at 3 h; Fig. S2, nitrogen adsorption/desorption isotherm of graphene nanoplate-MnO2 composite obtained at 3 h. See DOI: 10.1039/c1nr10229j

Porous Mn-doped cobalt oxide@C nanocomposite: a stable anode material for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kalubarme, Ramchandra S.; Jadhav, Sarika M.; Kale, Bharat B.; Gosavi, Suresh W.; Terashima, Chiaki; Fujishima, Akira

2018-07-01

Cobalt oxide is a transition metal oxide, well studied as an electrode material for energy storage applications, especially in supercapacitors and rechargeable batteries, due to its high charge storage ability. However, it suffers from low conductivity, which effectively hampers its long-term stability. In the present work, a simple strategy to enhance the conductivity of cobalt oxide is adopted to achieve stable electrochemical performance by means of carbon coating and Mn doping, via a simple and controlled, urea-assisted glycine-nitrate combustion process. Structural analysis of carbon coated Mn-doped Co3O4 (Mn-Co3O4@C) confirms the formation of nanoparticles (∼50 nm) with connected morphology, exhibiting spinel structure. The Mn-Co3O4@C electrode displays superior electrochemical performance as a Li-ion battery anode, delivering a specific capacity of 1250 mAh g‑1. Mn-Co3O4@C demonstrates excellent performance in terms of long-term stability, keeping charge storage ability intact even at high current rates due to the synergistic effects of fast kinetics—provided by enriched electronic conductivity, which allows ions to move freely to active sites and electrons from reaction sites to substrate during redox reactions—and high surface area combined with mesoporous architecture. The fully assembled battery device using Mn-Co3O4@C and standard LiCoO2 electrode shows 90% capacity retention over 100 cycles.

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

NASA Astrophysics Data System (ADS)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant

Selective Oxidation of a 0.1C-6Mn-2Si Third Generation Advanced High-Strength Steel During Dew-Point Controlled Annealing

NASA Astrophysics Data System (ADS)

Pourmajidian, Maedeh; McDermid, Joseph R.

2018-03-01

The present study investigates the selective oxidation of a 0.1C-6Mn-2Si medium-Mn advanced high-strength steel during austenization annealing heat treatments as a function of process atmosphere oxygen partial pressure and annealing time. It was determined that the surface oxide growth kinetics followed a parabolic rate law with the minimum rate belonging to the lowest oxygen partial pressure atmosphere at a dew point of 223 K (- 50 °C). The chemistry of the surface and subsurface oxides was studied using STEM + EELS on the sample cross sections, and it was found that the surface oxides formed under the 223 K (- 50 °C) dew-point atmosphere consisted of a layered configuration of SiO2, MnSiO3, and MnO, while in the case of the higher pO2 process atmospheres, only MnO was detected at the surface. Consistent with the Wagner calculations, it was shown that the transition to internal oxidation for Mn occurred under the 243 K (- 30 °C) and 278 K (+ 5 °C) dew-point atmospheres. However, the predictions of the external to internal oxidation for Si using the Wagner model did not correlate well with the experimental findings nor did the predictions of the Mataigne et al. model for multi-element alloys. Investigations of the internal oxide network at the grain boundaries revealed a multilayer oxide structure composed of amorphous SiO2 and crystalline MnSiO3, respectively, at the oxide core and outer shell. A mechanism for the formation of the oxide morphologies observed, based on kinetic and thermodynamic factors, was proposed. It is expected that only the fine and nodule-like MnO oxides formed on the surface of the samples annealed under the 278 K (+ 5 °C) dew-point process atmosphere for 60 and 120 seconds are sufficiently thin and of the desired dispersed morphology to promote reactive wetting by the molten galvanizing bath.

Illumina sequencing of fungi associated with manganese oxide deposits in cave systems

NASA Astrophysics Data System (ADS)

Zorn, B. T.; Santelli, C. M.; Carmichael, S. K.; Pepe-Ranney, C. P.; Roble, L.; Carmichael, M.; Bräuer, S.

2013-12-01

The environmental cycling of manganese (Mn) remains relatively poorly characterized when compared with other metals such as iron. However, fungi have been observed to produce Mn(III/IV) oxides resembling buserite, birnessite, and todorokite on the periphery of vegetative hyphae, hyphal branching points and at the base of fruiting bodies. Recent studies indicate that some of these oxides may be generated by a two-stage reaction with soluble Mn(II) and biogenic reactive oxygen species for some groups of fungi, in particular the Ascomycota. These oxides can provide a versatile protective barrier or aid in the capture of trace metals in the environment, although the exact evolutionary function and trigger is unclear. In this study, two caves in the southern Appalachians, a pristine cave and an anthropogenically impacted cave, were compared by analyzing fungal community assemblages in manganese oxide rich deposits. Quantitative PCR data indicated that fungi are present in a low abundance (<1%) in all locations sampled within the caves. Among amplified DNA sequences retrieved in an 18S rDNA clone library, over 88% were representative of the phylum Basidiomycota (predominantly Agaricomycetes), 2.74% of Ascomycota, 2.28% of Blastocladiomycota and Chytridiomycota, 0.46% of Zygomycota, and 3.65% of Eukarya or Fungi incertae sedis. Using Illumina's MiSeq to sequence amplicons of the fungal ITS1 gene has yielded roughly 100,000-200,000 paired-end reads per sample. These data are currently being analyzed to compare fungal communities before and after induced Mn oxidation in the field. In addition, sites within the pristine cave are being compared with analogous sites in the impacted cave. Culturing efforts have thus far yielded Mn oxide producing members of the orders Glomerales and Pleosporales as well as two Genus incertae sedis (Fungal sp. YECT1, and Fungal sp. YECT3, growing on discarded electrical tape) that do not appear to be closely related to any other known Mn

The structure of a one-electron oxidized Mn(iii)-bis(phenolate)dipyrrin radical complex and oxidation catalysis control via ligand-centered redox activity.

PubMed

Lecarme, Laureline; Chiang, Linus; Moutet, Jules; Leconte, Nicolas; Philouze, Christian; Jarjayes, Olivier; Storr, Tim; Thomas, Fabrice

2016-10-18

The tetradentate ligand dppH3, which features a half-porphyrin and two electron-rich phenol moieties, was prepared and chelated to manganese. The mononuclear Mn(iii)-dipyrrophenolate complex 1 was structurally characterized. The metal ion lies in a square pyramidal environment, the apical position being occupied by a methanol molecule. Complex 1 displays two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc + /Fc, which are assigned to ligand-centered processes. The one-electron oxidized species 1+ SbF6- was crystallized, showing an octahedral Mn(iii) center with two water molecules coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that the radical is delocalized over the whole aromatic framework. Complex 1+ SbF6- exhibits an S tot = 3/2 spin state due to the antiferromagnetic coupling between Mn(iii) and the ligand radical. The zero field splitting parameters are D = 1.6 cm -1 , E/D = 0.18(1), g ⊥ = 1.99 and g ∥ = 1.98. The dication 12+ is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a Mn(iii) metal center. Both 1 and 1+ SbF6- catalyze styrene oxidation in the presence of PhIO, but the nature of the main reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed predominantly when using 1+ SbF6-. We examined the ability of complex 1+ SbF6- to catalyze the isomerization of styrene oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case of 1+ SbF6-. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a catalyst based on a redox-active ligand.

Saturation kinetics in phenolic O-H bond oxidation by a mononuclear Mn(III)-OH complex derived from dioxygen.

PubMed

Wijeratne, Gayan B; Corzine, Briana; Day, Victor W; Jackson, Timothy A

2014-07-21

The mononuclear hydroxomanganese(III) complex, [Mn(III)(OH)(dpaq)](+), which is supported by the amide-containing N5 ligand dpaq (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) was generated by treatment of the manganese(II) species, [Mn(II)(dpaq)](OTf), with dioxygen in acetonitrile solution at 25 °C. This oxygenation reaction proceeds with essentially quantitative yield (greater than 98% isolated yield) and represents a rare example of an O2-mediated oxidation of a manganese(II) complex to generate a single product. The X-ray diffraction structure of [Mn(III)(OH)(dpaq)](+) reveals a short Mn-OH distance of 1.806(13) Å, with the hydroxo moiety trans to the amide function of the dpaq ligand. No shielding of the hydroxo group is observed in the solid-state structure. Nonetheless, [Mn(III)(OH)(dpaq)](+) is remarkably stable, decreasing in concentration by only 10% when stored in MeCN at 25 °C for 1 week. The [Mn(III)(OH)(dpaq)](+) complex participates in proton-coupled electron transfer reactions with substrates with relatively weak O-H and C-H bonds. For example, [Mn(III)(OH)(dpaq)](+) oxidizes TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol), which has a bond dissociation free energy (BDFE) of 66.5 kcal/mol, in MeCN at 25 °C. The hydrogen/deuterium kinetic isotope effect of 1.8 observed for this reaction implies a concerted proton-electron transfer pathway. The [Mn(III)(OH)(dpaq)](+) complex also oxidizes xanthene (C-H BDFE of 73.3 kcal/mol in dimethylsulfoxide) and phenols, such as 2,4,6-tri-t-butylphenol, with BDFEs of less than 79 kcal/mol. Saturation kinetics were observed for phenol oxidation, implying an initial equilibrium prior to the rate-determining step. On the basis of a collective body of evidence, the equilibrium step is attributed to the formation of a hydrogen-bonding complex between [Mn(III)(OH)(dpaq)](+) and the phenol substrates.

Mesoporous MnCeO x solid solutions for low temperature and selective oxidation of hydrocarbons

DOE PAGES

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

2015-10-15

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn 0.5Ce 0.5O x solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn 0.5Ce 0.5O xmore » solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

Mechanism of the Enantioselective Oxidation of Racemic Secondary Alcohols Catalyzed by Chiral Mn(III)–Salen Complexes

PubMed Central

Brown, M. Kevin; Blewett, Megan M.; Colombe, James R.; Corey, E. J.

2010-01-01

The experiments described here clarify the mechanism and origin of the enantioselectivity of the oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)–salen complexes using HOBr, Br2/H2O/KOAc or PhI(OAc)2/H2O/KBr as a stoichiometric oxidant. Key points of the proposed pathway include (1) the formation of a Mn(V)–salen dibromide, (2) its subsequent reaction with the alcohol to give an alkoxy-Mn(V) species, and (3) carbonyl-forming elimination to produce the ketone via a highly organized transition state with intramolecular transfer of hydrogen from carbon to an oxygen of the salen ligand. PMID:20666410

Catalytic oxidation of VOCs over Mn/TiO2/activated carbon under 185 nm VUV irradiation.

PubMed

Shu, Yajie; Xu, Yin; Huang, Haibao; Ji, Jian; Liang, Shimin; Wu, Muyan; Leung, Dennis Y C

2018-06-04

Volatile organic compounds (VOCs) are regarded as the major contributors to air pollution, and should be strictly regulated. Photocatalytic oxidation (PCO) is of great interest for the removal of VOCs owing to its strong oxidation capability. However, its application is greatly limited by catalytic deactivation. Vacuum Ultraviolet (VUV) irradiation provides a novel way to improve the photocatalytic activity while much O 3 will be generated which may cause secondary pollution. In this study, a multi-functional catalyst of Mn/TiO 2 /activated carbon (AC) was developed to eliminate and utilize O 3 , as well as enhance catalytic oxidation of VOC degradation via ozone-assisted catalytic oxidation (OZCO). The results indicate that Mn modified TiO 2 /AC (i.e. 0.1%Mn/20%TiO 2 /AC) achieved a toluene removal efficiency of nearly 86% with 100% elimination rate of O 3 . With the help of Mn/TiO 2 /AC catalyst, O 3 was catalytically decomposed and transformed into active species of O ( 1 D) and OH, thus enhancing toluene removal. The combination of VUV irradiation with multi-functional catalyst provides a novel and efficient way for the degradation of VOCs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

PubMed

Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

2015-05-13

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn 16 and Mn 18 clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexandropoulos, Dimitris I.; Moushi, Eleni E.; Papatriantafyllopoulou, Constantina

Here, the employment of cyanato (OCN -) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH) 2] (R = Me (1), Et (2)) and [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O 2CMe) 2·4H 2O, hmpH, NaOCN and NEt 3 in solvent MeOH or EtOH afford the isostructural complexes [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH)more » 2] (R = Me (1), Et (2)). The [Mn 16(μ 4-O) 4(μ 3-O) 4(μ-OMe) 4(μ 3-OR) 6(μ-OR) 6] 10+ core of representative complex 1 comprises a Mn II 4Mn III 4 double-cubane subunit attached on either side to two symmetry-related Mn IIMn III 3 defective dicubanes. A similar reaction of Mn(O 2CR) 2·4H 2O, hmpH, NaOCN and NEt 3, but in solvent MeCN, led instead to the formation of [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [Mn III 4(μ-O) 6] rodlike subunit attached on either side to two symmetry-related [Mn 7O 9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear Mn II/III complexes with structures different than these obtained from the use of the related azides.« less

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn 16 and Mn 18 clusters

DOE PAGES

Alexandropoulos, Dimitris I.; Moushi, Eleni E.; Papatriantafyllopoulou, Constantina; ...

2015-12-02

Here, the employment of cyanato (OCN -) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH) 2] (R = Me (1), Et (2)) and [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O 2CMe) 2·4H 2O, hmpH, NaOCN and NEt 3 in solvent MeOH or EtOH afford the isostructural complexes [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH)more » 2] (R = Me (1), Et (2)). The [Mn 16(μ 4-O) 4(μ 3-O) 4(μ-OMe) 4(μ 3-OR) 6(μ-OR) 6] 10+ core of representative complex 1 comprises a Mn II 4Mn III 4 double-cubane subunit attached on either side to two symmetry-related Mn IIMn III 3 defective dicubanes. A similar reaction of Mn(O 2CR) 2·4H 2O, hmpH, NaOCN and NEt 3, but in solvent MeCN, led instead to the formation of [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [Mn III 4(μ-O) 6] rodlike subunit attached on either side to two symmetry-related [Mn 7O 9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear Mn II/III complexes with structures different than these obtained from the use of the related azides.« less

BIOGENIC HYDROCARBONS IN THE ATMOSPHERIC BOUNDARY LAYER: A REVIEW

EPA Science Inventory

Nonmethane hydrocarbons are ubiquitous trace atmospheric constituents yet they control the oxidation capacity of the atmosphere. Both anthropogenic and biogenic processes contribute to the release of hydrocarbons to the atmosphere. In this manuscript, the state of the science ...

The Extent of CH4 Emission and Oxidation in Thermogenic and Biogenic Gas Hydrate Environments

NASA Astrophysics Data System (ADS)

Kastner, M.; Solem, C.; Bartlett, D.; MacDonald, I.; Valentine, D.

2003-12-01

The role of methane hydrate in the global methane budget is poorly understood, because relatively little is known about the transport of gaseous and dissolved methane through the seafloor into the ocean, from the water column into the atmosphere, and the extent of water-column methanotrophy that occurs en route. We characterize the transport and consumption of methane in three distinct gas hydrate environments, spanning the spectrum of thermogenic and biogenic methane occurrences: Bush Hill in the Gulf of Mexico, Eel River off the coast of Northern California, and the Noth and South Hydrate Ridges on the Cascadia Oregon margin. At all the sites studied a significant enrichment in δ 13CH4 with distance along isopycnals away from the methane source is observed, indicative of extensive aerobic bacterial methane oxidation in the water column. The effects of this process are principally pronounced in the mostly biogenic methane setting, with δ 13C-CH4 measured as high as -12 permil (PDB) between North and South Hydrate Ridge. The δ 13C-CH4 values ranged from -12 to -67 permil at Hydrate Ridge, -34 to -52 permil at Eel River, and -41 to -49 permil at Bush Hill. The large variation in methane carbon isotope ranges between the sites suggest that major differences exist in both the rates of aerobic methane oxidation and system openness at the studied locations. A mean kinetic isotope fractionation factor is being determined using a closed-system Rayleigh distillation model. An approximate regional methane flux from the ocean into the atmosphere is being estimated for the Gulf of Mexico, by extrapolation of the flux value from the Bush Hill methane plume over 390 plume locations having persistent oil slicks on the ocean surface, mapped by time series satellite data.

Nucleation and growth of electrodeposited Mn oxide rods for supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Clark, Michael; Ivey, Douglas G.

2015-09-01

The nucleation and growth of electrodeposited Mn oxide rods has been investigated by preparing deposits on Au coated Si at varying deposition times between 0.5 s and 10 min. The deposits were investigated using high resolution scanning and transmission electron microscopy. A model for the nucleation and growth of Mn oxide rods has been proposed. Nucleation begins as thin sheets along Au grain boundaries and triple points. As these nucleation sites are consumed, nucleation spreads across the grains. Nucleation of sheets in close proximity causes agglomeration and the formation of rounded particles. Some of these rounded particles then accelerate in growth, initially in all directions and then primarily in the direction normal to the sample surface. Accelerated growth normal to the sample surface leads to the formation of rods. As rods grow, the growth of other particles accelerates and they become rods themselves. Eventually the entire sample surface is covered with rods 15-20 μm long and about 2 μm wide. The sheet-like morphology of the deposits is retained at all stages of deposition. Electron diffraction analysis of 3 s and 6 s deposits shows that the sheets are initially amorphous and then begin to crystallize into a cubic spinel Mn3O4 crystal structure. High resolution imaging of the 6 s sample shows small crystalline regions (˜5 nm in size) within an amorphous matrix.

Measurements of PAN, PPN, and MPAN made during the 1994 and 1995 Nashville Intensives of the Southern Oxidant Study: Implications for regional ozone production from biogenic hydrocarbons

NASA Astrophysics Data System (ADS)

Roberts, James M.; Williams, Jonathan; Baumann, Karsten; Buhr, Martin P.; Goldan, Paul D.; Holloway, John; Hübler, Gerhard; Kuster, William C.; McKeen, Stuart A.; Ryerson, Thomas B.; Trainer, Michael; Williams, Eric J.; Fehsenfeld, Fredrick C.; Bertman, Steven B.; Nouaime, George; Seaver, Craig; Grodzinsky, Gil; Rodgers, Michael; Young, Valerie L.

1998-09-01

Isoprene and a variety of other reactive hydrocarbons are released in large quantities by vegetation in forested regions and are thought to participate in the NOx-catalyzed production of ozone, a serious air quality problem in North America and Europe [National Research Council, 1991]. The determination of the fraction of O3 formed from anthropogenic NOx and biogenic hydrocarbons (BHC) is a crucial step in the formulation of effective control strategies. Peroxymethacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed almost entirely from the atmospheric oxidation of isoprene in the presence of NOx and is an excellent indicator of recent ozone production from isoprene and therefore biogenic hydrocarbons. Measurements are presented here of MPAN, peroxyacetic nitric anhydride (PAN, CH3C(O)OONO2), peroxypropionic nitric anhydride (PPN, CH3CH2C(O)OONO2) and ozone from separate data sets acquired during the 1994 and 1995 Nashville intensive studies of the Southern Oxidant Study. It was found that PAN, a general product of HC-NOx photochemistry, could be well represented as a simple linear combination of contributions from BHC and anthropogenic hydrocarbon (AHC) chemistries as indicated by MPAN and PPN, respectively. The PAN:MPAN ratios found to be characteristic of BHC-dominated chemistry ranged from 6 to 10. The PAN:PPN ratios found to be characteristic of AHC-dominated chemistry ranged from 5.8 to 7.4. These BHC and AHC attributions were used to estimate the contributions of anthropogenic and biogenic hydrocarbons to regional tropospheric ozone production, and substantial BHC-O3 (50-60 ppbv) was estimated in cases where high NOx from power plants was present in areas of high BHC emission. This estimation method provides direct evidence of significant photochemical ozone production from the oxidation of biogenic hydrocarbons in the presence of NOx.

Effect of the nano-oxide layer as a Mn diffusion barrier in specular spin valves

NASA Astrophysics Data System (ADS)

Jang, S. H.; Kang, T.; Kim, H. J.; Kim, K. Y.

2002-07-01

In previous work an enhanced giant magnetoresistance (GMR) effect in spin valves (SVs) with a nano-oxide layer (NOL) after annealing at about 250-300 degC has been reported. We have shown that SVs with a NOL also have higher thermal stability of the MR ratio at 300 degC. From secondary-ion-mass spectroscopy and x-ray photoelectron spectroscopy depth profile analysis, the mechanism of the improved thermal stability of the SVs with a NOL is shown to be related to MnO formation within the NOL. Thus, Mn atoms from the FeMn layer are trapped, and Mn diffusion is inhibited by the NOL during annealing.

Electrocatalytic Water Oxidation Promoted by 3 D Nanoarchitectured Turbostratic δ-MnOx on Carbon Nanotubes.

PubMed

Zhang, Biaobiao; Li, Yuanyuan; Valvo, Mario; Fan, Lizhou; Daniel, Quentin; Zhang, Peili; Wang, Linqin; Sun, Licheng

2017-11-23

The development of manganese-based water oxidation electrocatalysts is desirable for the production of solar fuels, as manganese is earth-abundant, inexpensive, non-toxic, and has been employed by the Photosystem II in nature for a billion years. Herein, we directly constructed a 3 D nanoarchitectured turbostratic δ-MnO x on carbon nanotube-modified nickel foam (MnO x /CNT/NF) by electrodeposition and a subsequent annealing process. The MnO x /CNT/NF electrode gives a benchmark catalytic current density (10 mA cm -2 ) at an overpotential (η) of 270 mV under alkaline conditions. A steady current density of 19 mA cm -2 is obtained during electrolysis at 1.53 V for 1.0 h. To the best of our knowledge, this work represents the most efficient manganese-oxide-based water oxidation electrode and demonstrates that manganese oxides, as a structural and functional model of oxygen-evolving complex (OEC) in Photosystem II, can also become comparable to those of most Ni- and Co-based catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced permanganate in situ chemical oxidation through MnO2 particle stabilization: evaluation in 1-D transport systems.

PubMed

Crimi, Michelle; Quickel, Mark; Ko, Saebom

2009-02-27

In situ chemical oxidation using permanganate is an increasingly employed approach to organic contaminant remediation at hazardous waste sites. Manganese dioxide (MnO2) particles form as a by-product of the reaction of permanganate with contaminants and naturally-reduced subsurface materials. These particles are of interest because they have the potential to deposit in the subsurface and impact the flow regime in/around permanganate injection, including the well screen, filter pack, and the surrounding subsurface formation. Control of these particles can allow for improved oxidant injection and transport, and contact between the oxidant and contaminants of concern. Sodium hexametaphosphate (HMP) has previously been identified as a promising aid to stabilize MnO2 in solution when included in the oxidizing solution, increasing the potential to inhibit particle deposition and impact subsurface flow. The goal of the experimental studies described herein was to investigate the ability of HMP to prevent particle deposition in transport studies using four different types of porous media. Permanganate was delivered to a contaminant source zone (trichloroethylene) located within four different media types with variations in sand, clay, organic carbon, and iron oxides (as goethite) content. Deposition of MnO2 within the columns was quantified with distance from the source zone. Experiments were repeated in replicate columns with the inclusion of HMP directly with the oxidant delivery solution, and MnO2 deposition was again quantified. While total MnO2 deposition within the 60 cm columns did not change significantly with the addition of HMP, deposition within the contaminant source zone decreased by 25-85%, depending on the specific media type. The greatest differences in deposition were observed in the goethite-containing and clay-containing columns. Columns containing these two media types experienced completely plugged flow in the oxidant-only delivery systems; however

The role of biological uptake in iron and manganese cycling in Lake Baikal

USGS Publications Warehouse

Granina, L.Z.; Callender, E.

2006-01-01

The role of biological uptake in the internal cycling of Fe and Mn in Lake Baikal was quantified. Biological uptake, sedimentation consisting of the biogenic and lithogenic fluxes, and remineralization have been evaluated. The results of calculations show that about 5-10% of Fe and Mn accumulated in the lake are annually taken up by biota. More than 80% of this amount is again recycled after remineralization of biological material. At this, the biogenic fluxes of Fe and Mn are 2-4 times less compared to lithogenic ones. Thus not only is oxidation of Fe and Mn within the water column highly enriched in the oxygen that results in settling of Fe and Mn oxides, but also intensive biological uptake of these elements contributes to their fast removal from internal cycling. However, essential remineralization makes this process of minor importance to Fe and Mn cycling in Lake Baikal. ?? Springer 2006.

Effects of plant polyphenols and a-tocopherol on lipid oxidation, residual nitrites, biogenic amines, and N-nitrosamines formation during ripening and storage of dry-cured bacon

USDA-ARS?s Scientific Manuscript database

Effects of plant polyphenols (green tea polyphenols (GTP) and grape seed extract (GSE) and a-tocopherol on physicochemical parameters, lipid oxidation, residual nitrite, microbiological counts, biogenic amines, and N-nitrosamines were determined in bacons during dry-curing and storage. Results show ...

USER'S GUIDE TO THE PERSONAL COMPUTER VERSION OF THE BIOGENIC EMISSIONS INVENTORY SYSTEM (PC-BEIS2)

EPA Science Inventory

The document is a user's guide for an updated Personal Computer version of the Biogenic Emissions Inventory System (PC-BEIS2), allowing users to estimate hourly emissions of biogenic volatile organic compounds (BVOCs) and soil nitrogen oxide emissions for any county in the contig...

Bioturbation and Manganese Cycling in Hemipelagic Sediments

NASA Astrophysics Data System (ADS)

Aller, R. C.

1990-06-01

The activities of infaunal macrobenthos have major influences on the types, rates and distributions of diagenetic reactions involving manganese in relatively carbon-rich deep-sea and nearshore sediments. In some non-sulphidic hemipelagic deposits of the eastern equatorial Pacific (Panama Basin) biogenic reworking drives internal cycles of manganese, which can apparently account for up to ca. 100% of organic carbon oxidation and reduction of O2 supplied (diffusively) to the sea floor. Heterotrophic (carbon-based) manganese reduction is stimulated by simultaneous mixing of reactive organic matter and manganese oxide into suboxic-anoxic deposits. In sulphidic sediments, biogenic reworking must also enhance a lithotrophic pathway (sulphur-based) pathway of manganese reduction by promoting contact of manganese oxides and iron sulphides. Particle reworking dramatically alters the balance between aerobic and anaerobic decomposition pathways, promoting the utilization of O2 in the reoxidaton of reduced metabolites rather than direct oxidation of carbon. Irrigated burrows create microenvironments, which increase manganese reduction-oxidation and deplete Mn2+ from deeper pore waters. This may increase net Mn2+ production rates by removal of metabolites and potential co-precipitants with Mn2+. The occurrence and geometry of manganese oxide encrusted biogenic structures imply specific adaptations of infauna to manganese based microbial activity in hemipelagic sediments like the Panama Basin.

Triple-mixture of Zn, Mn, and Fe increases bioaccumulation and causes oxidative stress in freshwater neotropical fish.

PubMed

de Oliveira, Luciana Fernandes; Santos, Caroline; Risso, Wagner Ezequiel; Dos Reis Martinez, Claudia Bueno

2018-06-01

Metal bioaccumulation and oxidative stress biomarkers were determined in Prochilodus lineatus to understand the effects of short-term exposure to a triple-mixture of Zn, Mn, and Fe. Three independent tests were carried out, in which fish were exposed to 3 concentrations of Zn (0.18, 1.0, and 5.0 mg L -1 ), Mn (0.1, 0.5, and 5.0 mg L -1 ), and in the mix test to Fe (5.0 mg L -1 ) and a mixture of Zn (1.0 mg L -1 ) + Mn (0.5 mg L -1 ), with and without Fe. After exposure for 96 h, tissues were removed for metal bioaccumulation analysis and oxidative stress biomarkers were determined in liver, along with DNA damage in blood cells. Our results revealed that Zn and Mn were bioaccumulated in fish tissues after exposure to 5.0 mg L -1 , whereas Fe only bioaccumulated in muscle and gills after mixture exposure. Results indicated that 1 metal interfered with the other's bioaccumulation. In P. lineatus, 5 mg L -1 of both Mn and Fe were toxic, because damage was observed (lipid peroxidation [LPO] in liver and DNA damage in blood cells), whereas Zn induced liver responses (metallothionein [MT] and reduced glutathione [GSH] increases) to prevent damage. In terms of bioaccumulation and alterations of oxidative stress biomarkers, we showed that Zn, Mn, and Fe triple-mixture enhances individual metal toxicity in Neotropical fish P. lineatus. Environ Toxicol Chem 2018;37:1749-1756. © 2018 SETAC. © 2018 SETAC.

Arsenic release from Fe/Mn oxide-rich (model) soils/sediments - A comparison of single extraction procedures

NASA Astrophysics Data System (ADS)

Vanek, A.; Komarek, M.; Galuskova, I.

2012-04-01

Arsenic extractability in As-modified Fe(III) and Mn(III,IV) oxide-coated sands was tested using five widely used 2-h single extraction procedures: deionised water, 0.01 M CaCl2, 1 M NH4NO3, 0.1 M Na2HPO4 and 0.005 DTPA. In general, the highest As recoveries reaching 39-50% of total As concentration were observed for all extracting media in the birnessite (delta-MnO2) system, indicating relatively weak adsorption of As onto the Mn oxides. The Na2HPO4 extracts from the Fe oxide systems (i.e., associated with ferrihydrite and goethite) were highest in As, accounting for up to 34% of total As amount. Surprisingly, comparable recoveries of As (14-20%) yielded deionised water, CaCl2, NH4NO3, DTPA as extracting media for both ferrihydrite and goethite coatings. Deionised water and Na2HPO4 extractions are suggested for quick estimation of easily soluble, exchangeable and/or specifically adsorbed As in real soil/sediment samples.

New class of single-source precursors for the synthesis of main group-transition metal oxides: heterobimetallic Pb-Mn beta-diketonates.

PubMed

Zhang, Haitao; Yang, Jen-Hsien; Shpanchenko, Roman V; Abakumov, Artem M; Hadermann, Joke; Clérac, Rodolphe; Dikarev, Evgeny V

2009-09-07

Heterometallic lead-manganese beta-diketonates have been isolated in pure form by several synthetic methods that include solid-state and solution techniques. Two compounds with different Pb/Mn ratios, PbMn(2)(hfac)(6) (1) and PbMn(hfac)(4) (2) (hfac = hexafluoroacetylacetonate), can be obtained in quantitative yield by using different starting materials. Single crystal X-ray investigation revealed that the solid-state structure of 1 contains trinuclear molecules in which lead metal center is sandwiched between two [Mn(hfac)(3)] units, while 2 consists of infinite chains of alternating [Pb(hfac)(2)] and [Mn(hfac)(2)] fragments. The heterometallic structures are held together by strong Lewis acid-base interactions between metal atoms and diketonate ligands acting in chelating-bridging fashion. Spectroscopic investigation confirmed the retention of heterometallic structures in solutions of non-coordinating solvents as well as upon sublimation-deposition procedure. Thermal decomposition of heterometallic diketonates has been systematically investigated in a wide range of temperatures and annealing times. For the first time, it has been shown that thermal decomposition of heterometallic diketonates results in mixed-metal oxides, while both the structure of precursors and the thermolysis conditions have a significant influence on the nature of the resulting oxides. Five different Pb-Mn oxides have been detected by X-ray powder diffraction when studying the decomposition of 1 and 2 in the temperature range 500-800 degrees C. The phase that has been previously reported as "Pb(0.43)MnO(2.18)" was synthesized in the pure form by decomposition of 1, and crystallographically characterized. The orthorhombic unit cell parameters of this oxide, obtained by electron diffraction technique, have been subsequently refined using X-ray powder diffraction data. Besides that, a previously unknown lead-manganese oxide has been obtained at low temperature decomposition and short annealing

Catalytic oxidation of Hg(0) by MnOx-CeO2/γ-Al2O3 catalyst at low temperatures.

PubMed

Wang, Pengying; Su, Sheng; Xiang, Jun; You, Huawei; Cao, Fan; Sun, Lushi; Hu, Song; Zhang, Yun

2014-04-01

MnOx-CeO2/γ-Al2O3 (MnCe) selective catalytic reduction (SCR) catalysts prepared by sol-gel method were employed for low-temperature Hg(0) oxidation on a fixed-bed experimental setup. BET, XRD and XPS were used to characterize the catalysts. MnCe catalysts exhibited high Hg(0) oxidation activity at low temperatures (100-250 °C) under the simulated flue gas (O2, CO2, NO, SO2, HCl, H2O and balanced with N2). Only a small decrease in mercury oxidation was observed in the presence of 1200 ppm SO2, which proved that the addition of Ce helped resist SO2 poisoning. An enhancing effect of NO was observed due to the formation of multi-activity NOx species. The presence of HCl alone had excellent Hg(0) oxidation ability, while 10 ppm HCl plus 5% O2 further increased Hg(0) oxidation efficiency to 100%. Hg(0) oxidation on the MnCe catalyst surface followed the Langmiur-Hinshelwood mechanism, where reactions took place between the adsorbed active species and adsorbed Hg(0) to form Hg(2+). NH3 competed with Hg(0) for active sites on the catalyst surface, hence inhibiting Hg(0) oxidation. This study shows the feasibility of a single-step process integrating low-temperature SCR and Hg(0) oxidation from the coal combustion flue gas. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

PubMed

Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

2016-09-01

A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

Determination of the Mg/Mn ratio in foraminiferal coatings: An approach to correct Mg/Ca temperatures for Mn-rich contaminant phases

NASA Astrophysics Data System (ADS)

Hasenfratz, Adam P.; Martínez-García, Alfredo; Jaccard, Samuel L.; Vance, Derek; Wälle, Markus; Greaves, Mervyn; Haug, Gerald H.

2017-01-01

The occurrence of manganese-rich coatings on foraminifera can have a significant effect on their bulk Mg/Ca ratios thereby biasing seawater temperature reconstructions. The removal of this Mn phase requires a reductive cleaning step, but this has been suggested to preferentially dissolve Mg-rich biogenic carbonate, potentially introducing an analytical bias in paleotemperature estimates. In this study, the geochemical composition of foraminifera tests from Mn-rich sediments from the Antarctic Southern Ocean (ODP Site 1094) was investigated using solution-based and laser ablation ICP-MS in order to determine the amount of Mg incorporated into the coatings. The analysis of planktonic and benthic foraminifera revealed a nearly constant Mg/Mn ratio in the Mn coating of ∼0.2 mol/mol. Consequently, the coating Mg/Mn ratio can be used to correct for the Mg incorporated into the Mn phase by using the down core Mn/Ca values of samples that have not been reductively cleaned. The consistency of the coating Mg/Mn ratio obtained in this study, as well as that found in samples from the Panama Basin, suggests that spatial variation of Mg/Mn in foraminiferal Mn overgrowths may be smaller than expected from Mn nodules and Mn-Ca carbonates. However, a site-specific assessment of the Mg/Mn ratio in foraminiferal coatings is recommended to improve the accuracy of the correction.

Stable Isotope Analyses Suggest Biogenic Hydrocarbon Oxidation is a Major Source of Carbon Monoxide in Summertime Urban Environments

NASA Astrophysics Data System (ADS)

Vimont, I.; Turnbull, J. C.; Petrenko, V. V.; White, J. W. C.

2017-12-01

We present results from a study of carbon monoxide (CO) stable isotopes done at Indianapolis, Indiana as part of the INFLUX project. Our work shows that during the summer, CO production from oxidation of biogenically emitted volatile organic compounds (BVOC's) can equal CO emission from fossil fuel combustion. We hypothesize that the bulk of this VOC-produced CO burden is due to the oxidation of isoprene emitted from trees in, and surrounding, the city of Indianapolis. This result disagrees with modeled CO budget estimates by the Environmental Protection Agency's National Emissions Inventory (EPA NEI). However, recent studies of other gasses, in particular ozone, have produced similar estimates of the BVOC-produced CO burden (Cheng et al., 2017). One likely explanation for this result is the continual reduction of anthropogenic emissions through regulation.

Fabrication of band gap engineered nanostructured tri-metallic (Mn-Co-Ti) oxide thin films

NASA Astrophysics Data System (ADS)

Mansoor, Muhammad Adil; Yusof, Farazila Binti; Nay-Ming, Huang

2018-04-01

In continuation of our previous studies on photoelectrochemical (PEC) properties of titanium based composite oxide thin films, an effort is made to develop thin films of 1:1:2 manganese-cobalt-titanium oxide composite, Mn2O3-Co2O3-4TiO2 (MCT), using Co(OAc)2 and a bimetallic manganese-titanium complex, [Mn2Ti4(TFA)8(THF)6(OH)4(O)2].0.4THF (1), where OAc = acetato, TFA = trifluoroacetato and THF = tetrahydrofuran, via aerosol-assisted chemical vapour deposition (AACVD) technique. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) spectroscopic analyses confirmed formation of thin film of Mn2O3-Co2O3-4TiO2 composite material with uniformly distributed agglomerated particles. The average size of 39.5 nm, of the particles embedded inside agglomerates, was estimated by Scherer's equation. Further, UV-Vis spectroscopy was used to estimate the band gap of 2.62 eV for MCT composite thin film.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glaser, Mathias; Peisert, Heiko, E-mail: heiko.peisert@uni-tuebingen.de; Adler, Hilmar

2015-03-14

The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the chargemore » transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.« less

A hierarchical nanostructure consisting of amorphous MnO 2, Mn 3O 4 nanocrystallites, and single-crystalline MnOOH nanowires for supercapacitors

NASA Astrophysics Data System (ADS)

Hu, Chi-Chang; Hung, Ching-Yun; Chang, Kuo-Hsin; Yang, Yi-Lin

In this communication, a porous hierarchical nanostructure consisting of amorphous MnO 2 (a-MnO 2), Mn 3O 4 nanocrystals, and single-crystalline MnOOH nanowires is designed for the supercapacitor application, which is prepared by a simple two-step electrochemical deposition process. Because of the gradual co-transformation of Mn 3O 4 nanocrystals and a-MnO 2 nanorods into an amorphous manganese oxide, the cycle stability of a-MnO 2 is obviously enhanced by adding Mn 3O 4. This unique ternary oxide nanocomposite with 100-cycle CV activation exhibits excellent capacitive performances, i.e., excellent reversibility, high specific capacitances (470 F g -1 in CaCl 2), high power property, and outstanding cycle stability. The highly porous microstructures of this composite before and after the 10,000-cycle CV test are examined by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Novel Co- or Ni-Mn binary oxide catalysts with hydroxyl groups for NH3-SCR of NOx at low temperature

NASA Astrophysics Data System (ADS)

Gao, Fengyu; Tang, Xiaolong; Yi, Honghong; Zhao, Shunzheng; Wang, Jiangen; Shi, Yiran; Meng, Xiaomi

2018-06-01

Novel hydroxyl-containing Me-Mn binary oxides (Me = Co, Ni) were prepared for the selective catalytic reduction of NOx with NH3 by a combined complexation-esterification method. The binary oxides of Co-MnOx and Ni-MnOx with mixed crystal phases of Mn3O4 and Co3O4, Mn2O3 and NiMnO3 were obtained at 550 °C. SCR activity decreased in the order of Mn3O4-Co3O4-OH > Mn2O3-NiMnO3-OH > Mn2O3-OH > Mn3O4-OH, benefiting from the high concentration of chemisorbed oxygen and effective electron transformation of cations. Mn2O3-containing catalysts had better selectivity to N2 than those containing Mn3O4. Higher selectivity to N2O over Mn3O4-containing catalysts was attributed to the depth dehydrogenation of coordinated NH3 by the active oxygen species with lower Mnsbnd O band energy. The typical Eley-Rideal mechanism over Mn3O4-OH and Mn3O4-Co3O4-OH, and the additional formation pathway of NH4NO3 species over Mn2O3-OH and Mn2O3-NiMnO3-OH catalysts were proposed via the in-situ DRIFTS experiments. Although the Co and Ni elements had a good role in delaying the poisoning of SO2, these catalysts were eventually sulfated by SO2 over the postponement, which might due to the metal sulfate and ammonia hydrogensulfite species.

Conditions for the formation of pure birnessite during the oxidation of Mn(II) cations in aqueous alkaline medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boumaiza, Hella; Laboratoire de Chimie Physique et Microbiologie pour l'Environnement; Département de Génie Biologique et Chimique, Institut National des Sciences Appliquées et de Technologies

Birnessite was synthetized through redox reaction by mixing MnO{sub 4}{sup -}, Mn{sup 2+} and OH{sup -} solutions. The Mn(VII): Mn(II) ratio of 0.33 was chosen and three methods were used consisting in a quick mixing under vigorous stirring of two of the three reagents and then on the dropwise addition of the third one. The obtained solids were characterized by XRD, FTIR and XPS spectroscopies. Their average oxidation states were determined from ICP and CEC measurements while their surface properties were investigated by XPS. This study provides an increased understanding of the importance of dissolved oxygen in the formation ofmore » birnessite and hausmannite and shows the ways to obtain pure birnessite. The role of counter-ion ie. Na{sup +} or K{sup +} was also examined. - Graphical abstract: Pathways of birnessite formation. - Highlights: • Pure birnessite is prepared through a redox reaction. • Hausmannite formation is prevented by controlling dissolved O2. • The employed counterion influences the purity of birnessite. • Initial Mn(OH){sub 2} is oxidized by both MnO{sub 4}{sup -} and dissolved O{sub 2}.« less

Reactivity and O2 Formation by Mn(IV)- and Mn(V)-Hydroxo Species Stabilized within a Polyfluoroxometalate Framework.

PubMed

Schreiber, Roy E; Cohen, Hagai; Leitus, Gregory; Wolf, Sharon G; Zhou, Ang; Que, Lawrence; Neumann, Ronny

2015-07-15

Manganese(IV,V)-hydroxo and oxo complexes are often implicated in both catalytic oxygenation and water oxidation reactions. Much of the research in this area is designed to structurally and/or functionally mimic enzymes. On the other hand, the tendency of such mimics to decompose under strong oxidizing conditions makes the use of molecular inorganic oxide clusters an enticing alternative for practical applications. In this context it is important to understand the reactivity of conceivable reactive intermediates in such an oxide-based chemical environment. Herein, a polyfluoroxometalate (PFOM) monosubstituted with manganese, [NaH2(Mn-L)W17F6O55](q-), has allowed the isolation of a series of compounds, Mn(II, III, IV and V), within the PFOM framework. Magnetic susceptibility measurements show that all the compounds are high spin. XPS and XANES measurements confirmed the assigned oxidation states. EXAFS measurements indicate that Mn(II)PFOM and Mn(III)PFOM have terminal aqua ligands and Mn(V)PFOM has a terminal hydroxo ligand. The data are more ambiguous for Mn(IV)PFOM where both terminal aqua and hydroxo ligands can be rationalized, but the reactivity observed more likely supports a formulation of Mn(IV)PFOM as having a terminal hydroxo ligand. Reactivity studies in water showed unexpectedly that both Mn(IV)-OH-PFOM and Mn(V)-OH-PFOM are very poor oxygen-atom donors; however, both are highly reactive in electron transfer oxidations such as the oxidation of 3-mercaptopropionic acid to the corresponding disulfide. The Mn(IV)-OH-PFOM compound reacted in water to form O2, while Mn(V)-OH-PFOM was surprisingly indefinitely stable. It was observed that addition of alkali cations (K(+), Rb(+), and Cs(+)) led to the aggregation of Mn(IV)-OH-PFOM as analyzed by electron microscopy and DOSY NMR, while addition of Li(+) and Na(+) did not lead to aggregates. Aggregation leads to a lowering of the entropic barrier of the reaction without changing the free energy barrier. The

Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals

NASA Astrophysics Data System (ADS)

Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

2016-04-01

Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth.

Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals.

PubMed

Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

2016-04-01

Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth.

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

Effect of Mn on the Formation of Oxide Buildups Upon HVOF-Sprayed MCrAlY-Ceramic-Type Cermet Coatings

NASA Astrophysics Data System (ADS)

Huang, Tsai-Shang

2011-03-01

Thermal spray coatings have been widely used on hearth rolls in a continuous annealing line to improve steel sheet quality and to prolong the roll service life. One of the common defects formed on a working hearth roll is the oxide buildup. HVOF-sprayed CoCrAlY-CrB2-Y2O3 coating was used in this study to duplicate buildups by reacting with Fe and Mn oxides. The reaction was performed in a furnace at 900 °C with inert gases flowing through. After reacting for 8 days, large Mn-rich buildups were formed on the coating while the buildups without Mn were very small. Mn was shown to enhance the formation of buildups. Buildups from a hearth roll were also examined and compared with the laboratory ones.

Dissimilatory Fe(III) and Mn(IV) reduction.

PubMed Central

Lovley, D R

1991-01-01

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process. PMID:1886521

Critical Evaluations and Thermodynamic Optimizations of the MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 Systems

NASA Astrophysics Data System (ADS)

Kang, Youn-Bae; Jung, In-Ho

2017-06-01

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-Si-O system (MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 systems) are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25°C) to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Slag (molten oxide) was modeled using the modified quasichemical model in the pair approximation. Olivine (Fe2SiO4-Mn2SiO4) was modeled using two-sublattice model in the framework of the compound energy formalism (CEF), while rhodonite (MnSiO3-FeSiO3) and braunite (Mn7SiO_{12} with excess Mn2O3) were modeled as simple Henrian solutions. It is shown that the already developed models and databases of two spinel phases (cubic- and tetragonal-(Fe, Mn)3O4) using CEF [Kang and Jung, J. Phys. Chem. Solids (2016), vol. 98, pp. 237-246] can successfully be integrated into a larger thermodynamic database to be used in practically important higher order system such as silicate. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.

Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

PubMed

Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

2008-07-15

The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

A comparison study of the start-up of a MnOx filter for catalytic oxidative removal of ammonium from groundwater and surface water.

PubMed

Cheng, Ya; Li, Ye; Huang, Tinglin; Sun, Yuankui; Shi, Xinxin; Shao, Yuezong

2018-03-01

As an efficient method for ammonium (NH 4 + ) removal, contact catalytic oxidation technology has drawn much attention recently, due to its good low temperature resistance and short start-up period. Two identical filters were employed to compare the process for ammonium removal during the start-up period for ammonium removal in groundwater (Filter-N) and surface water (Filter-S) treatment. Two types of source water (groundwater and surface water) were used as the feed waters for the filtration trials. Although the same initiating method was used, Filter-N exhibited much better ammonium removal performance than Filter-S. The differences in catalytic activity among these two filters were probed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and compositional analysis. XRD results indicated that different manganese oxide species were formed in Filter-N and Filter-S. Furthermore, the Mn3p XPS spectra taken on the surface of the filter films revealed that the average manganese valence of the inactive manganese oxide film collected from Filter-S (FS-MnO x ) was higher than in the film collected from Filter-N (FN-MnO x ). Mn(IV) was identified as the predominant oxidation state in FS-MnO x and Mn(III) was identified as the predominant oxidation state in FN-MnO x . The results of compositional analyses suggested that polyaluminum ferric chloride (PAFC) used during the surface water treatment was an important factor in the mineralogy and reactivity of MnO x . This study provides the theoretical basis for promoting the wide application of the technology and has great practical significance. Copyright © 2017. Published by Elsevier B.V.

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

USGS Publications Warehouse

Brown, J.G.; Glynn, P.D.

2003-01-01

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Adsorption of arsenite and selenite using an inorganic ion exchanger based on Fe-Mn hydrous oxide.

PubMed

Szlachta, Małgorzata; Gerda, Vasyl; Chubar, Natalia

2012-01-01

The adsorption behaviour and mechanism of As(III) and Se(IV) oxyanion uptake using a mixed inorganic adsorbent were studied. The novel adsorbent, based on Fe(III)-Mn(III) hydrous oxides and manganese(II) carbonate, was synthesised using a hydrothermal precipitation approach in the presence of urea. The inorganic ion exchanger exhibited a high selectivity and adsorptive capacity towards As(III) (up to 47.6 mg/g) and Se(IV) (up to 29.0 mg/g), even at low equilibrium concentration. Although pH effects were typical for anionic species (i.e., the adsorption decreased upon pH increase), Se(IV) was more sensitive to pH changes than As(III). The rates of adsorption of both oxyanions were high. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) studies showed that the ion exchange adsorption of both anions took place via OH(-) groups, mainly from Fe(III) but also Mn(III) hydrous oxides. MnCO(3) did not contribute directly to As(III) and Se(IV) removal. A higher adsorptive capacity of the developed material towards As(III) was partly due to partial As(III) oxidation during adsorption. Copyright © 2011 Elsevier Inc. All rights reserved.

Biogenic Aldehydes as Therapeutic Targets for Cardiovascular Disease

PubMed Central

Nelson, Margaret-Ann M; Baba, Shahid P; Andersonc, Ethan J

2017-01-01

Aldehydes are continuously formed in biological systems through enzyme-dependent and spontaneous oxidation of lipids, glucose, and primary amines. These highly reactive, biogenic electrophiles can become toxic via covalent modification of proteins, lipids and DNA. Thus, agents that scavenge aldehydes through conjugation have therapeutic value for a number of major cardiovascular diseases. Several commonly-prescribed drugs (e.g., hydralazine) have been shown to have potent aldehyde-conjugating properties which may contribute to their beneficial effects. Herein, we briefly describe the major sources and toxicities of biogenic aldehydes in cardiovascular system, and provide an overview of drugs that are known to have aldehyde-conjugating effects. Some compounds of phytochemical origin, and histidyl-dipeptides with emerging therapeutic value in this area are also discussed. PMID:28528297

Bismuth Oxide Nanoparticles Partially Substituted with EuIII, MnIV, and SiIV: Structural, Spectroscopic, and Optical Findings.

PubMed

Ortiz-Quiñonez, José-Luis; Zumeta-Dubé, Inti; Díaz, David; Nava-Etzana, Noel; Cruz-Zaragoza, Epifanio; Santiago-Jacinto, Patricia

2017-03-20

Interest in nanostructured partially substituted bismuth oxides has been increasing over the last years. Research on new synthesis methods, properties, and possible uses for these oxides is needed. The objective of this paper is to synthesize β-Bi 2 O 3 , β-Bi 2 O 3 :Eu 3+ , β-Bi 2 O 3 :Mn 4+ , Bi 12 Bi 0.8 O 19.2 , Bi 12 Bi 0.8 O 19.2 /Li + , Bi 12 MnO 20 , and Bi 12 SiO 20 nanoparticles and to investigate their structural, spectroscopic, and optical changes. Some of the causes that generated their properties are also discussed. These materials are important because the doping or partial substitution of bismuth oxide with these cations (Eu 3+ , Mn 4+ , and Si 4+ ) modifies some properties such as optical absorption, reactivity toward CO 2 , among others. X-ray diffraction (in powders), high-resolution transmission electron microscopy, Fourier transform infrared (FTIR), resonance Raman scattering, diffuse reflectance, and solid-state magic-angle-spinning 29 Si NMR were used for the characterization of the synthesized materials. We found that partial substitution of yellow Bi 12 Bi 0.8 O 19.2 with Mn 4+ and Si 4+ changed the color to green and whitish, respectively. New bands in the Raman scattering and FTIR spectra of these oxides are deeply discussed. Raman scattering spectroscopy was a valuable and reliable technique to detect the Eu 3+ and Mn 4+ cations as dopants in the bismuth oxides. The 29 Si chemical shift (δ) in Bi 12 SiO 20 was -78.16 ppm, whereas in SiO 2 , it was around -110 ppm. This considerable shift in Bi 12 SiO 20 occurred because of an increased shielding of the Si nucleus in the Si(O) 4 tetrahedron. This shielding was provided by the low-electronegativity and highly polarizable Bi cations. The isovalent doping of β-Bi 2 O 3 nanoparticles with Eu 3+ enhanced their thermal stability over 400 °C. Variation in the optical absorption and reactivity toward the acidic CO 2 molecule of the partially substituted bismuth oxides was explained on the

Graphene oxide-dispersed pristine CNTs support for MnO2 nanorods as high performance supercapacitor electrodes.

PubMed

You, Bo; Li, Na; Zhu, Hongying; Zhu, Xiaolan; Yang, Jun

2013-03-01

A MnO2 -CNT-graphene oxide (MCGO) nanocomposite is fabricated using graphene oxide (GO) as a surfactant to directly disperse pristine carbon nanotubes (CNTs) for the subsequent deposition of MnO2 nanorods. The resulting MCGO nanocomposite is used as a supercapacitor electrode that shows ideal capacitive behavior (i.e., rectangular-shaped cyclic voltammograms), large specific capacitance (4.7 times higher than that of free MnO2 ) even at high mass loading (3.0 mg cm(-2) ), high energy density (30.4-14.2 Wh kg(-1) ), large power density (2.6-50.5 kW kg(-1) ), and still retains approximately 94 % of the initial specific capacitance after 1000 cycles. The advanced capacity, rate capability, and cycling stability may be attributed to the unique architecture, excellent ion wettability of GO with enriched oxygen-containing functional groups, high conductivity of CNTs, and their synergistic effects when combined with the other components. The results suggest that the MnO2 -CNT-GO hybrid nanocomposite architecture is very promising for next generation high-performance energy storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

A Raman and UV-Vis study of catecholamines oxidized with Mn(III)

NASA Astrophysics Data System (ADS)

Barreto, W. J.; Ponzoni, S.; Sassi, P.

1998-12-01

A UV-Vis and Raman spectroscopy study of three aminochromes generated through Mn 3+ oxidation of the dopamine, L-dopa and adrenaline molecules at physiological pH was performed. The UV-Vis spectra of the catecholamines oxidized using Mn 3+ in buffer solution at pH 7.2 show a band at ca. 300 nm, formed by two transitions at 280 nm and 300 nm assigned to an La and Lb transition respectively, and other at ca. 470 nm assigned to an n- π* transition localized in the carbonyl group. This assignment is suggested by the UV-Vis and Raman spectra of ortho-aminoquinone generated by MnO 2 oxidation of a dopamine aqueous acidic solution. The resonance Raman spectra of the three chromes at buffer pH 7.2 show a very similar feature and the most intense bands are observed in the spectral range 1100-1800 cm -1. The band around 1680 cm -1 for the three compounds is assigned to a ν(CO) stretching vibration, 1630 cm -1 to the ν(CC) ring mode, two bands at 1423, 1439 cm -1; 1427, 1438 cm -1 and 1456, 1475 cm -1 are assigned to a ν(CN +) vibration, for aminochrome, dopachrome and adrenochrome, respectively. The excitation profiles for the most intense bands for aminochrome and adrenochrome were obtained. The band assigned to the ν(CN +) present a red shift with respect to the visible band peak, however the band in adrenochrome at 1475 cm -1 shows a profile similar to ν(CO) and ν(CC) modes that reflects the methyl group effect on mixing this mode more effectively with the ν(CC) ring mode.

Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts.

PubMed

Morgan Chan, Zamyla; Kitchaev, Daniil A; Nelson Weker, Johanna; Schnedermann, Christoph; Lim, Kipil; Ceder, Gerbrand; Tumas, William; Toney, Michael F; Nocera, Daniel G

2018-06-05

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn 3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn 3+ may be introduced into MnO 2 by an electrochemically induced comproportionation reaction with Mn 2+ and that Mn 3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn 3+ -activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn 3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn 3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn 3+ (T d ) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO 2 polymorph incorporating Mn 3+ ions.

Electrochemical Trapping of Metastable Mn3+ Ions for Activation of MnO2 Oxygen Evolution Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tumas, William; Chan, Zamyla Morgan; Kitchaev, Daniil A.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+. We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies showmore » that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the d-MnO2 polymorph incorporating Mn3+ ions.« less

Facile Synthesis of Highly Efficient Amorphous Mn-MIL-100 Catalysts: Formation Mechanism and Structure Changes during Application in CO Oxidation.

PubMed

Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin

2018-06-21

A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts for CO oxidation. This study focused on explaining the crystalline-amorphous-crystalline transformations during thermolysis of Mn-MIL-100 and studying the structure changes during the CO oxidation reaction. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250 °C (a-Mn-250) showed a smaller specific surface area (4 m 2  g -1 ) but high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction. When a-Mn-250 was treated with reaction atmosphere at high temperature (giving used-a-Mn-250-S), the amorphous catalysts transformed into Mn 2 O 3 . Meanwhile, the BET surface area (164 m 2  g -1 ) and catalytic performance both sharply increased. In addition, used-a-Mn-250-S catalyst transformed from Mn 2 O 3 into Mn 3 O 4 , and this resulted in a slight decrease of catalytic activity in the presence of 1 vol % water vapor in the feed stream. A schematic mechanism of the structure changes during the reaction process was proposed. The success of the synthesis relies on the increase in BET surface area by using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a large quantity of surface active oxygen species, oxygen vacancies, and good low-temperature reduction behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

Quantum mechanics/molecular mechanics simulation of the ligand vibrations of the water-oxidizing Mn4CaO5 cluster in photosystem II.

PubMed

Nakamura, Shin; Noguchi, Takumi

2016-10-11

During photosynthesis, the light-driven oxidation of water performed by photosystem II (PSII) provides electrons necessary to fix CO 2 , in turn supporting life on Earth by liberating molecular oxygen. Recent high-resolution X-ray images of PSII show that the water-oxidizing center (WOC) is composed of an Mn 4 CaO 5 cluster with six carboxylate, one imidazole, and four water ligands. FTIR difference spectroscopy has shown significant structural changes of the WOC during the S-state cycle of water oxidation, especially within carboxylate groups. However, the roles that these carboxylate groups play in water oxidation as well as how they should be properly assigned in spectra are unresolved. In this study, we performed a normal mode analysis of the WOC using the quantum mechanics/molecular mechanics (QM/MM) method to simulate FTIR difference spectra on the S 1 to S 2 transition in the carboxylate stretching region. By evaluating WOC models with different oxidation and protonation states, we determined that models of high-oxidation states, Mn(III) 2 Mn(IV) 2 , satisfactorily reproduced experimental spectra from intact and Ca-depleted PSII compared with low-oxidation models. It is further suggested that the carboxylate groups bridging Ca and Mn ions within this center tune the reactivity of water ligands bound to Ca by shifting charge via their π conjugation.

Quantitative and qualitative sensing techniques for biogenic volatile organic compounds and their oxidation products.

PubMed

Kim, Saewung; Guenther, Alex; Apel, Eric

2013-07-01

The physiological production mechanisms of some of the organics in plants, commonly known as biogenic volatile organic compounds (BVOCs), have been known for more than a century. Some BVOCs are emitted to the atmosphere and play a significant role in tropospheric photochemistry especially in ozone and secondary organic aerosol (SOA) productions as a result of interplays between BVOCs and atmospheric radicals such as hydroxyl radical (OH), ozone (O3) and NOX (NO + NO2). These findings have been drawn from comprehensive analysis of numerous field and laboratory studies that have characterized the ambient distribution of BVOCs and their oxidation products, and reaction kinetics between BVOCs and atmospheric oxidants. These investigations are limited by the capacity for identifying and quantifying these compounds. This review highlights the major analytical techniques that have been used to observe BVOCs and their oxidation products such as gas chromatography, mass spectrometry with hard and soft ionization methods, and optical techniques from laser induced fluorescence (LIF) to remote sensing. In addition, we discuss how new analytical techniques can advance our understanding of BVOC photochemical processes. The principles, advantages, and drawbacks of the analytical techniques are discussed along with specific examples of how the techniques were applied in field and laboratory measurements. Since a number of thorough review papers for each specific analytical technique are available, readers are referred to these publications rather than providing thorough descriptions of each technique. Therefore, the aim of this review is for readers to grasp the advantages and disadvantages of various sensing techniques for BVOCs and their oxidation products and to provide guidance for choosing the optimal technique for a specific research task.

Characterization of sulfur oxidizing bacteria related to biogenic sulfuric acid corrosion in sludge digesters.

PubMed

Huber, Bettina; Herzog, Bastian; Drewes, Jörg E; Koch, Konrad; Müller, Elisabeth

2016-07-18

Biogenic sulfuric acid (BSA) corrosion damages sewerage and wastewater treatment facilities but is not well investigated in sludge digesters. Sulfur/sulfide oxidizing bacteria (SOB) oxidize sulfur compounds to sulfuric acid, inducing BSA corrosion. To obtain more information on BSA corrosion in sludge digesters, microbial communities from six different, BSA-damaged, digesters were analyzed using culture dependent methods and subsequent polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE). BSA production was determined in laboratory scale systems with mixed and pure cultures, and in-situ with concrete specimens from the digester headspace and sludge zones. The SOB Acidithiobacillus thiooxidans, Thiomonas intermedia, and Thiomonas perometabolis were cultivated and compared to PCR-DGGE results, revealing the presence of additional acidophilic and neutrophilic SOB. Sulfate concentrations of 10-87 mmol/L after 6-21 days of incubation (final pH 1.0-2.0) in mixed cultures, and up to 433 mmol/L after 42 days (final pH <1.0) in pure A. thiooxidans cultures showed huge sulfuric acid production potentials. Additionally, elevated sulfate concentrations in the corroded concrete of the digester headspace in contrast to the concrete of the sludge zone indicated biological sulfur/sulfide oxidation. The presence of SOB and confirmation of their sulfuric acid production under laboratory conditions reveal that these organisms might contribute to BSA corrosion within sludge digesters. Elevated sulfate concentrations on the corroded concrete wall in the digester headspace (compared to the sludge zone) further indicate biological sulfur/sulfide oxidation in-situ. For the first time, SOB presence and activity is directly relatable to BSA corrosion in sludge digesters.

Cobalt-Doped Perovskite-Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium-Oxygen Batteries.

PubMed

Liu, Xiao; Gong, Hao; Wang, Tao; Guo, Hu; Song, Li; Xia, Wei; Gao, Bin; Jiang, Zhongyi; Feng, Linfei; He, Jianping

2018-03-02

Perovskite-type oxides based on rare-earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite-type LaMnO 3 shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO 3 , the element cobalt is doped into perovskite-type LaMnO 3 through a sol-gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn 1-x Co x O 3 (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn 1-x Co x O 3 . If x=0.3, LaMn 0.7 Co 0.3 O 3 not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO 3 . Furthermore, the results demonstrate that LaMn 0.7 Co 0.3 O 3 is a promising cost-effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

2015-03-01

Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

Biogenic Aldehydes as Therapeutic Targets for Cardiovascular Disease.

PubMed

Nelson, Margaret-Ann M; Baba, Shahid P; Anderson, Ethan J

2017-04-01

Aldehydes are continuously formed in biological systems through enzyme-dependent and spontaneous oxidation of lipids, glucose, and primary amines. These highly reactive, biogenic electrophiles can become toxic via covalent modification of proteins, lipids and DNA. Thus, agents that scavenge aldehydes through conjugation have therapeutic value for a number of major cardiovascular diseases. Several commonly-prescribed drugs (e.g., hydralazine) have been shown to have potent aldehyde-conjugating properties which may contribute to their beneficial effects. Herein, we briefly describe the major sources and toxicities of biogenic aldehydes in cardiovascular system, and provide an overview of drugs that are known to have aldehyde-conjugating effects. Some compounds of phytochemical origin, and histidyl-dipeptides with emerging therapeutic value in this area are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of a large biogenic secondary organic aerosol event from eastern Canadian forests

NASA Astrophysics Data System (ADS)

Slowik, J. G.; Stroud, C.; Bottenheim, J. W.; Brickell, P. C.; Chang, R. Y.-W.; Liggio, J.; Makar, P. A.; Martin, R. V.; Moran, M. D.; Shantz, N. C.; Sjostedt, S. J.; van Donkelaar, A.; Vlasenko, A.; Wiebe, H. A.; Xia, A. G.; Zhang, J.; Leaitch, W. R.; Abbatt, J. P. D.

2010-03-01

Measurements of aerosol composition, volatile organic compounds, and CO are used to determine biogenic secondary organic aerosol (SOA) concentrations at a rural site 70 km north of Toronto. These biogenic SOA levels are many times higher than past observations and occur during a period of increasing temperatures and outflow from Northern Ontario and Quebec forests in early summer. A regional chemical transport model approximately predicts the event timing and accurately predicts the aerosol loading, identifying the precursors as monoterpene emissions from the coniferous forest. The agreement between the measured and modeled biogenic aerosol concentrations contrasts with model underpredictions for polluted regions. Correlations of the oxygenated organic aerosol mass with tracers such as CO support a secondary aerosol source and distinguish biogenic, pollution, and biomass burning periods during the field campaign. Using the Master Chemical Mechanism, it is shown that the levels of CO observed during the biogenic event are consistent with a photochemical source arising from monoterpene oxidation. The biogenic aerosol mass correlates with satellite measurements of regional aerosol optical depth, indicating that the event extends across the eastern Canadian forest. This regional event correlates with increased temperatures, indicating that temperature-dependent forest emissions can significantly affect climate through enhanced direct optical scattering and higher cloud condensation nuclei numbers.

Synthesis of α-Fe₂O₃ and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates.

PubMed

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Pellicer, Eva; Sort, Jordi

2018-02-11

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N₂ atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe₂O₃) foams are obtained from the metallic iron slurry independently of the N₂ flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N₂ flow. While the main phases for a N₂ flow rate of 180 L/h are α-Fe₂O₃ and FeMnO₃, the predominant phase for high N₂ flow rates (e.g., 650 L/h) is Fe₂MnO₄. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe₂MnO₄ foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N₂ flow rate (i.e., the amount of Fe₂MnO₄) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids.

Efficient removal of arsenic from water using a granular adsorbent: Fe-Mn binary oxide impregnated chitosan bead.

PubMed

Qi, Jianying; Zhang, Gaosheng; Li, Haining

2015-10-01

A novel sorbent of Fe-Mn binary oxide impregnated chitosan bead (FMCB) was fabricated through impregnating Fe-Mn binary oxide into chitosan matrix. The FMCB is sphere-like with a diameter of 1.6-1.8 mm, which is effective for both As(V) and As(III) sorption. The maximal sorption capacities are 39.1 and 54.2 mg/g, respectively, outperforming most of reported granular sorbents. The arsenic was mainly removed by adsorbing onto the Fe-Mn oxide component. The coexisting SO4(2-), HCO3(-) and SiO3(2-) have no great influence on arsenic sorption, whereas, the HPO4(2-) shows negative effects. The arsenic-loaded FMCB could be effectively regenerated using NaOH solution and repeatedly used. In column tests, about 1500 and 3200 bed volumes of simulated groundwater containing 233 μg/L As(V) and As(III) were respectively treated before breakthrough. These results demonstrate the superiority of the FMCB in removing As(V) and As(III), indicating that it is a promising candidate for arsenic removal from real drinking water. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparative study of biogenic and abiotic iron-containing materials

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z.; Shopska, M.; Paneva, D.; Kovacheva, D.; Kadinov, G.; Mitov, I.

2016-12-01

Series of iron-based biogenic materials prepared by cultivation of Leptothrix group of bacteria in different feeding media ( Sphaerotilus-Leptothrix group of bacteria isolation medium, Adler, Lieske and silicon-iron-glucose-peptone) were studied. Control samples were obtained in the same conditions and procedures but the nutrition media were not infected with bacteria, i.e. they were sterile. Room and low temperature Mössbauer spectroscopy, powder X-ray diffraction (XRD), and infrared spectroscopy (IRS) were used to reveal the composition and physicochemical properties of biomass and respective control samples. Comparative analysis showed differences in their composition and dispersity of present phases. Sample composition included different ratio of nanodimensional iron oxyhydroxide and oxide phases. Relaxation phenomena such as superparamagnetism or collective magnetic excitation behaviour were registered for some of them. The experimental data showed that the biogenic materials were enriched in oxyhydroxides of high dispersion. Catalytic behaviour of a selected biomass and abiotic material were studied in the reaction of CO oxidation. In situ diffuse-reflectance (DR) IRS was used to monitor the phase transformations in the biomass and CO conversion.

Practical performance and its efficiency of arsenic removal from groundwater using Fe-Mn binary oxide.

PubMed

Chang, Fangfang; Qu, Jiuhui; Liu, Ruiping; Zhao, Xu; Lei, Pengju

2010-01-01

A treatment unit packed by granular adsorbent of Fe-Mn binary oxide incorporated into diatomite (FMBO(1:1)-diatomite) was studied to remove arsenic from anaerobic groundwater without any pre-treatment or post-treatment. The raw anaerobic groundwater containing 35-45 microg/L of arsenic was collected from suburb of Beijing. Arsenic (III) constituted roughly 60%-80% of the total arsenic content. Approximately 7,000 bed volumes (ratio of effluent volume to adsorbent volume) treated water with arsenic concentration below 10 microg/L were produced in the operation period of four months. The regeneration of FMBO (1:1)-diatomite had been operated for 15 times. In the first stage, the regeneration process significantly improved the adsorption capacity of FMBO (1:1)-diatomite. With increased loading amount of Fe-Mn binary oxide, the adsorption capacity for arsenic decreased 20%-40%. Iron and manganese in anaerobic groundwater were oxidized and adsorptive filtrated by FMBO (1:1)-diatomite efficiently. The final concentrations of iron and manganese in effluents were nearly zero. The continued safe performance of the treatment units proved that adsorbent FMBO (1:1)-diatomite had high oxidation ability and exhibited strong adsorptive filtration.

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Raman studies of nanocomposites catalysts: temperature and pressure effects of CeAl, CeMn and NiAl oxides

NASA Astrophysics Data System (ADS)

da Silva, Antonio N.; Neto, Antonio B. S.; Oliveira, Alcemira C.; Junior, Manoel C.; Junior, Jose A. L.; Freire, Paulo T. C.; Filho, Josué M.; Oliveira, Alcineia C.; Lang, Rossano

2018-06-01

High temperature and pressure effects on the physicochemical properties of binary oxides catalysts were investigated. The nanocomposites catalysts comprising of CeAl, CeMn and NiAl were characterized through various physicochemical techniques. A study of the temperature and pressure induced phenomena monitored by Raman spectroscopy was proposed and discussed. Spectral modifications of the Raman modes belonging to the CeMn suggest structural changes in the solid due to the MnO2 phase oxidation with increasing temperature. The thermal expansion and lattice anharmonicity effects were observed on CeMn due to lack of stability of the lattice vacancies. The CeAl and NiAl composites presented crystallographic stability at low temperatures however, undertake a phase transformation of NiO/Al2O3 into NiAl2O4, mostly without any deformation in its structure with increasing the temperature. It was also inferred that the binary oxides are more stables in comparison with monoxides. Detailed pressure-dependent Raman measurements of the T2g phonon mode of CeMn and NiAl revealed that the pressure contributes to modify bonds length and reduces the particles sizes of the solids. On the contrary, high pressure on CeAl sample improved the stability with addition of Al2O3 in the CeO2 lattice. The results then suggest a good stability of CeAl and NiAl composite catalysts at high pressure and low temperature and show how to prospect of tuning the catalysis for surface reactions entirely through in situ spectroscopic investigations means.

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach.

PubMed

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO(2) composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO(2) nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. This journal is © The Royal Society of Chemistry 2011

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

PubMed

Neu, Heather M; Jung, Jieun; Baglia, Regina A; Siegler, Maxime A; Ohkubo, Kei; Fukuzumi, Shunichi; Goldberg, David P

2015-04-15

The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.

Conductive reduced graphene oxide/MnO2 carbonized cotton fabrics with enhanced electro -chemical, -heating, and -mechanical properties

NASA Astrophysics Data System (ADS)

Tian, Mingwei; Du, Minzhi; Qu, Lijun; Zhang, Kun; Li, Hongliang; Zhu, Shifeng; Liu, Dongdong

2016-09-01

Versatile and ductile conductive carbonized cotton fabrics decorated with reduced graphene oxide (rGO)/manganese dioxide (MnO2) are prepared in this paper. In order to endow multifunction to cotton fabric, graphene oxide (GO) is deposited on cotton fibers by simple dip-coating route. MnO2 nanoparticles are assembled on the surface of cotton fabric through in-situ chemical solution deposition. MnO2/GO@cotton fabrics are carbonized to achieve conductive fabric (MnO2/rGO@C). The morphologies and structures of obtained fabrics are characterized by SEM, XRD, ICP and element analysis, and their electro-properties including electro-chemical, electro-heating and electro-mechanical properties are evaluated. The MnO2/rGO@C yields remarkable specific capacitance of 329.4 mA h/g at the current density of 100 mA/g, which is more than 40% higher than that of the control carbonized cotton fabric (231 mA h/g). Regarding electro-heating properties, the temperature of MnO2/rGO@C fabric could be monotonically increased to the steady-state maximum temperatures (ΔTmax) of 36 °C within 5 min under the applied voltage 15 V while the ΔTmax = 17 °C of the control case. In addition, MnO2/rGO@C exhibits repeatable electro-mechanical properties and its normalized resistance (R-R0)/R0 could reach 0.78 at a constant strain (curvature = 0.6 cm-1). The MnO2/rGO@C fabric is versatile, scalable, and adaptable to a wide variety of smart textiles applications.

An intercomparison of biogenic emissions estimates from BEIS2 and BIOME: Reconciling the differences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkinson, J.G.; Emigh, R.A.; Pierce, T.E.

1996-12-31

Biogenic emissions play a critical role in urban and regional air quality. For instance, biogenic emissions contribute upwards of 76% of the daily hydrocarbon emissions in the Atlanta, Georgia airshed. The Biogenic Emissions Inventory System-Version 2.0 (BEIS2) and the Biogenic Model for Emissions (BIOME) are two models that compute biogenic emissions estimates. BEIS2 is a FORTRAN-based system, and BIOME is an ARC/INFO{reg_sign} - and SAS{reg_sign}-based system. Although the technical formulations of the models are similar, the models produce different biogenic emissions estimates for what appear to be essentially the same inputs. The goals of our study are the following: (1)more » Determine why BIOME and BEIS2 produce different emissions estimates; (2) Attempt to understand the impacts that the differences have on the emissions estimates; (3) Reconcile the differences where possible; and (4) Present a framework for the use of BEIS2 and BIOME. In this study, we used the Coastal Oxidant Assessment for Southeast Texas (COAST) biogenics data which were supplied to us courtesy of the Texas Natural Resource Conservation Commission (TNRCC), and we extracted the BEIS2 data for the same domain. We compared the emissions estimates of the two models using their respective data sets BIOME Using TNRCC data and BEIS2 using BEIS2 data.« less

Trace Elements in Manganese Minerals as Potential Biosignatures on Mars

NASA Astrophysics Data System (ADS)

Lanza, N.; Clegg, S. M.; Cousin, A.; Forni, O.; Kirk, M. F.; Lamm, S. N.; Ollila, A.; Wiens, R. C.

2017-12-01

Observations from the Curiosity rover in Gale crater, Mars have shown the presence of high abundances of manganese (>3 wt% MnO) within sedimentary rocks throughout the traverse. Such high Mn abundances point to the past presence of abundant liquid water and strongly oxidizing conditions. On Earth, these types of environments are almost always habitable and are frequently inhabited by microbes. Given its close association with life and habitable environments on Earth, manganese has long been considered a potential biosignature for Mars. However, high concentrations of martian Mn have only recently been observed. In addition to the observations in Gale crater, high abundances of Mn have also been observed in Endeavor crater by the Opportunity rover and in the paired martian meteorites NWA 7034 and 7533 (`Black Beauty'), suggesting that Mn deposits may be more widespread on Mars than previously thought. The goal of this work is to determine whether there are unique signatures from rover payload instruments that can distinguish Mn-rich deposits as biogenic in origin (i.e., produced by life) from abiogenic Mn deposits. Importantly, Mn-oxides are known to scavenge trace metals from water because of their surface charge properties. We hypothesize that the presence and abundance of specific trace elements are the critical, distinguishing evidence for identifying the biogenic origin of Mn-bearing materials. A suite of natural rocks containing Mn-rich minerals with a range of Mn redox states was selected for analysis with laser-induced breakdown spectroscopy (LIBS). Samples with a biogenic origin had mixed valence redox states between Mn3+ and Mn4+ as inferred by mineralogy. Trace elements Ba, Li, Sr, and Rb were quantified and the presence or absence of Zn and Cu was ascertained by examining key LIBS peaks. Results show that samples with a known microbial origin had moderate Mn abundances >30 wt% MnO and higher Li and Ba. These results suggest that high Mn abundance alone

Effect of Ir-Mn composition on exchange bias and thermal stability of spin valves with nano-oxide layers

NASA Astrophysics Data System (ADS)

Liu, Y. F.; Cai, J. W.; Lai, W. Y.; Yu, G. H.

2008-05-01

The Ir-Mn bottom-pinned spin valves with nano-oxide layers (NOLs), Ta /Ni81Fe19/Ir-Mn/Co90Fe10/NOL/Co90Fe10/Cu/Co90Fe10/NOL/Ta, were fabricated by dc magnetron sputtering. The magnetoresistance (MR), magnetization, and exchange bias have been studied as a function of Ir-Mn composition and annealing temperature. It was observed that the spin valves with the Ir-Mn layer containing relatively low Mn content (58.9-72.4at.% Mn) show the best thermal endurance. For these samples, the Mn diffusion is effectively hampered by the NOL with a large MR value of about 12.5% even after annealing at 300°C. On the other hand, the exchange bias field of the pinned CoFe layer shows a maximum at Mn content of about 72.4at.%, which is different from the widely adopted composition, Ir-80at.% Mn, optimized from the top-pinned NiFe /Ir-Mn system. Moreover, the blocking temperature of the Ir -Mn/CoFe system with 72.4at.% Mn is higher than that with 80.6at.% Mn. The present results suggest that the Ir -Mn/CoFe pinning system with Mn content at about 72% renders the most favorable exchange bias and the best thermal stability for the bottom-pinned specular spin valves.

Non-Metallic Ti Oxides and MnS/FeS2 Complex Precipitation in Ti-Killed Steel

NASA Astrophysics Data System (ADS)

Chen, Jieyun; Zhao, Dan; Li, Huigai; Zheng, Shaobo

Titanium deoxidized experiments can be carried in vacuum induction furnace by adding Ti-Fe alloy in molten steel to simulate strip casting. Sub-rapid solidification samples were obtained in the method of suing copper mold. The morphology, the chemical composition and the structures of nanometer precipitations were carried out to investigate by transmission electron microscope (TEM) with Energy Dispersive X ray Spectrum (EDX) and by collecting diffraction patterns with carbon extraction specimens. It has been found that titanium oxides were TiO monoclinic, Ti4O7 anorthic and TiO2 orthogonal structure in one nanometer inclusion, as the composite oxide was precipitated MnS/FeS2 cubic structure during sub-rapid solidification. Thermodynamic calculation analysis showed that it was possible to precipitate different kinds of nonstoichiometric TiOx. The solid solution between MnS/FeS2 will precipitate on the surface of titanium oxides because of good coherency relationship.

Development and assessement of the GECKO-A multiphase modelling tool for the atmospheric oxidation of biogenic organic compounds

NASA Astrophysics Data System (ADS)

Valorso, Richard; Raventos-Duran, Teresa; Aumont, Bernard; Camredon, Marie; Ng, Nga L.; Seinfeld, John H.

2010-05-01

The evaluation of the impacts of secondary organics on pollution episodes, climate and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various stages down to the ultimate oxidation products. The fully explicit representation of hydrocarbon oxidation, from the initial compounds to the final product CO2, requires a very large number of chemical reactions and intermediate species, far in excess of the number that can be reasonably written manually. We developed a "self generating approach" to explicitly describe (i) the gas phase oxidation schemes of organic compounds under general tropospheric conditions and (ii) the partitioning of secondary organics between gas and condensed phases. This approach was codified in a computer program, GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). This method allows prediction of multiphase mass budget using first principles. However, due to computational limitations, fully explicit chemical schemes can only be generated for species up to C8. We recently implemented a reduction protocol in GECKO-A to allow the generation of oxidation schemes for long chain organics. This protocol was applied to develop highly detailed oxidation schemes for biogenic compounds. The relevance of the generated schemes was assessed using experiments performed in the Caltech smog chamber for various NOx conditions. The first results show a systematic overestimation of the simulated SOA concentrations by GECKO-A. Several hypotheses were tested to find the origin of the discrepancies beetwen model and measurements.

Manganese Porphyrin, MnTE-2-PyP5+, Acts as a Pro-Oxidant to Potentiate Glucocorticoid-Induced Apoptosis in Lymphoma Cells

PubMed Central

Jaramillo, Melba C.; Briehl, Margaret M.; Crapo, James D.; Haberle, Ines Batinic; Tome, Margaret E.

2012-01-01

Using current chemotherapy protocols, over 55% of lymphoma patients fail treatment. Novel agents are needed to improve lymphoma survival. The manganese porphyrin, MnTE-2-PyP5+, augments glucocorticoid-induced apoptosis in WEHI7.2 murine thymic lymphoma cells, suggesting that it may have potential as a lymphoma therapeutic. However, the mechanism by which MnTE-2-PyP5+ potentiates glucocorticoid-induced apoptosis is unknown. Previously, we showed that glucocorticoid treatment increases the steady state levels of hydrogen peroxide ([H2O2]ss) and oxidizes the redox environment in WEHI7.2 cells. In the current study, we found that when MnTE-2-PyP5+ is combined with glucocorticoids, it augments dexamethasone-induced oxidative stress however, it does not augment the [H2O2]ss levels. The combined treatment depletes GSH, oxidizes the 2GSH:GSSG ratio, and causes protein glutathionylation to a greater extent than glucocorticoid treatment alone. Removal of the glucocorticoid-generated H2O2 or depletion of glutathione by BSO prevents MnTE-2-PyP5+ from augmenting glucocorticoid-induced apoptosis. In combination with glucocorticoids, MnTE-2-PyP5+ glutathionylates p65 NF-κB and inhibits NF-κB activity. Inhibition of NF-κB with SN50, an NF-κB inhibitor, enhances glucocorticoid-induced apoptosis to the same extent as MnTE-2-PyP5+. Taken together, these findings indicate that: 1) H2O2 is important for MnTE-2-PyP5+ activity; 2) Mn-TE-2-PyP5+ cycles with GSH; and 3) MnTE-2-PyP5+ potentiates glucocorticoid-induced apoptosis by glutathionylating and inhibiting critical survival proteins, including NF-κB. In the clinic, over-expression of NF-κB is associated with a poor prognosis in lymphoma. MnTE-2-PyP5+ may therefore, synergize with glucocorticoids to inhibit NF-κB and improve current treatment. PMID:22330065

A search for biogenic trace gases in the atmosphere of Mars

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Mckay, Christopher P.

1989-01-01

The detection of certain trace gases in the atmosphere of Mars may serve as a possible indicator of microbial life on the surface of Mars. Candidate biogenic gases include methane CH4, ammonia NH3, nitrous oxide N2O, and several reduced sulfur species. Chemical thermodynamic equilibrium and photochemical calculations preclude the presence of these gases in any measurable concentrations in the atmosphere of Mars in the absence of biogenic production. A search for these gases utilizing either high resolution (spectral and spatial) spectroscopy from a Mars orbiter, such as the Observer, and or in situ measurements from a Mars lander or rover, is proposed.

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0-9.0), temperature (5-45°C), and ionic strength (0-4 M). The overall rate constant, k, in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: - d[H 2S] T/dt = k[H 2S] τ[MnO 2] . The rate constant, k, for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M -1 min -1, or 0.0244 m -2 1 min -1 when [MnO 2] is expressed in surface area (m 2/L). The energies of activation were found to be 14 ± 1 KJ mol -1 and 10 ± 1 KJ mol -1, respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO - and H 2S. As the concentration of HS - increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na +, Mg 2+, Ca 2+, Cl -, and SO 2-4) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

Evolution of Oxide Inclusions in Si-Mn Killed Steels During Hot-Rolling Process

NASA Astrophysics Data System (ADS)

Yang, Wen; Guo, Changbo; Zhang, Lifeng; Ling, Haitao; Li, Chao

2017-10-01

The evolution of oxide inclusions in Si-Mn killed steels refined by slags of different basicity during a four-pass industrial hot-rolling process was investigated using an automated microscopy system. High-basicity refining slag induced the formation of CaO- and Al2O3-containing inclusions, while refining slag with 0.8 basicity induced dominant inclusions of SiO2 and MnO-SiO2. CaO-SiO2-Al2O3 inclusions mainly formed endogenously during solidification and cooling of Ca-containing steels, where Ca originated from slag-steel reactions. However, the larger-sized higher-CaO inclusions originated from slag entrainment. Different inclusions presented different hot-rolling behaviors. The inclusion composition changed by deformation and new phase formation. The dominant oxide types were unchanged under refinement by low-basicity slag; however, they changed under refinement with high-basicity slag. The deformation index of inclusions decreased with increasing accumulated reduction (AR) of the steel. The difference in deformation index between different inclusion types was the largest in the first rolling stage and decreased in subsequent stages. SiO2-CaO and SiO2-MnO-CaO inclusions had larger deformation indices during hot rolling but smaller indices in the last two stages. High-basicity slag increased inclusion complexity; from the perspective of cold-drawing performance, low-basicity refining slag is better for the industrial production of tire-cord steels.

DNA@Mn3(PO4)2 Nanoparticles Supported with Graphene Oxide as Photoelectrodes for Photoeletrocatalysis

NASA Astrophysics Data System (ADS)

Gao, Lixia; Xie, Jiale; Ma, Xiaoqing; Li, Man; Yu, Ling

2017-01-01

A novel deoxyribose nucleic acid (DNA)-based photoelectrode consisting of DNA@Mn3(PO4)2 nanoparticles on graphene oxide (GO) sheets was successfully fabricated for photoelectrocatalysis. DNA served as a soft template to guide the nucleation and growth of Mn3(PO4)2 nanoparticles in the synthesis of Mn3(PO4)2 nanoparticles. More importantly, the DNA also serves as semiconductor materials to adjust charge transport. Under UV light irradiation (180-420 nm, 15 mW/cm2), the photocurrent density of DNA@ Mn3(PO4)2/GO electrodes reached 9 μA/cm2 at 0.7 V bias (vs. SCE). An applied bias photon-to-current efficiency (ABPE) of 0.18% can be achieved, which was much higher than that of other control electrodes (<0.04%). In this DNA-based photoelectrode, well-matched energy levels can efficiently improve charge transfer and reduce the recombination of photogenerated electron-hole pairs.

Late-Quaternary changes of biogenic fluxes in the pacific sector of the Southern Ocean

NASA Astrophysics Data System (ADS)

Giglio, F.; Langone, L.; Capotondi, L.; Morigi, C.; Focaccia, P.; Frignani, M.; Ravaioli, M.

2003-04-01

During the last decade the research project BIOSESO of the Italian National Research Program for Antarctica (PNRA) has collected 13 gravity cores and 3 box-cores along a N-S transect at about 175^oE in the Southern Ocean. In this presentation we discuss the results from 6 sediment cores sampled between 62^oS and 71^oS. This area embraces the Polar Front and the Marginal Ice Zone. The data set includes the contents of organic carbon, biogenic silica, CaCO_3 and some metals (Ba, Al, Fe, Mn) involved in the biogeochemical cycles. Chronologies were based on 230Thex profiles and the boundaries of the isotope stages were set assuming that biological productivity was enhanced during periods of less ice cover. Then , 230Thex, organic carbon, biogenic silica and biogenic Ba distributions were compared to the glacial-interglacial stage boundaries and corresponding ages of the δ18O record of Martinson et al. (1987). At the sampling sites sediment accumulation rates range between 0.2 to 3.8 cm ka-1. The higher values characterize the interglacial stages and the southern stations. Processes of sediment redistribution at sea bottom were enlightened by a comparison of measured and expected fluxes of 230Thex . The Polar Front zone is characterized by winnowing, whereas sediments along the continental slope of the Ross Sea are mainly subject to focussing processes. The environmental factors that drive changes of biogenic particle fluxes during glacial-interglacial transitions have been investigated.

What spectroscopy reveals concerning the Mn oxidation levels in the oxygen evolving complex of photosystem II: X-ray to near infra-red.

PubMed

Pace, Ron J; Jin, Lu; Stranger, Rob

2012-08-28

Photosystem II (PS II), found in oxygenic photosynthetic organisms, catalyses the most energetically demanding reaction in nature, the oxidation of water to molecular oxygen and protons. The water oxidase in PS II contains a Mn(4)Ca cluster (oxygen evolving complex, OEC), whose catalytic mechanism has been extensively investigated but is still unresolved. In particular the precise Mn oxidation levels through which the cluster cycles during functional turnover are still contentious. In this, the first of several planned parts, we examine a broad range of published data relating to this question, while considering the recent atomic resolution PS II crystal structure of Umena et al. (Nature, 2011, 473, 55). Results from X-ray, UV-Vis and NIR spectroscopies are considered, using an approach that is mainly empirical, by comparison with published data from known model systems, but with some reliance on computational or other theoretical considerations. The intention is to survey the extent to which these data yield a consistent picture of the Mn oxidation states in functional PS II - in particular, to test their consistency with two current proposals for the mean redox levels of the OEC during turnover; the so called 'high' and 'low' oxidation state paradigms. These systematically differ by two oxidation equivalents throughout the redox accumulating catalytic S state cycle (states S(0)···S(3)). In summary, we find that the data, in total, substantially favor the low oxidation proposal, particularly as a result of the new analyses we present. The low oxidation state scheme is able to resolve a number of previously 'anomalous' results in the observed UV-Visible S state turnover spectral differences and in the resonant inelastic X-ray spectroscopy (RIXS) of the Mn pre-edge region of the S(1) and S(2) states. Further, the low oxidation paradigm is able to provide a 'natural' explanation for the known sensitivity of the OEC Mn cluster to cryogenic near infra-red (NIR

Mn K-Edge XANES and Kβ XES Studies of Two Mn–Oxo Binuclear Complexes: Investigation of Three Different Oxidation States Relevant to the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Visser, Hendrik; Anxolabéhère-Mallart, Elodie; Bergmann, Uwe; Glatzel, Pieter; Robblee, John H.; Cramer, Stephen P.; Girerd, Jean-Jacques; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono

Thermodynamic Evaluation and Optimization of the MnO-B2O3 and MnO-B2O3-SiO2 Systems and Its Application to Oxidation of High-Strength Steels Containing Boron

NASA Astrophysics Data System (ADS)

Kim, Young-Min; Jung, In-Ho

2015-06-01

A complete literature review, critical evaluation, and thermodynamic optimization of phase equilibrium and thermodynamic properties of all available oxide phases in the MnO-B2O3 and MnO-B2O3-SiO2 systems at 1 bar pressure are presented. Due to the lack of the experimental data in these systems, the systematic trend of CaO- and MgO-containing systems were taken into account in the optimization. The molten oxide phase is described by the Modified Quasichemical Model. A set of optimized model parameters of all phases is obtained which reproduces all available and reliable thermodynamic and phase equilibrium data. The unexplored binary and ternary phase diagrams of the MnO-B2O3 and MnO-B2O3-SiO2 systems have been predicted for the first time. The thermodynamic calculations relevant to the oxidation of advanced high-strength steels containing boron were performed to find that B can form liquid B2O3-SiO2-rich phase in the annealing furnace under reducing N2-H2 atmosphere, which can significantly influence the wetting behavior of liquid Zn in Zn galvanizing process.

Biogenic nitric oxide emission from a spruce forest soil in mountainous terrain

NASA Astrophysics Data System (ADS)

Falge, Eva; Bargsten, Anika; Behrendt, Thomas; Meixner, Franz X.

2010-05-01

The process-based spatial simulation model SVAT-CN was used to estimate biogenic nitric oxide (NO) emission by soils of a Norway spruce forest (Weidenbrunnen) in the Fichtelgebirge, Germany. SVAT-CN core is a combination of a multiple-layer soil water balance model and a multi-layered canopy gas exchange model. The soil modules comprise a flexible hybrid between a layered bucket model and classical basic liquid flow theory. Further soil processes include: heat transport, distribution of transpiration demand proportionally to soil resistance, reduction of leaf physiological parameters with limiting soil moisture. Spruce forest soils usually are characterized by a thick organic layer (raw humus), with the topmost centimetres being the location where most of the biogenic NO is produced. Within individual spruce forest stands the understory might be composed of patches characterized by different species (e.g. Vaccinium myrtillus, Picea abies, Deschampsia caespitosa), and NO production potentials. The effect of soil physical and chemical parameters and understory types on NO emission from the organic layer was investigated in laboratory incubation and fumigation experiments on soils sampled below the various understory covers found at the Weidenbrunnen site. Results from the laboratory experiments were used to parameterize multi-factorial regression models of soil NO emission with respect to its response to soil temperature and moisture. Parameterization of the spatial model SVAT-CN includes horizontal heterogeneity of over- and understory PAI, understory species distribution, soil texture, bulk density, thickness of organic layer. Simulations are run for intensive observations periods of 2007 and 2008 of the EGER (ExchanGE processes in mountainous Regions) project, a late summer/fall and an early summer period, providing estimates for different understory types (young spruce, blueberry, grass, and moss/litter patches). Validation of the model is being carried out at

Sorption of arsenic to biogenic iron (oxyhydr)oxides produced in circumneutral environments

NASA Astrophysics Data System (ADS)

Sowers, Tyler D.; Harrington, James M.; Polizzotto, Matthew L.; Duckworth, Owen W.

2017-02-01

Arsenic (As) is a widespread and problematic pollutant that can be derived from natural or anthropogenic sources. Iron (oxyhydr)oxides readily sorb As and thus play critical roles in As cycling in terrestrial environments; however, little is known about the affinity and mechanism of As sorption by biogenic iron (oxyhydr)oxides formed in circumneutral environments. To investigate this, we conducted sorption isotherm and kinetics experiments to compare As(V) and As(III) sorption to synthetic 2-line ferrihydrite and iron biominerals harvested from the hyporheic zone of an uncontaminated creek. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify both As(V) and As(III), and X-ray absorption spectroscopy (XAS) was utilized to obtain As and Fe K-edge spectra for As(V) and As(III) sorbed to environmentally collected and laboratory produced Fe(III) minerals. All environmental Fe(III) biominerals were determined to be structurally similar to 2-line ferrihydrite. However, environmental Fe(III) biominerals have a surface area normalized affinity for As(V) and for As(III) that is greater than or equivalent to synthetic 2-line ferrihydrite. Whereas the extent of sorption was similar for As(III) on all minerals, As(V) sorption to environmental Fe(III) biominerals was approximately three times higher than what was observed for synthetic 2-line ferrihydrite. Structural modeling of EXAFS spectra revealed that the same surface complexation structure was formed by As(V) and by As(III) on environmental Fe(III) biominerals and ferrihydrite. These results suggest that, despite similarities in binding mechanisms, Fe(III) biominerals may be more reactive sorbents that synthetic surrogates often used to model environmental reactivity.

Pure MnTBAP selectively scavenges peroxynitrite over superoxide: Comparison of pure and commercial MnTBAP samples to MnTE-2-PyP in two different models of oxidative stress injuries, SOD-specific E. coli model and carrageenan-induced pleurisy

PubMed Central

Batinić-Haberle, Ines; Cuzzocrea, Salvatore; Rebouças, Júlio S.; Ferrer-Sueta, Gerardo; Mazzon, Emanuela; Di Paola, Rosanna; Radi, Rafael; Spasojević, Ivan; Benov, Ludmil; Salvemini, Daniela

2009-01-01

MnTBAP is often referred to as an SOD mimic in numerous models of oxidative stress. We have recently reported that pure MnTBAP does not dismute superoxide, but commercial/ill-purified samples are able to perform O2•− dismutation with low-to-moderate efficacy via non-innocent Mn-containing impurities. Herein, we show that neither commercial nor pure MnTBAP could substitute for SOD enzyme in the SOD-deficient E. coli model, while MnTE-2-PyP-treated SOD-deficient E. coli grew as well as wild-type strain. This SOD-specific system indicates that MnTBAP does not act as an SOD mimic in vivo. In another model, carrageenan-induced pleurisy in mice, inflammation was evidenced by increased pleural fluid exudate, and neutrophil infiltration and activation: these events were blocked by 0.3 mg/kg of MnTE-2-PyP and to a slightly lesser extent with 10 mg/kg of MnTBAP. Also, 3-nitrotyrosine formation, an indication of the peroxynitrite existence in vivo, was blocked by both compounds; again MnTE-2-PyP was 33-fold more effective. Pleurisy model data indicate that MnTBAP exert some protective actions in common with MnTE-2-PyP, which are not O2•−-related, and can be fully rationalized if one considers that the common biological role shared by MnTBAP and MnTE-2-PyP is related to their reduction of peroxynitrite and carbonate radical, the latter arising from ONOO− adduct with CO2. The log kcat (O2•−) value for MnTBAP is estimated to be about 3.16, which is ~5 and ~7 orders of magnitude smaller than the SOD activity of the potent SOD mimic MnTE-2-PyP and Cu, Zn-SOD, respectively. This very low value indicates that MnTBAP is very inefficient in dismuting superoxide to be of any biological impact, which was confirmed in the SOD-deficient E. coli model. Peroxynitrite scavenging ability of MnTBAP, however, is only ~2.5 orders of magnitude smaller than that of MnTE-2-PyP and is not significantly affected by the presence of the SOD-active impurities in commercial MnTBAP sample

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation

DOE PAGES

Charnawskas, Joseph C.; Alpert, Peter A.; Lambe, Andrew; ...

2017-01-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil-fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles’ organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without presence of sulfate or soot particles. Corresponding particle glass transition (T g) and full deliquescence relative humidity (FDRH) were estimated by a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibitmore » a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid inducing ice nucleation. Naphthalene SOA coated soot particles acted as IN above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate further renders this even less likely. Furthermore, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during preindustrial times or in pristine areas.« less

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

PubMed

Charnawskas, Joseph C; Alpert, Peter A; Lambe, Andrew T; Berkemeier, Thomas; O'Brien, Rachel E; Massoli, Paola; Onasch, Timothy B; Shiraiwa, Manabu; Moffet, Ryan C; Gilles, Mary K; Davidovits, Paul; Worsnop, Douglas R; Knopf, Daniel A

2017-08-24

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (T g ) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective T g and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.