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Sample records for biogenic mn oxides

  1. Biogenic Mn-Oxides in Subseafloor Basalts

    PubMed Central

    Ivarsson, Magnus; Broman, Curt; Gustafsson, Håkan; Holm, Nils G.

    2015-01-01

    The deep biosphere of the subseafloor basalts is recognized as a major scientific frontier in disciplines like biology, geology, and oceanography. Recently, the presence of fungi in these environments has involved a change of view regarding diversity and ecology. Here, we describe fossilized fungal communities in vugs in subseafloor basalts from a depth of 936.65 metres below seafloor at the Detroit Seamount, Pacific Ocean. These fungal communities are closely associated with botryoidal Mn oxides composed of todorokite. Analyses of the Mn oxides by Electron Paramagnetic Resonance spectroscopy (EPR) indicate a biogenic signature. We suggest, based on mineralogical, morphological and EPR data, a biological origin of the botryoidal Mn oxides. Our results show that fungi are involved in Mn cycling at great depths in the seafloor and we introduce EPR as a means to easily identify biogenic Mn oxides in these environments. PMID:26107948

  2. Formation of Nano-crystalline Todorokite from Biogenic Mn Oxides

    SciTech Connect

    Feng, X.; Zhu, M; Ginder-Vogel, M; Ni, C; Parikh, S; Sparks, D

    2010-01-01

    Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO{sub 6} octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite ({delta}-MnO{sub 2}), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c* axis and a lack of c* periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide {yields} 10-{angstrom} triclinic phyllomanganate {yields} todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.

  3. Formation of nano-crystalline todorokite from biogenic Mn oxides

    NASA Astrophysics Data System (ADS)

    Feng, Xiong Han; Zhu, Mengqiang; Ginder-Vogel, Matthew; Ni, Chaoying; Parikh, Sanjai J.; Sparks, Donald L.

    2010-06-01

    Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO 6 octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite (δ-MnO 2), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c∗ axis and a lack of c∗ periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide → 10-Å triclinic phyllomanganate → todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.

  4. Coupled biotic-abiotic Mn(II) oxidation pathway mediates the formation and structural evolution of biogenic Mn oxides

    NASA Astrophysics Data System (ADS)

    Learman, D. R.; Wankel, S. D.; Webb, S. M.; Martinez, N.; Madden, A. S.; Hansel, C. M.

    2011-10-01

    Manganese (Mn) oxides are among the strongest oxidants and sorbents in the environment, impacting the transport and speciation of metals, cycling of carbon, and flow of electrons within soils and sediments. The oxidation of Mn(II) to Mn(III/IV) oxides has been primarily attributed to biological processes, due in part to the faster rates of bacterial Mn(II) oxidation compared to observed mineral-induced and other abiotic rates. Here we explore the reactivity of biogenic Mn oxides formed by a common marine bacterium ( Roseobacter sp. AzwK-3b), which has been previously shown to oxidize Mn(II) via the production of extracellular superoxide. Oxidation of Mn(II) by superoxide results in the formation of highly reactive colloidal birnessite with hexagonal symmetry. The colloidal oxides induce the rapid oxidation of Mn(II), with dramatically accelerated rates in the presence of organics, presumably due to mineral surface-catalyzed organic radical generation. Mn(II) oxidation by the colloids is further accelerated in presence of both organics and light, implicating reactive oxygen species in aiding abiotic oxidation. Indeed, the enhancement of Mn(II) oxidation is negated when the colloids are reacted with Mn(II) in the presence of superoxide dismutase, an enzyme that scavenges the reactive oxygen species (ROS) superoxide. The reactivity of the colloidal phase is short-lived due to the rapid evolution of the birnessite from hexagonal to pseudo-orthogonal symmetry. The secondary particulate triclinic birnessite phase exhibits a distinct lack of Mn(II) oxidation and subsequent Mn oxide formation. Thus, the evolution of initial reactive hexagonal birnessite to non-reactive triclinic birnessite imposes the need for continuous production of new colloidal hexagonal particles for Mn(II) oxidation to be sustained, illustrating an intimate dependency of enzymatic and mineral-based reactions in Mn(II) oxidation. Further, the coupled enzymatic and mineral-induced pathways are linked

  5. Sorption of Ferrioxime B to Synthetic and Biogenic layer type Mn Oxides

    NASA Astrophysics Data System (ADS)

    Duckworth, O. W.; Bargar, J. R.; Sposito, G.

    2005-12-01

    Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effect of solid-phase Mn(IV), we studied the sorption reaction of ferrioxamine B [principally the species, Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore, desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over the pH range between 5 and 9. After 72 h equilibration time at pH 8, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-Ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the X-ray absorption spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed with DFOB, but instead is incorporated into the mineral structure, thus implying that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron.

  6. The role of biogenic Fe-Mn oxides formed in situ for arsenic oxidation and adsorption in aquatic ecosystems.

    PubMed

    Bai, Yaohui; Yang, Tingting; Liang, Jinsong; Qu, Jiuhui

    2016-07-01

    As(III&V), Mn(II), and Fe(II) may occur simultaneously in some groundwater and surface water. Studying their redox reactions and interactions is essential to unravel the biogeochemical cycles of these metal ions in aquatic ecosystems and to find effective methods to remove them simultaneously in drinking water treatment. Here, the formation of biogenic Fe-Mn oxides (BFMO, defined as a mixture of biogenic Mn oxide (BMO) and Fe oxide) as well as its oxidation and adsorption of As in a Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe (Pseudomonas sp. QJX-1) system were investigated. Batch experiments and structure characterization revealed that the BFMO was formed via a sequential precipitation of Fe oxide and BMO. The first formed Fe oxide was identified as FeOOH (lepidocrocite) and the latter formed BMO was identified as MnO2 (similar to hexagonal birnessite). In the BFMO mixture, the BMO part was mainly responsible for As(III) oxidation, and the Fe oxide part dominated As adsorption. Remarkably, the BMO could oxidize Fe(II) to form FeOOH, which may improve As adsorption. The optimum Mn(II)/Fe(II) ratio for As removal was approximately 1:3 (mol/mol). Taken together, in Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe ecosystems, the in situ formation of BFMO could eliminate or decrease Fe(II), Mn(II), and As(III&V) species simultaneously. Therefore, based on this study, new approaches may be developed for As removal from water containing high concentrations of Fe(II) and Mn(II).

  7. Removal of multi-heavy metals using biogenic manganese oxides generated by a deep-sea sedimentary bacterium - Brachybacterium sp. strain Mn32.

    PubMed

    Wang, Wenming; Shao, Zongze; Liu, Yanjun; Wang, Gejiao

    2009-06-01

    A deep-sea manganese-oxidizing bacterium, Brachybacterium sp. strain Mn32, showed high Mn(II) resistance (MIC 55 mM) and Mn(II)-oxidizing/removing abilities. Strain Mn32 removed Mn(II) by two pathways: (1) oxidizing soluble Mn(II) to insoluble biogenic Mn oxides - birnessite (delta-MnO(2) group) and manganite (gamma-MnOOH); (2) the biogenic Mn oxides further adsorb more Mn(II) from the culture. The generated biogenic Mn oxides surround the cell surfaces of strain Mn32 and provide a high capacity to adsorb Zn(II) and Ni(II). Mn(II) oxidation by strain Mn32 was inhibited by both sodium azide and o-phenanthroline, suggesting the involvement of a metalloenzyme which was induced by Mn(II). X-ray diffraction analysis showed that the crystal structures of the biogenic Mn oxides were different from those of commercial pyrolusite (beta-MnO(2) group) and fresh chemically synthesized vernadite (delta-MnO(2) group). The biogenic Mn oxides generated by strain Mn32 showed two to three times higher Zn(II) and Ni(II) adsorption abilities than commercial and fresh synthetic MnO(2). The crystal structure and the biogenic MnO(2) types may be important factors for the high heavy metal adsorption ability of strain Mn32. This study provides potential applications of a new marine Mn(II)-oxidizing bacterium in heavy metal bioremediation and increases our basic knowledge of microbial manganese oxidation mechanisms.

  8. Production of biogenic Mn oxides by Leptothrix discophora SS-1 in a chemically defined growth medium and evaluation of their Pb adsorption characteristics

    SciTech Connect

    Nelson, Y.M.; Lion, L.W.; Ghiorse, W.C.; Shuler, M.L.

    1999-01-01

    Biogenic Mn oxides were produced by the bacterium Leptothrix discophora SS-1 (= ATCC 3182) in a chemically defined mineral salts medium, and the Pb binding and specific surface area of these oxides were characterized. Growth of SS-1 in the defined medium with pyruvate as a carbon and energy source required the addition of vitamin B{sub 12}. Complete oxidation of Mn(II) within 60 h required the addition of {ge}0.1 {micro}M FeSO{sub 4}. Pb adsorption isotherms were determined for the biogenic Mn oxides (and associated cells with their extracellular polymer) and compared to the Pb adsorption isotherms of cells and exopolymer alone, as well as to abiotic Mn oxides. The Pb adsorption to cells and exopolymer with biogenic Mn oxides at pH 6.0 and 25 C was 2 orders of magnitude greater than the Pb adsorption to cells and exopolymer alone. The Pb adsorption to the biogenic Mn oxide was two to five times greater than the Pb adsorption to a chemically precipitated abiotic Mn oxide and several orders of magnitude greater than the Pb adsorption to two commercially available crystalline MnO{sub 2} minerals. The N{sub 2} Brunauer-Emmet-Teller specific surface areas of the biogenic Mn oxide and fresh Mn oxide precipitate were significantly greater than those of the commercial Mn oxide minerals. The Pb adsorption capacity of the biogenic Mn oxide also exceeded that of a chemically precipitated colloidal hydrous Fe oxide under similar solution conditions. These results show that amorphous biogenic Mn oxides similar to those produced by SS-1 may play a significant rule in the control of trace metal phase distribution in aquatic systems.

  9. A specific Ce oxidation process during sorption of rare earth elements on biogenic Mn oxide produced by Acremonium sp. strain KR21-2

    NASA Astrophysics Data System (ADS)

    Tanaka, Kazuya; Tani, Yukinori; Takahashi, Yoshio; Tanimizu, Masaharu; Suzuki, Yoshinori; Kozai, Naofumi; Ohnuki, Toshihiko

    2010-10-01

    Sorption of rare earth elements (REEs) and Ce oxidation on natural and synthetic Mn oxides have been investigated by many researchers. Although Mn(II)-oxidizing microorganisms are thought to play an important role in the formation of Mn oxides in most natural environments, Ce oxidation by biogenic Mn oxide and the relevance of microorganisms to the Ce oxidation process have not been well understood. Therefore, in this study, we conducted sorption experiments of REEs on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. The distribution coefficients, Kd(REE), between biogenic Mn oxide (plus hyphae) and 10 mmol/L NaCl solution showed a large positive Ce anomaly and convex tetrad effect variations at pH 3.8, which was consistent with previous works using synthetic Mn oxide. The positive Ce anomaly was caused by oxidation of Ce(III) to Ce(IV) by the biogenic Mn oxide, which was confirmed by analysis of the Ce L III-edge XANES spectra. With increasing pH, the positive Ce anomaly and convex tetrad effects became less pronounced. Furthermore, negative Ce anomalies were observed at a pH of more than 6.5, suggesting that Ce(IV) was stabilized in the solution (<0.2 μm) phase, although Ce(III) oxidation to Ce(IV) on the biogenic Mn oxide was confirmed by XANES analysis. It was demonstrated that no Ce(III) oxidation occurred during sorption on the hyphae of strain KR21-2 by the Kd(REE) patterns and XANES analysis. The analysis of size exclusion HPLC-ICP-MS showed that some fractions of REEs in the filtrates (<0.2 μm) after sorption experiments were bound to organic molecules (40 and <670 kDa fractions), which were possibly released from hyphae. A line of our data indicates that the negative Ce anomalies under circumneutral pH conditions arose from Ce(III) oxidation on the biogenic Mn oxide and subsequent complexation of Ce(IV) with organic ligands. The suppression of tetrad effects is also explained by the complexation of REEs with organic ligands. The results of

  10. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    NASA Astrophysics Data System (ADS)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

  11. Characterization and reactivity of biogenic manganese oxides for ciprofloxacin oxidation.

    PubMed

    Tu, Jinjun; Yang, Zhendong; Hu, Chun; Qu, Jiuhui

    2014-05-01

    Biogenic manganese oxides (BioMnOx) were synthesized by the oxidation of Mn(II) with Mn-oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn(II) dosages, and were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The crystal structure and Mn oxidation states of BioMnOx depended on the initial pH and Mn(II) dosages of the medium. The superoxide radical (O(·-)2) was observed in Mn-containing (III/IV) BioMnOx suspensions by electron spin resonance measurements. BioMnOx(0.4)-7, with mixed valence of Mn(II/III/IV) and the strongest O(·-)2 signals, was prepared in the initial pH 7 and Mn(II) dosage of 0.4 mmol/L condition, and exhibited the highest activity for ciprofloxacin degradation and no Mn(II) release. During the degradation of ciprofloxacin, the oxidation of the Mn(II) formed came from biotic and abiotic reactions in BioMnOx suspensions on the basis of the Mn(II) release and O(·-)2 formation from different BioMnOx. The degradation process of ciprofloxacin was shown to involve the cleavage of the hexatomic ring having a secondary amine and carbon-carbon double bond connected to a carboxyl group, producing several compounds containing amine groups as well as small organic acids.

  12. Effect of Mn(II) on the structure and reactivity of biogenic uraninite.

    PubMed

    Veeramani, Harish; Schofield, Eleanor J; Sharp, Jonathan O; Suvorova, Elena I; Ulrich, Kai-Uwe; Mehta, Apurva; Giammar, Daniel E; Bargar, John R; Bernier-Latmanit, Rizlan

    2009-09-01

    The efficacy of a site remediation strategy involving the stimulaton of microbial U(VI) reduction hinges in part upon the long-term stability of the product, biogenic uraninite, toward environmental oxidants. Geological sedimentary uraninites (nominal formula UO2) reportedly contain abundant cation impurities that enhance their resistance to oxidation. By analogy, incorporation of common groundwater solutes into biogenic uraninite could also impart stability-enhancing properties. Mn(II) is a common groundwater cation, which has a favorable ionic radiusfor substitution reactions. The structure and reactivity of Mn(II)-reacted biogenic uraninite are investigated in this study. Up to 4.4 weight percent Mn(II) was found to be structurally bound in biogenic uraninite. This Mn(II) incorporation was associated with decreasing uraninite particle size and structural order. Importantly, the equilibrium solubility of Mn-reacted uraninite was halved relative to unreacted uraninite, demonstrating changes in thermodynamic properties, while the dissolution rate was up to 38-fold lower than that of unreacted biogenic uraninite. We conclude that structuralincorporation of Mn(II) into uraninite has an important stabilizing effect leading to the prediction that other groundwater solutes may similarly stabilize biogenic uraninite.

  13. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    SciTech Connect

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  14. Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

  15. Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

  16. [Formation and reactions of biogenic manganese oxides with heavy metals in environment].

    PubMed

    Meng, You-Ting; Zheng, Yuan-Ming; Zhang, Li-Mei; He, Ji-Zheng

    2009-02-15

    Manganese (Mn) oxides are common minerals in natural environments that may play an important role in the biogeochemical cycles of heavy metals. Increasing evidences have shown that Mn (II) oxidation is a microbially-mediated process, and the Mn oxidizing microorganisms are thus recognized as the major drivers of the global Mn cycle. The major pathway for bacterial Mn (II) oxidation is catalysed by a multicopper oxidizing enzyme family. The primary Mn (IV) biooxides are phyllomanganate-like minerals most similar to delta-MnO2 or acid birnessite. Manganese oxides are known to have high sorption capacities for a wide variety of metal ions and considered to be the important environmental oxidant to many metal ions. This paper reviewed the mechanisms of biogenic manganese oxides formation and their reactions with heavy metal ions in environment.

  17. Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH

    NASA Astrophysics Data System (ADS)

    Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

    2014-05-01

    The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (δ-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in

  18. Biogenic Methane from Coal: The Oxidation Factor

    NASA Astrophysics Data System (ADS)

    Gallagher, L. K.; Glossner, A. W.; Landkamer, L.; Figueroa, L. A.; Mandernack, K. W.; Munakata Marr, J.

    2011-12-01

    Vast reserves of coal represent an untapped resource that can be used to produce methane gas, a cleaner energy alternative compared to standard fossil fuels. Microorganisms have demonstrated the ability to utilize coal as a carbon source, producing biogenic methane. With increasing demand for cleaner energy resources, understanding and enhancing biogenic methane production has become an area of active research. The conversion of coal to methane by microorganisms has been demonstrated experimentally by a number of research groups, but the state of the coal used as a substrate has not always been reported and may impact biogenic methane production. Microcosm experiments were designed in order to assess how the oxidation state of coal might influence methane production (e.g. as in a dewatered coal-bed natural gas system). Oxidized and un-oxidized coal samples from the Powder River Basin were incubated in microcosms inoculated with an enrichment culture that was derived from coal. Microcosms were characterized by headspace gas analysis, organic acid production, functional gene abundance (qPCR), and pyrosequencing of the 16S rRNA gene. Although the microbial consortium demonstrated the ability to utilize both oxidized and un-oxidized coal as a sole carbon source to generate methane, it was produced in higher quantities from the un-oxidized coal. This microbial community was dominated by Methanobacteriaceae (45%), epsilon-Proteobacteria (32%) and delta-Proteobacteria (13%). The results of this study provide a basis to develop strategies to enhance biogenic methane production from coal, as well as demonstrate the need for careful substrate preparation for inter-study comparisons.

  19. Sorption of Ferric Iron from Ferrioxamine B to Synthetic and Biogenic Layer Type Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Duckworth, O.; John, B.; Sposito, G.

    2006-12-01

    Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effects of predominantly Mn(IV) oxides, we studied the sorption reaction of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(III, IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over at pH 8. After 72 hours equilibration time, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the EXAFS spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to into the mineral structure at multiple sites with no evidence of DFOB complexation, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron in marine and terrestrial environments.

  20. 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.

  1. Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

    NASA Astrophysics Data System (ADS)

    Duckworth, Owen W.; Bargar, John R.; Sposito, Garrison

    2008-07-01

    Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB +, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB + at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.

  2. Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

    USGS Publications Warehouse

    Fuller, Christopher C.; Bargar, John R.

    2014-01-01

    The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using extended X-ray absorption fine structure (EXAFS) and microfocused synchrotron X-ray fluorescence (μSXRF) mapping, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and microfocused EXAFS spectra of Zn in the biogenic Mn oxide coating are indicative of Zn forming triple-corner-sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to the decrease in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in the solid/solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating that desorption is not controlled by dissolution of secondary Zn phases. In summary, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process of Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present.

  3. Morphology, structure, and metal binding mechanisms of biogenic manganese oxides in a superfund site treatment system.

    PubMed

    Duckworth, O W; Rivera, N A; Gardner, T G; Andrews, M Y; Santelli, C M; Polizzotto, M L

    2017-01-25

    Manganese oxides, which may be biogenically produced in both pristine and contaminated environments, have a large affinity for many trace metals. In this study, water and Mn oxide-bearing biofilm samples were collected from the components of a pump and treat remediation system at a superfund site. To better understand the factors leading to their formation and their effects on potentially toxic metal fate, we conducted a chemical, microscopic, and spectroscopic characterization of these biofilm samples. Scanning electron microscopy revealed the presence of Mn oxides in close association with biological structures with morphologies consistent with fungi. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) revealed the oxides to be a mixture of layer and tunnel structure Mn(iv) oxides. In addition, XAS suggested that Ba, Co, and Zn all primarily bind to oxides in the biofilm in a manner that is analogous to synthetic or laboratory grown bacteriogenic Mn oxides. The results indicate that Mn oxides produced by organisms in the system may effectively scavenge metals, thus highlighting the potential utility of these organisms in designed remediation systems.

  4. 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

  5. Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

    USGS Publications Warehouse

    Bargar, J.R.; Fuller, C.C.; Marcus, M.A.; Brearley, A.J.; Perez De la Rosa, M.; Webb, S.M.; Caldwell, W.A.

    2009-01-01

    The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick ?? 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-?? basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mn oxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments. ?? 2008 Elsevier Ltd.

  6. Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ

    SciTech Connect

    Bargar, John; Fuller, Christopher; Marcus, Matthew A.; Brearley, Adrian J.; Perez De la Rosa, M.; Webb, Samuel M.; Caldwell, Wendel A.

    2008-03-19

    The microbial catalysis of Mn(II) oxidation is believed to be a dominant source of abundant sorption- and redox-active Mn oxides in marine, freshwater, and subsurface aquatic environments. In spite of their importance, environmental oxides of known biogenic origin have generally not been characterized in detail from a structural perspective. Hyporheic zone Mn oxide grain coatings at Pinal Creek, Arizona, a metals-contaminated stream, have been identified as being dominantly microbial in origin and are well studied from bulk chemistry and contaminant hydrology perspectives. This site thus presents an excellent opportunity to study the structures of terrestrial microbial Mn oxides in detail. XRD and EXAFS measurements performed in this study indicate that the hydrated Pinal Creek Mn oxide grain coatings are layer-type Mn oxides with dominantly hexagonal or pseudo-hexagonal layer symmetry. XRD and TEM measurements suggest the oxides to be nanoparticulate plates with average dimensions on the order of 11 nm thick x 35 nm diameter, but with individual particles exhibiting thickness as small as a single layer and sheets as wide as 500 nm. The hydrated oxides exhibit a 10-A basal-plane spacing and turbostratic disorder. EXAFS analyses suggest the oxides contain layer Mn(IV) site vacancy defects, and layer Mn(III) is inferred to be present, as deduced from Jahn-Teller distortion of the local structure. The physical geometry and structural details of the coatings suggest formation within microbial biofilms. The biogenic Mnoxides are stable with respect to transformation into thermodynamically more stable phases over a time scale of at least 5 months. The nanoparticulate layered structural motif, also observed in pure culture laboratory studies, appears to be characteristic of biogenic Mn oxides and may explain the common occurrence of this mineral habit in soils and sediments.

  7. 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

  8. A comparison of the sorption reactivity of bacteriogenic and mycogenic Mn oxide nanoparticles.

    PubMed

    Droz, Boris; Dumas, Naomi; Duckworth, Owen W; Peña, Jasquelin

    2015-04-07

    Biogenic MnO2 minerals affect metal fate and transport in natural and engineered systems by strongly sorbing metals ions. The ability to produce MnO2 is widely dispersed in the microbial tree of life, leading to potential differences in the minerals produced by different organisms. In this study, we compare the structure and reactivity of biogenic Mn oxides produced by the biofilm-forming bacterium Pseudomonas putida GB-1 and the white-rot fungus Coprinellus sp. The rate of Mn(II) oxidation, and thus biomineral production, was 45 times lower for Coprinellus sp. (5.1 × 10(-2) mM d(-1)) than for P. putida (2.32 mM d(-1)). Both organisms produced predominantly Mn(IV) oxides with hexagonal-sheet symmetry, low sheet stacking, small particle size, and Mn(II/III) in the interlayer. However, we found that mycogenic MnO2 could support a significantly lower quantity of Ni sorbed via inner-sphere coordination at vacancy sites than the bacteriogenic MnO2: 0.09 versus 0.14 mol Ni mol(-1) Mn. In addition, 50-100% of the adsorbed Ni partitioned to the MnO2, which accounts for less than 20% of the sorbent on a mass basis. The vacancy content, which appears to increase with the kinetics of MnO2 precipitation, exerts significant control on biomineral reactivity.

  9. BIOGENIC NITRIC OXIDE EMISSIONS FROM CROPLAND SOILS

    EPA Science Inventory

    Emissions of nitric oxide (NO) were determined during late spring and summer 1995 and the spring of 1996 from four agricultural soils on which four different crops were grown. These agricultural soils were located at four different sites throughout North Carolina. Emission rates ...

  10. 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.

  11. 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

  12. Effects of Cobalt on Manganese Oxidation by Pseudomonas putida MnB1

    NASA Astrophysics Data System (ADS)

    Pena, J.; Bargar, J.; Sposito, G.

    2005-12-01

    The oxidation of Mn(II) in the environment is thought to occur predominantly through biologically mediated pathways. During the stationary phase of growth, the well-characterized freshwater and soil bacterium Pseudomonas putida MnB1 oxidizes soluble Mn(II) to a poorly crystalline layer type Mn(IV) oxide. These Mn oxide particles (2 - 5 nm thickness) are deposited in a matrix of extracellular polymeric substances (EPS) surrounding the cell, creating a multi-component system distinct from commonly studied synthetic Mn oxides. Accurate characterization of the reactivity of these biomineral assemblages is essential to understanding trace metal biogeochemistry in natural waters and sediments. Moreover, these biogenic oxides may potentially be used for the remediation of surface and ground waters impacted by mining, industrial pollution, and other anthropogenic activities. In this study, we consider the interactions between Co, P. putida MnB1, and its biogenic Mn oxide. Cobalt is a redox-active transition metal which exists in the environment as Co(II) and Co(III). While Co is not generally found in the environment at toxic concentrations, it may be released as a byproduct of mining activities (e.g. levels of up to 20 μM are found in Pinal Creek, AZ, a stream affected by copper mining). In addition, the radionuclide 60Co, formed by neutron activation in nuclear reactors, is of concern at Department of Energy sites, such as that at Hanford, and has several industrial applications, including radiotherapy. We address the following questions: Do high levels of Co inhibit enzymatic processes such as Mn(II) oxidation? Can the multicopper oxidase enzyme involved in Mn(II) oxidation facilitate Co(II) oxidation? Lastly, does the organic matter surrounding the oxides affect Co or Mn oxide reactivity? These issues were approached via wet chemical analysis, synchrotron radiation X-ray diffraction (SR-XRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy. In the

  13. 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

  14. XPS determination of Mn oxidation states in Mn (hydr)oxides

    SciTech Connect

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-01

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a common layered structure that occurs readily in Nature but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and widths of each oxidation state, composed of a packet of correlated component peaks, were allowed vary. whereas widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated with close agreement between Mn3s and Mn3p, whereas Mn2p3/2 gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than Mn2p. Consequently, fitting the Mn3p and Mn3s lines yields robust quantification of oxidation states over a range of hydrous Mn oxide polytypes and compositions. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line is not appropriate for birnessites.

  15. XPS determination of Mn oxidation states in Mn (hydr)oxides

    NASA Astrophysics Data System (ADS)

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-01

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic and redox activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a layered structure that occurs commonly in soils but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and peak-widths of each oxidation state, composed of a packet of correlated component peaks, were allowed to vary. Peak-widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated, with close agreement between Mn3s and Mn3p analyses, whereas calculations based on the Mn2p3/2 spectra gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than that for Mn2p. Consequently, fitting the Mn3p and Mn3s lines yielded robust quantification of oxidation states over a range of Mn (hydr)oxide phases. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line was found to be not appropriate for birnessites.

  16. Thermodynamic constraints on the oxidation of biogenic UO2 by Fe(III) (Hydr)oxides.

    PubMed

    Ginder-Vogel, Matthew; Criddle, Craig S; Fendorf, Scott

    2006-06-01

    Uranium mobility in the environment is partially controlled by its oxidation state, where it exists as either U(VI) or U(IV). In aerobic environments, uranium is generally found in the hexavalent form, is quite soluble, and readily forms complexes with carbonate and calcium. Under anaerobic conditions, common metal respiring bacteria can reduce soluble U(VI) species to sparingly soluble UO2 (uraninite); stimulation of these bacteria, in fact, is being explored as an in situ uranium remediation technique. However, the stability of biologically precipitated uraninite within soils and sediments is not well characterized. Here we demonstrate that uraninite oxidation by Fe(III) (hydr)oxides is thermodynamically favorable under limited geochemical conditions. Our analysis reveals that goethite and hematite have a limited capacity to oxidize UO2(biogenic) while ferrihydrite can lead to UO2(biogenic) oxidation. The extent of UO2(biogenic) oxidation by ferrihydrite increases with increasing bicarbonate and calcium concentration, but decreases with elevated Fe(II)(aq) and U(VI)(aq) concentrations. Thus, our results demonstrate that the oxidation of UO2(biogenic) by Fe(III) (hydr)oxides may transpire under mildly reducing conditions when ferrihydrite is present.

  17. Biogenic nitrogen and carbon in Fe-Mn-oxyhydroxides from an Archean chert, Marble Bar, Western Australia

    NASA Astrophysics Data System (ADS)

    Pinti, Daniele L.; Hashizume, Ko; Orberger, Beate; Gallien, Jean-Paul; Cloquet, Christophe; Massault, Marc

    2007-02-01

    To quantify and localize nitrogen (N) and carbon (C) in Archean rocks from the Marble Bar formation, Western Australia, and to gain insights on their origin and potential biogenicity, we conducted nuclear reaction analyses (NRA) and carbon and nitrogen isotope ratio measurements on various samples from the 3460-Myr-old Fe-rich Marble Bar chert. The Marble Bar chert formed during the alteration of basaltic volcanoclastic rocks with Fe- and Si-rich hydrothermal fluids, and the subsequent precipitation of magnetite, carbonates, massive silica, and, locally, sulfides. At a later stage, the magnetite, sulfides, and carbonates were replaced by Fe-Mn-oxyhydroxides. Nuclear reaction analyses indicate that most of the N and C resides within these Fe-Mn-oxyhydroxides, but a minor fraction is found in K-feldspars and Ba-mica dispersed in the silica matrix. The N and C isotopic composition of Fe-oxides suggests the presence of a unique biogenic source with δ 15NAIR values from +6.0 +/- 0.5‰ to 7.3 +/- 1.1‰ and a δ 13CPDB value of -19.9 +/- 0.1‰. The C and N isotope ratios are similar to those observed in Proterozoic and Phanerozoic organic matter. Diffusion-controlled fractionation of N and C released during high combustion temperatures indicates that these two elements are firmly embedded within the iron oxides, with activation energies of 18.7 +/- 3.7 kJ/mol for N and 13.0 +/- 3.8 kJ/mol for C. We propose that N and C were chemisorbed on iron and were subsequently embedded in the crystals during iron oxidation and crystal growth. The Fe-isotopic composition of the Marble Bar chert (δ 56Fe = -0.38 +/- 0.02‰) is similar to that measured in iron oxides formed by direct precipitation of iron from hydrothermal plumes in contact with oxygenated waters. To explain the N and C isotopic composition of Marble Bar chert, we propose either (1) a later addition of N and C at the end of Archean when oxygen started to rise or (2) an earlier development of localized oxygenated

  18. 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.

  19. 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

  20. Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation

    SciTech Connect

    Isaacman-VanWertz, Gabriel; Yee, Lindsay D.; Kreisberg, Nathan M.; Wernis, Rebecca; Moss, Joshua A.; Hering, Susanne V.; de Sa, Suzanne; Martin, Scot T.; Alexander, Mikaela L.; Palm, Brett B.; Hu, Weiwei; Campuzano-Jost, Pedro; Day, Douglas; Jimenez, Jose L.; Riva, Matthieu; Surratt, Jason D.; Viegas, Juarez; Manzi, Antonio; Edgerton, Eric S.; Baumann, K.; Souza, Rodrigo A.; Artaxo, Paulo; Goldstein, Allen H.

    2016-08-23

    Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within similar to 25% across measurement sites.

  1. Nanometer Scale Morphology of Bacteriogenic Mn Oxides

    NASA Astrophysics Data System (ADS)

    Perez, M.; Obraztsova, A.; Tebo, B. M.; Bargar, J. R.

    2005-12-01

    Manganese oxides, which are ubiquitous in surface waters, soils, and sediments, are believed to result from the bacterially catalyzed oxidation of Mn(II) to Mn(IV). Bacteriogenic Mn oxides exhibit high surface areas and degrade or oxidize a variety of organic and inorganic compounds. Via these reactions, Mn oxides influence the biogeochemical cycling of micronutrients and help to control the composition of natural waters. Recent EXAFS (extended X-ray absorption fine structure) and WAXS (wide angle X-ray scattering) investigations of bacteriogenic Mn oxides indirectly suggest that particles are as small as 10 or 20 nm , . However, no detailed systematic quantitative measurements of bacteriogenic Mn oxide particle sizes and morphology have been reported. We have characterized manganese oxides produced by the marine sporeforming bacterium Bacillus sp., strain SG-1 using SAXS (small angle X-ray scattering) and TEM (transmission electron microscopy). TEM measurements indicate that the particles are layered structures having basal-plane widths of several hundred nm. WAXS measurements indicate that particles are extremely thin, ~1nm thick, which corresponds to a single Mn oxide layer. The particles appear to have particularly high aspect ratios, with the majority of all structural MnO6 octahedral units exposed to solution. Furthermore, it follows that basal plane sites are the overwhelmingly dominant surface binding sites. Particles with such small dimensions often have properties that are intermediate between those of molecular clusters and bulk materials. Therefore, the reactivity of natural manganese oxides is expected to differ substantially from that of synthetic crystalline analogs.

  2. Mn4+ emission in pyrochlore oxides

    DOE PAGES

    Du, Mao-Hua

    2015-01-01

    For the existing Mn4+ 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 Mn4+ emission in rare-earth hafnate, zirconate, and stannate pyrochlore oxides (RE2Hf2O7, RE2Zr2O7, and RE2Sn2O7). We show how the different sizes of the RE3+ cation in these pyrochlores affect the local structure of the distorted MnO6 octahedron, the Mn–O hybridization, and the Mn4+ emission energy. The Mn4+ emission energies of many pyrochlores are found to be higher than those currently known for Mn4+ doped oxides and should be closer to thatmore » of Y2O3:Eu3+ (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 Mn4+ emission energy. Our result shows that searching for materials that allow significant O–Mn–O bond angle distortion in a MnO6 octahedron is an effective approach to find new Mn4+ activated red phosphors with potential to replace the relatively expensive Y2O3:Eu3+ phosphor.« less

  3. 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

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

    SciTech Connect

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

    2011-02-21

    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 mine 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.

  5. Biological oxidation of Mn(II) coupled with nitrification for removal and recovery of minor metals by downflow hanging sponge reactor.

    PubMed

    Cao, Linh Thi Thuy; Kodera, Hiroya; Abe, Kenichi; Imachi, Hiroyuki; Aoi, Yoshiteru; Kindaichi, Tomonori; Ozaki, Tomonori; Ohashi, Akiyoshi

    2015-01-01

    Biogenic manganese oxides (bio-MnO₂) have been shown to absorb minor metals. Bioreactor cultivation of heterotrophic manganese oxidizing bacteria (MnOB), which produce bio-MnO₂ via oxidation of Mn (II), can be expected to be involved in a promising system for removal and recovery of minor metals from wastewater. However, MnOB enrichment in wastewater treatment is difficult. This study investigated whether MnOB can be cultivated when coupled with nitrification in a system in which soluble microbial products (SMP) from nitrifiers are provided to MnOB as a substrate. A downflow hanging sponge (DHS) reactor was applied for MnOB cultivation with ammonium (NH₄⁺) and Mn (II) continuously supplied. During long-term operation, Mn (II) oxidation was successfully established at a rate of 48 g Mn m⁻³ d⁻¹ and bio-MnO₂ that formed on the sponges were recovered from the bottom of the reactor. The results also revealed that Ni and Co added to the influent were simultaneously removed. Microbial 16S rRNA gene clone analysis identified nitrifiers supporting MnOB growth and showed that only one clone of Bacillus subtilis, which was affiliated with a known MnOB cluster, was present, suggesting the existence of other novel bacteria with the ability to oxidize Mn (II).

  6. 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

  7. Diversity and As-adsorption properties of Mn(II)-oxidizing bacteria within tropical wetlands of the Mekong Delta

    NASA Astrophysics Data System (ADS)

    Ying, S. C.; Kocar, B. D.; Fendorf, S.; Francis, C. A.

    2007-12-01

    Manganese (Mn) and iron (Fe) oxides are ubiquitous minerals that occur under similar redox conditions in terrestrial systems and have high sorptive capacities for many trace metals, including arsenic (As). In most natural environments, Fe oxidation is dominated by abiotic processes, while Mn oxides are primarily formed via bacterial Mn(II) oxidation, and both processes can profoundly impact the mobility of metal(loid) contaminants. Deciphering the mechanisms involved in arsenic transport within soils and sediments is essential for aiding many Southeast Asian countries, including Cambodia, where naturally occurring As is in groundwater at concentrations well above the WHO recommended limit. Although numerous past studies have characterized the effects of As adsorption onto Fe and Mn oxides individually, it is unknown whether, in the presence of both oxides, there is preferential adsorption of As onto one oxide over the other. In the present study, we examine the competitive retention of As(III) and As(V) on goethite and biogenic Mn oxides using Donnan membranes--where each oxides is isolated by a semi-permeable membrane through which arsenic can migrate. Mn(II)-oxidizing bacteria, isolated from several Mn-rich sites along the Mekong River and wetland areas within the Mekong delta, were dominated by a diverse array of Bacillus strains that rapidly oxidize Mn(II) within three to five days in liquid culture. The results of this study not only expand our knowledge of the diversity and biogeochemical importance of terrestrial Mn(II)-oxidizing bacteria, but also contribute to our understanding the relative impact of Fe and Mn oxides on arsenic retention within natural wetlands.

  8. Oxidative UO2 dissolution induced by soluble Mn(III).

    PubMed

    Wang, Zimeng; Xiong, Wei; Tebo, Bradley M; Giammar, Daniel E

    2014-01-01

    The stability of UO2 is critical to the success of reductive bioremediation of uranium. When reducing conditions are no longer maintained, Mn redox cycling may catalytically mediate the oxidation of UO2 and remobilization of uranium. Ligand-stabilized soluble Mn(III) was recently recognized as an important redox-active intermediate in Mn biogeochemical cycling. This study evaluated the kinetics of oxidative UO2 dissolution by soluble Mn(III) stabilized by pyrophosphate (PP) and desferrioxamine B (DFOB). The Mn(III)-PP complex was a potent oxidant that induced rapid UO2 dissolution at a rate higher than that by a comparable concentration of dissolved O2. However, the Mn(III)-DFOB complex was not able to induce oxidative dissolution of UO2. The ability of Mn(III) complexes to oxidize UO2 was probably determined by whether the coordination of Mn(III) with ligands allowed the attachment of the complexes to the UO2 surface to facilitate electron transfer. Systematic investigation into the kinetics of UO2 oxidative dissolution by the Mn(III)-PP complex suggested that Mn(III) could directly oxidize UO2 without involving particulate Mn species (e.g., MnO2). The expected 2:1 reaction stoichiometry between Mn(III) and UO2 was observed. The reactivity of soluble Mn(III) in oxidizing UO2 was higher at lower ratios of pyrophosphate to Mn(III) and lower pH, which is probably related to differences in the ligand-to-metal ratio and/or protonation states of the Mn(III)-pyrophosphate complexes. Disproportionation of Mn(III)-PP occurred at pH 9.0, and the oxidation of UO2 was then driven by both MnO2 and soluble Mn(III). Kinetic models were derived that provided excellent fits of the experimental results.

  9. 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

    2017-03-10

    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.

  10. Influence of Mn oxides on the reduction of U(VI) by the metal-reducing bacterium Shewanella putrefaciens

    SciTech Connect

    Fredrickson, Jim K.; Zachara, John M.; Kennedy, David W.; Liu, Chongxuan; Duff, Martine C.; Hunter, David; Dohnalkova, Alice

    2002-09-16

    Dissimilatory metal-reducing bacteria (DMRB) enzymatically reduce Fe(III), Mn(III/IV), U(VI), and other polyvalent metals during anaerobic respiration. Previous investigations of the bacterial reduction of U(VI) in the presence of goethite (a-FeOOH) found that, in spite of potential competition as an electron acceptor, goethite had little impact on the bacterial reduction of U(VI) to insoluble U(IV). Mn(III/IV) oxides are also electron acceptors for DMRB but are stronger oxidants than Fe(III) oxides. Differences in the solubility of oxidized Mn and U challenges predictions of their biogeochemical behavior during redox cycling. The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by a subsurface bacterium Shewanella putrefaciens CN32 was investigated using synthetic Mn(III/IV) oxides [pyrolusite ({beta}-MnO{sub 2}), bixbyite (Mn{sub 2}O{sub 3}) and K{sup +}-birnessite (K{sub 4}Mn{sub 14}O{sub 27} {center_dot} 8H{sub 2}O)]. In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO{sub 2}(s)) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence, or in the presence of gibbsite [Al(OH){sub 3}] added as a non-redox reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43-100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial-Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. In the absence of Mn(III/IV) oxides, UO{sub 2}(s) accumulated as copius fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments?.

  11. Immobilization of Mn(II) via Homogeneous and Heterogeneous Oxidation

    NASA Astrophysics Data System (ADS)

    Kang, N.; Jeong, H. Y.; Park, M.; Kim, K. H.; Lee, S.; Choi, H. J.

    2015-12-01

    This study investigated the immobilization of Mn(II) via homogeneous and heterogeneous oxidation by air. A series of kinetic experiments were performed with stirred batch reactors equipped with air spargers. The reactions were initiated by adding Mn(II) stock solutions to pH-buffered solutions amended with dissolved Fe(II), Fe oxyhydroxides, or Mn oxides. Under experimental conditions, the homogeneous oxidation of Mn(II) itself was minimal over pH 6.5-8.5. However, when dissolved Fe(II) was present, the immobilization of Mn occurred, with the extent becoming greater at higher pH. By Mn-K edge XAS analysis, the Mn removal at pH 6.5 was due to the oxidation of labile Mn(II) into insoluble Mn(III) solids, which was catalyzed by the homogeneous oxidation of Fe(II). On the other hand, Mn(II) at pH 7.0-8.5 remained largely unoxidized; instead, it was immobilized by forming co-precipitates with Fe(III) oxyhydroxides. Goethite, HFO, Mn2O3, and MnO2 were added to mediate the heterogeneous oxidation of Mn(II). In the presence of goethite and HFO, dissolved Mn was initially quickly decreased, and later gradually decreased. In both batches, the initial removal was due to the surface complexation of Mn(II) with Fe oxyhydroxides. On the other hand, the later removal in goethite-amend batches resulted from the formation of co-precipitates with Fe(III) oxyhydroxides, whereas the later removal in HFO-amended batches was due to the heterogeneous oxidation of Mn(II) into Mn(III) solids. When Mn2O3 and MnO2 were used as heterogeneous catalysts, XAS analysis did not provide mechanistic insight into Mn removal. Nonetheless, Mn2O3 was found to immobilize Mn(II) under oxic conditions. Notably, MnO2 was far more effectively immobilize Mn(II) under both oxic and anoxic conditions, pointing to its superior oxidative capability. Acknowledgement: Financial support was provided by "R&D Project on Environmental Management of Geologic CO2 Storage" from the KEITI (Project Number: 2014001810003).

  12. 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.

  13. Methyl Chavicol: Characterization of its Biogenic Emission Rate, Abundance, and Oxidation Products in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Bouvier-Brown, N. C.; Goldstein, A. H.; Worton, D. R.; Matross, D. M.; Gilman, J.; Kuster, W.; Degouw, J.; Cahill, T. M.; Holzinger, R.

    2008-12-01

    We report quantitative measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments: gas chromatograph with mass spectrometer detector (GC-MS), proton transfer reaction mass spectrometer (PTR-MS), and thermal desorption aerosol GC-MS (TAG). Previously identified as a potential bark beetle disruptant, methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light and temperature dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4-68 % of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72-10.2 μ gCg-1h-1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many species. We propose this newly- characterized biogenic compound should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  14. Indirect UO2 oxidation by Mn(II)-oxidizing spores of Bacillus sp. strain SG-1 and the effect of U and Mn concentrations.

    PubMed

    Chinni, Satyavathi; Anderson, Craig R; Ulrich, Kai-Uwe; Giammar, Daniel E; Tebo, Bradley M

    2008-12-01

    Manganese oxides are widespread in the environment and their surface reactivity has the potential to modifythe geochemical behavior of uranium. We have investigated the effect of different concentrations of U and Mn on the coupled biogeochemical oxidation-reduction reactions of U and Mn. Experiments conducted in the presence of Mn(II)-oxidizing spores from Bacillus sp. strain SG-1 and 5% headspace oxygen show that the Mn oxides produced by these spores can rapidly oxidize UO2. Thirty to fifty times more UO2 is oxidized in the presence of Mn oxides compared to Mn oxide free controls. As a consequence of this U02 oxidation, Mn oxides are reduced to soluble Mn(II) that can be reoxidized by SG-1 spores. SG-1 spores cannot directly oxidize U02, but U02 oxidation proceeds rapidly with Mn(II) concentrations of <5 microM. The rate of UO2 oxidation is equal to the rate of MnO2 reduction with UO2 oxidation controlled by the initial concentrations of UO2, dissolved Mn(II) (in systems with spores), or Mn(IV) oxides (in systems containing preformed MnO2). U(VI) and UO2 decrease the Mn(II) oxidation rate in different ways by inhibiting the Mn(II)-oxidizing enzyme or decreasing the available Mn(II). These results emphasize the need to consider the impact of Mn(II)-oxidizing bacteria when predicting the potential for U02 oxidation in the subsurface.

  15. Secondary Organic Aerosol Formation by Molecular-Weight Building Reactions of Biogenic Oxidation Products

    NASA Astrophysics Data System (ADS)

    Barsanti, K.; Guenther, A.; Matsunaga, S.; Smith, J.

    2006-12-01

    Understanding the chemical composition of atmospheric organic aerosols (OA) remains one of the significant challenges to accurately representing OA in air quality and climate models. Meeting this challenge will require further understanding of secondary organic aerosols (SOA), of which biogenic emissions are thought to be major precursors. Of recent interest is the significance of higher-molecular weight (MW) compounds (i.e., "oligomers"). Theoretical, laboratory, and field study results suggest that relatively volatile oxidation products may contribute to SOA formation through multi-phase MW- building reactions. The significance of such reactions for biogenic SOA formation, including for newly considered precursors such as isoprene, is explored in this work. Theoretical and field studies are employed to: 1) identify MW-building reactions that may contribute to SOA formation in the atmosphere, 2) identify MW-building reaction products in ambient samples, and 3) parameterize atmospheric SOA formation by MW-building reactions of biogenic oxidation products. Likely reactions of biogenic oxidation products include ester, amide, and peroxyhemiacetal formation. Each of the proposed reactions involves known oxidation productions of biogenic precursors (e.g., carboxylic acids and aldehydes) reacting with one another and/or other atmospheric constituents (e.g., sulfuric acid and ammonia) to form higher-MW/lower-volatility products that can condense to form SOA. It has been suggested that products of MW-building reactions can revert to the parent reactants during sampling and analysis. Thus, relatively volatile compounds detected in ambient particle samples in fact may be decomposition products of higher-MW products. The contribution of relatively volatile biogenic oxidation products to SOA via ester, amide, and peroxyhemiacetal formation, as determined by studies based on fundamental thermodynamics and gas/particle partitioning theory, will be discussed; in addition to

  16. 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.

  17. 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

  18. 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.

  19. Biogenic terbium oxide nanoparticles as the vanguard against osteosarcoma

    NASA Astrophysics Data System (ADS)

    Iram, Sana; Khan, Salman; Ansary, Abu Ayoobul; Arshad, Mohd; Siddiqui, Sahabjada; Ahmad, Ejaz; Khan, Rizwan H.; Khan, Mohd Sajid

    2016-11-01

    The synthesis of inner transition metal nanoparticles via an ecofriendly route is quite difficult. This study, for the first time, reports synthesis of terbium oxide nanoparticles using fungus, Fusarium oxysporum. The biocompatible terbium oxide nanoparticles (Tb2O3 NPs) were synthesized by incubating Tb4O7 with the biomass of fungus F. oxysporum. Multiple physical characterization techniques, such as UV-visible and photoluminescence spectroscopy, TEM, SAED, and zeta-potential were used to confirm the synthesis, purity, optical and surface characteristics, crystallinity, size, shape, distribution, and stability of the nanoemulsion of Tb2O3 NPs. The Tb2O3 NPs were found to inhibit the propagation of MG-63 and Saos-2 cell-lines (IC50 value of 0.102 μg/mL) and remained non-toxic up to a concentration of 0.373 μg/mL toward primary osteoblasts. Cell viability decreased in a concentration-dependent manner upon exposure to 10 nm Tb2O3 NPs in the concentration range 0.023-0.373 μg/mL. Cell toxicity was evaluated by observing changes in cell morphology, cell viability, oxidative stress parameters, and FACS analysis. Morphological examinations of cells revealed cell shrinkage, nuclear condensation, and formation of apoptotic bodies. The level of ROS within the cells-an indicator of oxidative stress was significantly increased. The induction of apoptosis at concentrations ≤ IC50 was corroborated by 4‧,6-diamidino-2-phenylindole dihydrochloride (DAPI) staining (DNA damage and nuclear fragmentation). Flow-cytometric studies indicated that the response was dose dependent with a threshold effect.

  20. Rapid deposition of oxidized biogenic compounds to a temperate forest

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-02-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m-2ṡs-1). GEOS-Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

  1. Rapid deposition of oxidized biogenic compounds to a temperate forest

    PubMed Central

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-01-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (∼1 nmol m−2⋅s−1). GEOS−Chem, a widely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS−Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases. PMID:25605913

  2. Rapid Deposition of Oxidized Biogenic Compounds to a Temperate Forest

    NASA Technical Reports Server (NTRS)

    Nguyen, Tran B.; Crounse, John D.; Teng, Alex P.; St. Clair, Jason M.; Paulot, Fabien; Wolfe, Glenn M.; Wennberg, Paul O.

    2015-01-01

    We report fluxes and dry deposition velocities for 16 atmospheric compounds above a southeastern United States forest, including: hydrogen peroxide (H2O2), nitric acid (HNO3), hydrogen cyanide (HCN), hydroxymethyl hydroperoxide, peroxyacetic acid, organic hydroxy nitrates, and other multifunctional species derived from the oxidation of isoprene and monoterpenes. The data suggest that dry deposition is the dominant daytime sink for small, saturated oxygenates. Greater than 6 wt %C emitted as isoprene by the forest was returned by dry deposition of its oxidized products. Peroxides account for a large fraction of the oxidant flux, possibly eclipsing ozone in more pristine regions. The measured organic nitrates comprise a sizable portion (15%) of the oxidized nitrogen input into the canopy, with HNO3 making up the balance. We observe that water-soluble compounds (e.g., strong acids and hydroperoxides) deposit with low surface resistance whereas compounds with moderate solubility (e.g., organic nitrates and hydroxycarbonyls) or poor solubility (e.g., HCN) exhibited reduced uptake at the surface of plants. To first order, the relative deposition velocities of water-soluble compounds are constrained by their molecular diffusivity. From resistance modeling, we infer a substantial emission flux of formic acid at the canopy level (approx. 1 nmol m(exp.-2)·s(exp.-1)). GEOS-Chem, awidely used atmospheric chemical transport model, currently underestimates dry deposition for most molecules studied in this work. Reconciling GEOS-Chem deposition velocities with observations resulted in up to a 45% decrease in the simulated surface concentration of trace gases.

  3. Biogenic methanol and its impacts on tropospheric oxidants

    NASA Astrophysics Data System (ADS)

    Tie, Xuexi; Guenther, Alex; Holland, Elisabeth

    2003-09-01

    We use a global chemical transport model (MOZART-2) to estimate the effects of surface emissions of methanol on tropospheric oxidants. The importance of methanol in tropospheric chemistry is two fold. First, methanol has a relatively large surface emission with an estimated global emission of 70 to 350 Tg methanol/year. The estimated methanol flux is comparable to other major hydrocarbon surface emissions such as isoprene and total monoterpenes, but the chemical lifetime of methanol is several days (in the boundary layer) to a few weeks (in the upper troposphere), which is much longer than the chemical lifetime of isoprene or monoterpenes (For example, the chemical lifetime of isoprene is about 2 hours). With a surface emission of 104 to 312 Tg methanol/year (encompasses estimated uncertainty in methanol emissions), the calculation shows that on average, the inclusion of methanol emission produces approximately 1-2% increase in O3, 1-3% decrease in OH, 3-5% increase in HO2, and 3-9% increase in CH2O globally. The maximum perturbation to the oxidants occurs in the tropical upper troposphere. However, the uncertainty associated with current methanol emission estimates produces significantly different model predictions of tropospheric oxidant distributions.

  4. 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

  5. Actinomycetes mediated biogenic synthesis of metal and metal oxide nanoparticles: Progress and challenges.

    PubMed

    Manimaran, Manickavelu; Kannabiran, Krishnan

    2017-03-07

    Actinomycetes mediated biogenic synthesis of metal nanoparticles and their antimicrobial activities are well documented. Actinomycetes facilitate both intracellular and extracellular metal nanoparticles synthesis and are efficient candidates for the production of polydispersed, stable and ultra-small size metal nanoparticles. Secondary metabolites and new chemical entities derived from actinomycetes have not been extensively studied for the synthesis of metal/ metal oxide nanoparticles. The present review focuses on biogenic synthesis of metal nanoparticles from actinomycetes and the scope for exploring actinomycetes derived compounds (enzymes, organics acids and bioactive compounds) as metal and metal oxide reducing agents for the synthesis of desired nanoparticles. This review also focuses on challenges faced in the applications nanoparticles and the methods to synthesise biogenic metal nanoparticles with desired physiochemical properties such as ultra-small size, large surface to mass ratio, high reactivity etc. Methods to evade their toxicity and unique interactions with biological systems to improve their chance as an alternative therapeutic agent in medical and pharmaceutical industry are also discussed. This article is protected by copyright. All rights reserved.

  6. Biogenic isoprene and implications for oxidant levels in Beijing during the 2008 Olympic Games

    NASA Astrophysics Data System (ADS)

    Chang, C.-C.; Shao, M.; Chou, C. C. K.; Liu, S.-C.; Wang, J.-L.; Lee, K.-Z.; Lai, C.-H.; Zhu, T.; Lin, P.-H.

    2013-10-01

    As the host of the 2008 Summer Olympic Games, Beijing implemented a series of stringent, short-term air quality control measures to reduce the emissions of anthropogenic air pollutants. Large reductions in the daily average concentrations of primary pollutants, e.g., non-methane hydrocarbons (NMHCs) and nitrogen oxides (NOx) of approximately 50% were observed at the air quality observatory of Peking University. Nevertheless, high levels of ozone were present during the control period. Although anthropogenic precursors were greatly reduced, the meteorological conditions in summer, including high temperature and light flux, are conducive to the production of large amounts of biogenic isoprene, which is extremely reactive. The diurnal pattern of isoprene showed daily maximum mixing ratios of 0.83 ppbv at noon and a minimum at night, reflecting its primarily biogenic properties. Using the ratio of isoprene to vehicle exhaust tracers, approximately 92% of the daytime isoprene was estimated from biogenic sources, and only 8% was attributed to vehicular emissions. In terms of OH reactivity and the ozone formation potential (OFP), biogenic isoprene with its midday surge can contribute approximately 20% of the total OFPs and 40-50% of the total OH reactivities of the 65 measured NMHCs during the midday hours. The discrepancy between decreased precursor levels and the observed high ozone was most likely caused by a combination of many factors. The changes in the partition among the components of oxidation products (O3, NO2 and NOz) and the contribution of air pollutants from regional sources outside Beijing should be two primary reasons. Furthermore, the influences of biogenic isoprene as well as the non-linearity of O3-VOC-NOx chemistry are other major concerns that can reduce the effectiveness of the control measures for decreasing ozone formation. Although anthropogenic precursors were greatly reduced during the Olympic Games, sufficient biogenic isoprene and moderate NOx

  7. Environmental estrogen Bisphenol A adsorption/oxidation on Graphene oxide/MnO2 (GO/MnO2) nanocomposite

    NASA Astrophysics Data System (ADS)

    Bele, Sotiria I.; Deliyanni, Eleni A.

    2015-04-01

    The environmental fate and decontamination of Bisphenol A (BPA), an environmental estrogen that is used as a monomer in plastic industry, are of emerging concern. This study focused on the kinetics, influencing factors and pathways of its adsorption and oxidative decomposition by MnO2. Additionally, Graphene oxide/MnO2 (GO/MnO2) nanocomposite was prepared and tested as a kind of adsorbent and/or catalysts for oxidative decomposition of Bisphenol A (BPA). A suspension of graphene oxide/manganese sulfate (GO/MnSO4) produced by the modified Hummers method was in situ transformed into GO/MnO2 nanocomposite in combination with KMnO4. It is found that MnO2 nanoparticles are uniformly distributed in the structure of GO. The surface chemistry and the porous texture of the prepared nanocomposite were characterized by thermal analysis (DTA), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscope (SEM) and Nitrogen adsorption (BET). The nanocomposite presented superior catalytic activities, much higher than that of the bare MnO2 for the decomposition of BPA in the presence of H2O2. The high activity of GO/MnO2 nanocomposite for the decomposition of BPA could be related to the synergistic effect of GO and MnO2 with the assistance of H2O2 according to the adsorption-oxidation-desorption mechanism.

  8. Biogenic oxides from neutrophilic iron bacteria and possibilities for application in the nanotechnology

    NASA Astrophysics Data System (ADS)

    Angelova, R.; Blagoev, B.; Slavov, L.; Iliev, M.; Groudeva, V.; Nedkov, I.

    2014-11-01

    The aim of this study is to obtain and characterize the ferric oxides/(oxy)hydroxides formed after cultivation of bacteria under laboratory conditions. The pure cultures of these bacteria isolated from natural habitats are identified by the methods of classical and molecular taxonomy as strains of the Leptothrix genus. Adler (AM) and Silicon iron glucose peptone (SIGP) media are the most appropriate ones for obtaining the iron oxides. The characterization of the oxides and sheaths is performed by different physical methods. The sheaths are formed in a SIGP medium. Light micrograph images and SEM revealed the average size and diameter of the sheaths. The XRD measurements showed the composition of the oxides obtained, as well as the average size of the iron particles (up to 30 nm). The TEM micrographs showed the shape of the biogenic nanoparticles, while the magnetic measurements demonstrated the superparamagnetic character of the magnetic part of the biomaterials. The new biogenic materials are promising for application in magneto electronic for building biosensors.

  9. 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

  10. The Irony of Iron - Biogenic Iron Oxides as an Iron Source to the Ocean.

    PubMed

    Emerson, David

    2015-01-01

    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.

  11. Estimates for biogenic non-methane hydrocarbons and nitric oxide emissions in the Valley of Mexico

    NASA Astrophysics Data System (ADS)

    Velasco, Erik

    Biogenic non-methane hydrocarbons (NMHC), 2-methyl-3-buten-2-ol (methylbutenol or MBO) and nitrogen oxide (NO) emissions were estimated for the Valley of Mexico developing a spatially and temporally resolved emission inventory for air quality models. The modeling domain includes all the Metropolitan Mexico City Area, the surrounding forests and agriculture fields. The estimates were based on several sources of land use and land cover data and a biogenic emission model; the biomass density and tree characteristics were obtained from reforestation program data. The biogenic emissions depend also on climatic conditions, mainly temperature and solar radiation. The temperature was obtained from a statistical revision of the last 10 yr data reported by the Mexico City Automatic Atmospheric Monitoring Network, while the solar radiation data were obtained from measurements performed in a typical oak forest in the Valley and from sources of total solar radiation data for Mexico City. The results indicated that 7% of total hydrocarbon emissions in Mexico Valley are due to vegetation and NO emissions from soil contribute with 1% to the total NO x emissions.

  12. Role of biogenic sulfide in attenuating zinc oxide and copper nanoparticle toxicity to acetoclastic methanogenesis.

    PubMed

    Gonzalez-Estrella, Jorge; Puyol, Daniel; Sierra-Alvarez, Reyes; Field, Jim A

    2015-01-01

    Soluble ions released by zinc oxide (ZnO) and copper (Cu(0)) nanoparticles (NPs) have been associated with toxicity to methanogens. This study evaluated the role of biogenic sulfide in attenuating ZnO and Cu(0) NP toxicity to methanogens. Short- and long-term batch experiments were conducted to explore ZnO and Cu(0) NPs toxicity to acetoclastic methanogens in sulfate-containing (0.4mM) and sulfate-free conditions. ZnO and Cu(0) were respectively 14 and 7-fold less toxic in sulfate-containing than in sulfate-free assays as indicated by inhibitory constants (Ki). The Ki with respect to residual soluble metal indicated that soluble metal was well correlated with toxicity irrespective of the metal ion source or presence of biogenic sulfide. Long-term assays indicated that ZnO and Cu(0) NPs caused different effects on methanogens. ZnO NPs without protection of sulfide caused a chronic effect, whereas Cu(0) NPs caused an acute effect and recovered. This study confirms that biogenic sulfide effectively attenuates ZnO and Cu(0) NPs toxicity to methanogens by the formation of metal sulfides.

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

    SciTech Connect

    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. 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.

  14. Mn(II,III) oxidation and MnO2 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

  15. 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.

  16. Effect of Mn valence on crystal structure of La-Mn-O perovskite oxides

    NASA Astrophysics Data System (ADS)

    Yao, Takeshi; Ito, Toyoji; Kokubo, Tadashi

    1995-05-01

    La:Mn = 1:1 mixtures of lanthanum oxide and manganese carbonate were heat-treated under various oxygen partial pressures at 1400 C or 1300 C. The Mn valence of the samples was measured by a chemical analysis, and the crystal structures were refined by the powder x-ray diffraction and the Rietveld analysis. A novel orthorhombic perovskite phase, belonging to the space group Pbnm and containing Mn(2+) ions, was formed by heat-treatment under low oxygen partial pressures. The structure was very close to a cubic symmetry. It is supposed that the micro Jahn-Teller effects of Mn(2+) ions were nearly canceled by one another.

  17. 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.

  18. Biogenic Fabrication of Iron/Iron Oxide Nanoparticles and Their Application

    NASA Astrophysics Data System (ADS)

    Siddiqi, Khwaja Salahuddin; ur Rahman, Aziz; Tajuddin; Husen, Azamal

    2016-11-01

    Enshrined in this review are the biogenic fabrication and applications of coated and uncoated iron and iron oxide nanoparticles. Depending on their magnetic properties, they have been used in the treatment of cancer, drug delivery system, MRI, and catalysis and removal of pesticides from potable water. The polymer-coated iron and iron oxide nanoparticles are made biocompatible, and their slow release makes them more effective and lasting. Their cytotoxicity against microbes under aerobic/anaerobic conditions has also been discussed. The magnetic moment of superparamagnetic iron oxide nanoparticles changes with their interaction with biomolecules as a consequence of which their size decreases. Their biological efficacy has been found to be dependent on the shape, size, and concentration of these nanoparticles.

  19. 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.

  20. Electronic structure of Mn and Fe oxides

    NASA Astrophysics Data System (ADS)

    Harrison, Walter

    2008-03-01

    We present a clear, simple tight-binding representation of the electronic structure and cohesive energy (energy of atomization) of MnO, Mn2O3, and MnO2, in which the formal charge states Mn^2+, Mn^3+, and Mn^4+, respectively, occur. It is based upon localized cluster orbitals for each Mn and its six oxygen neighbors. This approach is fundamentally different from local-density theory (or LDA+U), and perhaps diametrically opposite to Dynamical Mean Field Theory. Electronic states were calculated self-consistently using existing parameters [1], but it is found that the charge density is quite insensitive to charge state, so that the starting parameters are adequate. The cohesive energy per Mn is dominated by the transfer of two s electrons to oxygen p states, the same for all three compounds. The differing transfer of majority d electrons to oxygen p states, and the coupling between them, accounts for the observed variation in cohesion in the series. The same description applies to the perovskites, such as LaxSr1-xMnO3, and can be used for FeO, Fe2O3 (and FeO2), Because the formulation is local, it is equally applicable to impurities, defects and surfaces. [1] Walter A. Harrison, Elementary Electronic Structure, World Scientific (Singapore, 1999), revised edition (2004).

  1. Synthesis and microstructure of porous Mn-oxides

    NASA Astrophysics Data System (ADS)

    Musić, Svetozar; Ristić, Mira; Popović, Stanko

    2009-04-01

    Porous Mn-oxide particles were synthesized by urea processing in combination with the thermal treatment of the precursor precipitated. The samples were characterized by XRD, FT-IR, DTA, FE-SEM and EDS. Upon heating of the precursor at 600 °C, α-Mn 2O 3 particles containing nanopores (cheese-like) were obtained. Most nanopores varied from ˜20 to 60 nm, and some were close to ˜100 nm in size. The α-Mn 2O 3 particles showed a strong twinning effect. At 1100 °C, Mn 3O 4 particles, obtained as a single crystal phase, formed a microporous 3D structure.

  2. Deposition of biogenic iron minerals in a methane oxidizing microbial mat.

    PubMed

    Wrede, Christoph; Kokoschka, Sebastian; Dreier, Anne; Heller, Christina; Reitner, Joachim; Hoppert, Michael

    2013-01-01

    The syntrophic community between anaerobic methanotrophic archaea and sulfate reducing bacteria forms thick, black layers within multi-layered microbial mats in chimney-like carbonate concretions of methane seeps located in the Black Sea Crimean shelf. The microbial consortium conducts anaerobic oxidation of methane, which leads to the formation of mainly two biomineral by-products, calcium carbonates and iron sulfides, building up these chimneys. Iron sulfides are generated by the microbial reduction of oxidized sulfur compounds in the microbial mats. Here we show that sulfate reducing bacteria deposit biogenic iron sulfides extra- and intracellularly, the latter in magnetosome-like chains. These chains appear to be stable after cell lysis and tend to attach to cell debris within the microbial mat. The particles may be important nuclei for larger iron sulfide mineral aggregates.

  3. Cr(OH)₃(s) Oxidation Induced by Surface Catalyzed Mn(II) Oxidation

    SciTech Connect

    Namgung, Seonyi; Kwon, M.; Qafoku, Nikolla; Lee, Gie Hyeon

    2014-09-16

    This study examined the feasibility of Cr(OH)₃(s) oxidation mediated by surface catalyzed Mn(II) oxidation under common groundwater pH conditions as a potential pathway of natural Cr(VI) contaminations. Dissolved Mn(II) (50 μM) was reacted with or without synthesized Cr(OH)₃(s) (1.0 g/L) at pH 7 – 9 under oxic or anoxic conditions. In the absence of Cr(OH)₃(s), homogeneous Mn(II) oxidation by dissolved O₂ was not observed at pH ≤ 8.0 for 50 d. At pH 9.0, by contrast, dissolved Mn(II) was completely removed within 8 d and precipitated as hausmannite. When Cr(OH)₃(s) was present, this solid was oxidized and released substantial amounts of Cr(VI) as dissolved Mn(II) was added into the suspension at pH ≥ 8.0 under oxic conditions. Our results suggest that Cr(OH)₃(s) was readily oxidized by a newly formed Mn oxide as a result of Mn(II) oxidation catalyzed on Cr(OH)₃(s) surface. XANES analysis of the residual solids after the reaction between 1.0 g/L Cr(OH)₃(s) and 204 μM Mn(II) at pH 9.0 for 22 d revealed that the product of surface catalyzed Mn(II) oxidation resembled birnessite. The rate and extent of Cr(OH)₃(s) oxidation was likely controlled by those of surface catalyzed Mn(II) oxidation as the production of Cr(VI) increased with increasing pH and initial Mn(II) concentrations. This study evokes the potential environmental hazard of sparingly soluble Cr(OH)₃(s) that can be a source of Cr(VI) in the presence of dissolved Mn(II).

  4. Oxidation of ambient biogenic secondary organic aerosol by hydroxyl radicals: Effects on cloud condensation nuclei activity

    NASA Astrophysics Data System (ADS)

    Wong, J. P. S.; Lee, A. K. Y.; Slowik, J. G.; Cziczo, D. J.; Leaitch, W. R.; Macdonald, A.; Abbatt, J. P. D.

    2011-11-01

    Changes in the hygroscopicity of ambient biogenic secondary organic aerosols (SOA) due to controlled OH oxidation were investigated at a remote forested site at Whistler Mountain, British Columbia during July of 2010. Coupled photo-oxidation and cloud condensation nuclei (CCN) experiments were conducted on: i) ambient particles exposed to high levels of gas-phase OH, and ii) the water-soluble fraction of ambient particles oxidized by aqueous-phase OH. An Aerodyne Aerosol Mass Spectrometer (AMS) monitored the changes in the chemical composition and degree of oxidation (O:C ratio) of the organic component of ambient aerosol due to OH oxidation. The CCN activity of size-selected particles was measured to determine the hygroscopicity parameter ($\\kappa$org,CCN) for particles of various degrees of oxygenation. In both cases, the CCN activity of the oxidized material was higher than that of the ambient particles. In general, $\\kappa$org,CCN of the aerosol increases with its O:C ratio, in agreement with previous laboratory measurements.

  5. Inter-relationships of MnO 2 precipitation, siderophore-Mn (III) complex formation, siderophore degradation, and iron limitation in Mn (II)-oxidizing bacterial cultures

    NASA Astrophysics Data System (ADS)

    Parker, Dorothy L.; Morita, Takami; Mozafarzadeh, Mylene L.; Verity, Rebecca; McCarthy, James K.; Tebo, Bradley M.

    2007-12-01

    To examine the pathways that form Mn (III) and Mn (IV) in the Mn (II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn (IV)O 2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn (III) complex or insoluble Mn (IV)O 2 minerals - but not both simultaneously. PVD-Mn (III) was present, and MnO 2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn (III) arose by predominantly ligand-mediated air oxidation of Mn (II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn (III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn (III), a process linked to the production of both MnO 2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn (III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO 2 to appear. These results suggest that P. putida cultures produce soluble Mn (III) or MnO 2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO 2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn (III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn (III) versus MnO 2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.

  6. 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.

  7. Adsorption of antimony(V) onto Mn(II)-enriched surfaces of manganese-oxide and FeMn binary oxide.

    PubMed

    Liu, Ruiping; Xu, Wei; He, Zan; Lan, Huachun; Liu, Huijuan; Qu, Jiuhui; Prasai, Tista

    2015-11-01

    Manganese(IV) oxide [Mn(IV)] potentially oxidizes antimony(III) [Sb(III)] to antimony(V) [Sb(V)] and improves Sb removal by FeMn binary oxide (FMBO) through an oxidation-adsorption mechanism. This study focused on the effect of Mn(IV) reductive dissolution by potassium sulfite (K2SO3) on Sb(V) adsorption onto manganese oxide (Mn-oxide) and FMBO. The maximum Sb(V) adsorption (Qmax,Sb(V)) increased from 1.0 to 1.1 mmol g(-1) for FMBO and from 0.4 to 0.6 mmol g(-1) for Mn-oxide after pretreatment with 10 mmol L(-1) K2SO3. The addition of 2.5 mmol L(-1) Mn(2+) also significantly improved Sb(V) adsorption, and the observed Qmax,Sb(V) increased to 1.4 and 1.0 mmol g(-1) for FMBO and Mn-oxide, respectively, with pre-adsorbed Mn(2+). Neither K2SO3 nor Mn(2+) addition had any effect on Sb(V) adsorption onto iron oxide (Fe-oxide). Mn(2+) introduced by either Mn(IV) dissolution or addition tended to form outer-sphere surface complexes with hydroxyl groups on Mn-oxide surfaces (MnOOH). Mn(2+) at 2.5 mmol L(-1) shifted the isoelectric point (pHiep) from 7.5 to 10.2 for FMBO and from 4.8 to 9.2 for Mn-oxide and hence benefited Sb(V) adsorption. The adsorption of Sb(V) onto Mn(2+)-enriched surfaces contributed to the release of Mn(2+), and the X-ray photoelectron spectra also indicated increased binding energy of Mn 2p3/2 after the adsorption of Sb(V) onto K2SO3-pretreated FMBO and Mn-oxide. Sb(V) adsorption involved the formation of inner-sphere complexes and contributed to the release of Mn(2+). In the removal of Sb(III) by Mn-based oxides, the oxidation of Sb(III) to Sb(V) by Mn(IV) oxides had an effect; however, Mn(IV) dissolution and Mn(2+)-enrichment also played an important role.

  8. 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.

  9. 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.

  10. 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.

  11. Oxidative Dissolution of Biogenic Uraninite in Groundwater at Old Rifle, CO

    SciTech Connect

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

    2011-09-12

    Reductive bioremediation is currently being explored as a possible strategy for uranium contaminated aquifers such as the Old Rifle site (Colorado, USA). The stability of U(IV) phases under oxidizing conditions is a key to the performance of this procedure. Biogenic uraninite, a bioreduction product for which kinetic and thermodynamic parameters are known, was deployed into wells using a novel membrane-walled cell to observe the rates and mechanisms of oxidative dissolution in situ in aquifers with different dissolved oxygen conditions. Observed in-aquifer dissolution rates were at least 50 to 100 times lower than measured in laboratory continuous flow reactors with artificial ground water. Upon retrieval, uraninite was found to have similar structure and stoichiometry as the parent material and to be free of U(VI), indicating dissolution occurs via oxidation and removal of surface atoms. Reactive transport modeling suggests that molecular diffusion is likely to be an important factor in limiting the rates of in-aquifer oxidation, and the presence of biomass enhances this effect. Interaction of ground water solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results constrain in-aquifer oxidation rates and indicate U(VI) is more stable in oxic ground water than previously expected.

  12. Microbially mediated formation of a new REE enriched Mn-oxide, Ytterby mine, Sweden

    NASA Astrophysics Data System (ADS)

    Sjöberg, Susanne; Allard, Bert; Rattray, Jayne E.; Callac, Nolwenn; Skelton, Alasdair; Ivarsson, Magnus; Karlsson, Stefan; Sjöberg, Viktor; Dupraz, Christophe

    2016-04-01

    Characterization of a black substance seeping from fractured bedrock in a subterranean tunnel revealed a new, microbially mediated, secondary manganese oxide mineralisation, highly enriched in rare earth elements (REEs). This tunnel is dry and at shallow depth and was built to convert the former Ytterby mine, known for the discovery of yttrium (Y), scandium (Sc) and five rare earth elements, into a fuel deposit for the Swedish Armed Forces. As the type locality of these rare earth elements, the Ytterby mine gave its name to yttrium, ytterbium, erbium and terbium. Geochemical analysis shows that the substance is enriched in REEs with concentrations one to two orders of magnitude higher than the surrounding rocks. Elemental analysis and X-ray diffraction establish that the main component is a manganese oxide of the birnessite type (general formula: [Na,Ca]0.5[Mn(III),Mn(IV)]2O4xAq). There are also minor fractions of calcite, some other manganese oxides, feldspars, quartz and about 1% organic matter, but no iron oxides. Leaching studies (sequential and selective) were performed in order to establish how the minor components are associated with the matrix (in the lattice or merely adsorbed on the outer surface). It shows that the Ytterby birnessite contains about 1% REEs in the lattice, as well as calcium but no sodium. Formation of birnessite by manganese oxidizing bacteria is well-known (e.g. Tebo et al, 2004). Quantitative PCR shows that the total number of bacteria in the Ytterby substance is in the order 1010 cells per g substance while the water feeding the fracture has in the order of 106 cells per ml groundwater. qPCR data further confirm that manganese oxidizing microorganisms are present and that the abundance varies with the seasons. Analysis of the precipitated manganese using electron paramagnetic resonance spectroscopy shows that the substance is composed of two or more components, with one part having a biogenic signature. The occurrence of C31 to C35

  13. Mn4+ emission in pyrochlore oxides

    SciTech Connect

    Du, Mao-Hua

    2015-01-01

    For the existing Mn4+ 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 Mn4+ emission in rare-earth hafnate, zirconate, and stannate pyrochlore oxides (RE2Hf2O7, RE2Zr2O7, and RE2Sn2O7). We show how the different sizes of the RE3+ cation in these pyrochlores affect the local structure of the distorted MnO6 octahedron, the Mn–O hybridization, and the Mn4+ emission energy. The Mn4+ emission energies of many pyrochlores are found to be higher than those currently known for Mn4+ doped oxides and should be closer to that of Y2O3:Eu3+ (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 Mn4+ emission energy. Our result shows that searching for materials that allow significant O–Mn–O bond angle distortion in a MnO6 octahedron is an effective approach to find new Mn4+ activated red phosphors with potential to replace the relatively expensive Y2O3:Eu3+ phosphor.

  14. 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.

  15. 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.

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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.

  18. 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.

  19. 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.

  20. 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.

  1. Water independent SO2 oxidation by Stabilised Criegee Intermediates from Biogenic Alkenes

    NASA Astrophysics Data System (ADS)

    Newland, Mike; Rickard, Andrew; Vereecken, Luc; Evans, Mat; Muñoz, Amalia; Ródenas, Milagros; Bloss, William

    2015-04-01

    Biogenic VOCs account for about 90% of global VOC emissions and these are dominated by the unsaturated hydrocarbons: isoprene (600 Tg yr-1) and monoterpenes (100 Tg yr-1). Stabilized Criegee Intermediates (SCI) are thought to be formed in the atmosphere mainly from reactions of unsaturated hydrocarbons with ozone. SCI have been shown in laboratory experiments to rapidly oxidise SO2 (k > 2x10-11 cm3 s-1) and NO2 (k = 7x10-12 cm3 s-1), providing a potentially important gas phase oxidation route for these species in the atmosphere. The importance of the SCI reaction with traces gases has been shown in modelling work to be critically dependent on the ratio of the rate constants for the reaction of the SCI with these trace gases and with H2O. Such modelling work has suggested that the SCI + SO2 reaction is only likely to be important in regions with high alkene emissions, e.g. forests, and that elsewhere SCI are likely to be almost entirely quenched by reaction with water, thus negating their importance as trace gas oxidants. However, it has been shown in laboratory experiments with small SCI that the reaction rate of SCI with water is structure dependent, with anti-CH3CHOO reacting fast with H2O (k > 1x10-14 cm3 s-1), and syn-CH3CHOO reacting orders of magnitude slower (k < 2x10-16 cm3 s-1). Here we present results from a series of ozonolysis experiments performed at the EUPHORE atmospheric simulation chamber in Valencia. These experiments measure the loss of SO2, in the presence of various biogenic alkenes (isoprene and three monoterpenes: α-pinene, β-pinene and limonene), as a function of water vapour. The SO2 loss shows a dependence on relative humidity for all systems studied, decreasing with increasing relative humidity. However, for all species, there also appears to be a fraction of the SO2 loss that shows a much lower sensitivity to relative humidity. We quantify the relative rates of reaction of the SCI produced in the ozonolysis of these biogenics with

  2. Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis

    PubMed Central

    Jin, Kyoungsuk; Chu, Arim; Park, Jimin; Jeong, Donghyuk; Jerng, Sung Eun; Sim, Uk; Jeong, Hui-Yun; Lee, Chan Woo; Park, Yong-Sun; Yang, Ki Dong; Kumar Pradhan, Gajendra; Kim, Donghun; Sung, Nark-Eon; Hee Kim, Sun; Nam, Ki Tae

    2015-01-01

    The oxygen evolution reaction (OER) is considered a major bottleneck in the overall water electrolysis process. In this work, highly active manganese oxide nano-catalysts were synthesized via hot injection. Facile surface treatment generated Mn(III) species on monodisperse 10 nm MnO nanocrystals (NCs). Size dependency of MnO NCs on OER activity was also investigated. Surprisingly, the partially oxidized MnO NCs only required 530 mV @ 5 mA cm−2 under near neutral conditions. PMID:25998696

  3. 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.

  4. 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...

  5. Effect of MnO2 morphology on the catalytic oxidation of toluene over Ag/MnO2 catalysts

    NASA Astrophysics Data System (ADS)

    Li, Jiamin; Qu, Zhenping; Qin, Yuan; Wang, Hui

    2016-11-01

    The Ag/MnO2 catalysts with different morphologies (wire-like, rod-like and tube-like) are used as toluene oxidation catalysts in an attempt to investigate how the structures of support affect the interaction of Ag and MnO2, and thus the toluene catalytic activity. Analysis by TEM, H2-TPR and XPS measurements reveals that the structures of MnO2 influence the particle size and dispersion of silver particles and the combination of silver particles with MnO2. Meanwhile, the addition of Ag regulates the performance of MnO2. The small particle size and hemispherically shaped Ag particles are easily to form and homogeneously dispersed on the surface of wire-like MnO2. And this specific form of Ag shows the strongest interaction with MnO2, which promotes the low-temperature reducibility of support and generated more lattice oxygen in metal oxides. The Ag/MnO2 nanowires sample exhibits the highest reactivity for toluene oxidation with a complete conversion at 220 °C. Therefore, the excellent catalytic performance of Ag/MnO2 nanowires catalyst for toluene oxidation is clearly connected with the interaction between the Ag and MnO2, which is determined by the morphology of MnO2 support.

  6. 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.

  7. Morphology of biogenic iron oxides records microbial physiology and environmental conditions: toward interpreting iron microfossils.

    PubMed

    Krepski, S T; Emerson, D; Hredzak-Showalter, P L; Luther, G W; Chan, C S

    2013-09-01

    Despite the abundance of Fe and its significance in Earth history, there are no established robust biosignatures for Fe(II)-oxidizing micro-organisms. This limits our ability to piece together the history of Fe biogeochemical cycling and, in particular, to determine whether Fe(II)-oxidizers played a role in depositing ancient iron formations. A promising candidate for Fe(II)-oxidizer biosignatures is the distinctive morphology and texture of extracellular Fe(III)-oxyhydroxide stalks produced by mat-forming microaerophilic Fe(II)-oxidizing micro-organisms. To establish the stalk morphology as a biosignature, morphologic parameters must be quantified and linked to the microaerophilic Fe(II)-oxidizing metabolism and environmental conditions. Toward this end, we studied an extant model organism, the marine stalk-forming Fe(II)-oxidizing bacterium, Mariprofundus ferrooxydans PV-1. We grew cultures in flat glass microslide chambers, with FeS substrate, creating opposing oxygen/Fe(II) concentration gradients. We used solid-state voltammetric microelectrodes to measure chemical gradients in situ while using light microscopy to image microbial growth, motility, and mineral formation. In low-oxygen (2.7-28 μm) zones of redox gradients, the bacteria converge into a narrow (100 μm-1 mm) growth band. As cells oxidize Fe(II), they deposit Fe(III)-oxyhydroxide stalks in this band; the stalks orient directionally, elongating toward higher oxygen concentrations. M. ferrooxydans stalks display a narrow range of widths and uniquely biogenic branching patterns, which result from cell division. Together with filament composition, these features (width, branching, and directional orientation) form a physical record unique to microaerophilic Fe(II)-oxidizer physiology; therefore, stalk morphology is a biosignature, as well as an indicator of local oxygen concentration at the time of formation. Observations of filamentous Fe(III)-oxyhydroxide microfossils from a ~170 Ma marine Fe

  8. 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).

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 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...

  15. 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...

  16. 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...

  17. 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...

  18. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  19. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  20. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  1. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  2. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  3. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  4. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  5. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  6. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  7. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  8. 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.

  9. 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.

  10. Composition and arsenic-attenuating capacity of biogenic iron (hydr)oxide flocs at the Lava Cap Mine Superfund Site, Nevada County, CA.

    NASA Astrophysics Data System (ADS)

    Foster, A. L.; Ona-Nguema, G.; Tufano, K.; Brown, G. E.

    2008-12-01

    The Lava Cap Mine Site (LCMS) is on the National Priority List due to the elevated human health risk presented by the catastrophic release of several thousand cubic meters of arsenic (As) enriched tailings (average: 500 ppm As ) from the site. These tailings were released into a creek and lake (former tailings retention pond) in a low-density residential area where ground water is the primary source of drinking water. Although oxidation of iron (Fe) sulfides (pyrite and arsenopyrite) from tailings are the main sources of As and Fe, buffering by carbonate minerals prevents formation of acidic waters. Macroscopic accumulations of fluffy Fe (hydr)oxide are observed suspended in the water column or at the sediment-water interface in creeks, ponds, and seeps of the LCMS. Microscopic analysis indicates that the Fe (hydr)oxide is predominantly associated with the sheaths of bacteria identified as members of the genus Leptothrix, which are known to enzymatically oxidize Fe and manganese (Mn) under oligotrophic, near-neutral, sub oxic conditions. Both Fe- encrusted Leptothrix sheaths (which are largely devoid of cells) and free aggolmerations of Fe hydr(oxide) support morphologically distinct Eubacteria whose identity is currently under investigation. Dried biogenic Fe (hydr)oxide averages 4.4 % organic carbon, 20.2 % Fe, and 0.91% As (9100 ppm), making it attractive as a potential natural biosorbent for As and Fe. Water flow rate is a very important control on the amount of As retained in biogenic Fe (hydr)oxide flocs, based on monitoring of a natural passive bioreactor system. In addition, a pond with nearly stagnant water accumulated approximately one order of magnitude more As (dried) than a seep site with faster-running water, even though there was only a 5-fold difference in their median filtered (0.45 micron) arsenic concentrations. Most Probable Number estimates and analysis of PCR amplicons of Eubacterial DNA indicate that populations of Fe-, As-, and sulfate

  11. MnOx/Graphene for the Catalytic Oxidation and Adsorption of Elemental Mercury.

    PubMed

    Xu, Haomiao; Qu, Zan; Zong, Chenxi; Huang, Wenjun; Quan, Fuquan; Yan, Naiqiang

    2015-06-02

    MnOx/graphene composites were prepared and employed to enhance the performance of manganese oxide (MnOx) for the capture of elemental mercury (Hg(0)) in flue gas. The composites were characterized using FT-IR, XPS, XRD, and TEM, and the results showed that the highly dispersed MnOx particles could be readily deposited on graphene nanosheets via hydrothermal process described here. Graphene appeared to be an ideal support for MnOx particles and electron transfer channels in the catalytic oxidation of Hg(0) at a high efficiency. Thus, MnOx/graphene-30% sorbents exhibited an Hg(0) removal efficiency of greater than 90% at 150 °C under 4% O2, compared with the 50% removal efficiency of pure MnOx. The mechanism of Hg(0) capture is discussed, and the main Hg(0) capture mechanisms of MnOx/graphene were catalytic oxidation and adsorption. Mn is the main active site for Hg(0) catalytic oxidation, during which high valence Mn (Mn(4+) or Mn(3+)) is converted to low valence Mn (Mn(3+) or Mn(2+)). Graphene enhanced the electrical conductivity of MnOx, which is beneficial for catalytic oxidation. Furthermore, MnOx/graphene exhibited an excellent regenerative ability, and is a promising sorbent for capturing Hg(0).

  12. Catalytic Oxidation of NO over MnOx-CeO₂ and MnOx-TiO₂ Catalysts.

    PubMed

    Zeng, Xiaolan; Huo, Xiaoyue; Zhu, Tianle; Hong, Xiaowei; Sun, Ye

    2016-11-14

    A series of MnOx-CeO₂ and MnOx-TiO₂ catalysts were prepared by a homogeneous precipitation method and their catalytic activities for the NO oxidation in the absence or presence of SO₂ were evaluated. Results show that the optimal molar ratio of Mn/Ce and Mn/Ti are 0.7 and 0.5, respectively. The MnOx-CeO₂ catalyst exhibits higher catalytic activity and better resistance to SO₂ poisoning than the MnOx-TiO₂ catalyst. On the basis of Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), and scanning transmission electron microscope with mapping (STEM-mapping) analyses, it is seen that the MnOx-CeO₂ catalyst possesses higher BET surface area and better dispersion of MnOx over the catalyst than MnOx-TiO₂ catalyst. X-ray photoelectron spectroscopy (XPS) measurements reveal that MnOx-CeO₂ catalyst provides the abundance of Mn(3+) and more surface adsorbed oxygen, and SO₂ might be preferentially adsorbed to the surface of CeO₂ to form sulfate species, which provides a protection of MnOx active sites from being poisoned. In contrast, MnOx active sites over the MnOx-TiO₂ catalyst are easily and quickly sulfated, leading to rapid deactivation of the catalyst for NO oxidation. Furthermore, temperature programmed desorption with NO and O₂ (NO + O₂-TPD) and in situ diffuse reflectance infrared transform spectroscopy (in situ DRIFTS) characterizations results show that the MnOx-CeO₂ catalyst displays much stronger ability to adsorb NOx than the MnOx-TiO₂ catalyst, especially after SO₂ poisoning.

  13. Eco-friendly decoration of graphene oxide with biogenic silver nanoparticles: antibacterial and antibiofilm activity

    NASA Astrophysics Data System (ADS)

    de Faria, Andreia Fonseca; de Moraes, Ana Carolina Mazarin; Marcato, Priscyla Daniely; Martinez, Diego Stéfani Teodoro; Durán, Nelson; Filho, Antônio Gomes Souza; Brandelli, Adriano; Alves, Oswaldo Luiz

    2014-02-01

    This work reports on preparation, characterization, and antibacterial activity of graphene oxide (GO) decorated with biogenic silver nanoparticles (Bio-AgNPs) produced by the fungus Fusarium oxysporum. This nanocomposite (Bio-GOAg) was prepared by an ex situ process through the physical mixture of a GO dispersion with the previously prepared Bio-AgNPs. The adsorption of the Bio-AgNPs onto the GO sheets was confirmed by transmission electron microscopy. The average size of the Bio-AgNPs anchored onto the GO surface was found to be 3.5 nm. The antibacterial activity of the Bio-GOAg nanocomposite against Gram-positive and Gram-negative microorganisms was investigated and a very promising result was found for the Gram-negative strains. In addition, the Bio-GOAg nanocomposite displayed a very strong biocidal activity against the Salmonella typhimurium strain at a concentration of 2.0 μg/mL. The antibiofilm activity toward S. typhimurium adhered on stainless steel surfaces was also investigated. The results showed 100 % inhibition of the adhered cells after exposure to the Bio-GOAg nanocomposite for 1 h.

  14. Secondary Organic Aerosol Formation and Organic Nitrate Yield from NO3 Oxidation of Biogenic Hydrocarbons

    PubMed Central

    2014-01-01

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m3 indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38–65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m–3, suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location’s mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed. PMID:25229208

  15. The effects of fire on biogenic emissions of methane and nitric oxide from wetlands

    NASA Technical Reports Server (NTRS)

    Levine, Joel S.; Cofer, Wesley R., III; Sebacher, Daniel I.; Rhinehart, Robert P.; Winstead, Edward L.; Sebacher, Shirley; Hinkle, C. Ross; Schmalzer, Paul A.; Koller, Albert M., Jr.

    1990-01-01

    Enhanced emissions of methane (CH4) and nitric oxide (NO) were measured following three controlled burns in a Florida wetlands in 1987 and 1988. Wetlands are the major global source of methane resulting from metabolic activity of methanogenic bacteria. Methanogens require carbon dioxide, acetate, or formate for their growth and the metabolic production of methane. All three water-soluble compounds are produced in large concentrations during biomass burning. Postfire methane emissions exceeded 0.15 g CH 4/sq m per day. Preburn and postburn measurements of soil nutrients indicate significant postburn increases in soil ammonium, from 8.35 to 13.49 parts per million (ppm) in the upper 5 cm of the Juncus marsh and from 8.83 to 23.75 ppm in the upper 5 cm of the Spartina marsh. Soil nitrate concentrations were found to decrease in both marshes after the fire. These measurements indicate that the combustion products of biomass burning exert an important 'fertilizing' effect on the biosphere and on the biogenic production of environmentally significant atmospheric gases.

  16. 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

  17. Biogenic nanoparticles: copper, copper oxides, copper sulphides, complex copper nanostructures and their applications.

    PubMed

    Rubilar, Olga; Rai, Mahendra; Tortella, Gonzalo; Diez, Maria Cristina; Seabra, Amedea B; Durán, Nelson

    2013-09-01

    Copper nanoparticles have been the focus of intensive study due to their potential applications in diverse fields including biomedicine, electronics, and optics. Copper-based nanostructured materials have been used in conductive films, lubrification, nanofluids, catalysis, and also as potent antimicrobial agent. The biogenic synthesis of metallic nanostructured nanoparticles is considered to be a green and eco-friendly technology since neither harmful chemicals nor high temperatures are involved in the process. The present review discusses the synthesis of copper nanostructured nanoparticles by bacteria, fungi, and plant extracts, showing that biogenic synthesis is an economically feasible, simple and non-polluting process. Applications for biogenic copper nanoparticles are also discussed.

  18. Chemical and biological reduction of Mn (III)-pyrophosphate complexes: Potential importance of dissolved Mn (III) as an environmental oxidant

    NASA Astrophysics Data System (ADS)

    Kostka, Joel E.; Luther, George W., III; Nealson, Kenneth H.

    1995-03-01

    Dissolved Mn (III) is a strong oxidant which could play an important role in the biogeochemistry of aquatic environments, but little is known about this form of Mn. Mn(III) was shown to form a stable complex with pyrophosphate which is easily measured by uv-vis spectrophotometry. The Mn(III)-pyrophosphate complex was produced at concentrations of 5 μM to 10 mM Mn at neutral pH. Inorganic electron donors, Fe(II) and sulfide, abiotically reduced Mn(III)-pyrophosphate in seconds with a stoichiometry of 1:1 and near 1:2 reductant:Mn (III), respectively. Shewanella putrefaciens strain MR-1 catalyzed the reduction of Mn(III)-pyrophosphate with formate or lactate as electron donors. Reduction of Mn(III) catalyzed by MR-1 was inhibited under aerobic conditions but only slightly under anaerobic conditions upon addition of the alternate electron acceptor, nitrate. MR-1 catalyzed reduction was also inhibited by metabolic inhibitors including formaldehyde, tetrachlorosalicylanilide (TCS), carbonyl cyanide m-chlorophenylhydrazone (CCCP), 2- n-heptyl-4-hydroxyquinoline N-oxide (HQNO), but not antimycin A. When formate or lactate served as electron donor for Mn(III) reduction, carbon oxidation to CO 2 was coupled to the respiration of Mn (III). Using the incorporation of 3H-leucine into the TCA-insoluble fraction of culture extracts, it was shown that Mn (III) reduction was coupled to protein synthesis in MR-1. These data indicate that Mn (III) complexes may be produced under conditions found in aquatic environments and that the reduction of Mn(III) can be coupled to the cycling of Fe, S, and C.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O. T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.

    2017-02-01

    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 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

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

    SciTech Connect

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O. T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.

    2017-01-01

    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 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

    This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

  2. Microstructural characterizations of different Mn-oxide nanoparticles used as models in toxicity studies

    NASA Astrophysics Data System (ADS)

    Gotić, Marijan; Jurkin, Tanja; Musić, Svetozar; Unfried, Klaus; Sydlik, Ulrich; Bauer-Šegvić, Anamarija

    2013-07-01

    Mn-oxide microstructures were investigated by XRD, FT-IR, TEM, FE SEM and EDS techniques. The oxidation of the aqueous solutions of manganese (II) chloride by hydrogen peroxide was employed to synthesize pure 20-30-nm pseudospherical hausmannite (Mn3O4) nanoparticles and manganite (γ-MnOOH) nanowires. The α-MnO2 nanotubes and nanorods were hydrothermally synthesized starting from a KMnO4 precursor, then modified with the addition of divalent metal cations Mn2+, Cu2+, Ni2+ and Fe2+. The modification with Mn2+ induced the transformation of α-MnO2 nanotube into 3D β-MnO2 (pyrolusite) prismatic nanoparticles, whereas the low-crystalline α-MnO2 nanorods were transformed into disk-like γ-MnO2 nanoparticles. The modification with Cu2+ and Ni2+ induced the structural transformation of α-MnO2 into a mixture of MnO2 polymorphs. The modification with Cu2+ decreased, whereas the modification with Ni2+ improved the crystallinity of MnO2. The modification with Fe2+ induced the structural transformation of α-MnO2 into γ-MnO2, a decrease in crystallinity and the segregation of α-Fe2O3 (hematite). Thus the modification of MnO2 with Fe2+ (Mn2+) divalent metal cations that can be oxidized into Fe3+ (Mn4+) by a KMnO4 precursor differs significantly in comparison with, in this case, non-oxidizable cations such as Cu2+ and Ni2+. On the other hand, the advantage that the modification of MnO2 with Mn2+ produces chemically identical compounds with different morphology can be used as a model system for toxicity studies. In this work the preliminary measurements of intracellular oxidative stress in epithelial cells induced by manganese oxide nanoparticles are reported.

  3. Quantum Monte-Carlo Study of Mn and Mn-oxide clusters.

    NASA Astrophysics Data System (ADS)

    Kino, Hiori; Wagner, Lucas K.; Mitas, Lubos

    2007-03-01

    Many molecules and clusters of Mn and Mn-oxide have not only interesting physical properties but also can be found in enzymes as important components in biochemical reactions. The electronic structure calculations of these systems are difficult and, for example, choice of exchange-correlation functionals in Density Functional Theory can significantly influence both ground state geometries and spin-state predictions. Therefore, highly accurate calculation is very desirable for these systems. Experimentally, it is established that the Mn dimer is a van der Waals system with weak binding, however, the spin multiplicity has not been settled unambiguously with possibilities covering a range from singlet, triplet, etc, up to 2S+1=11. On the other hand, MnnOn molecules are quite well understood as being a high-spin system, but their geometries depend on the exchange-correlation functionals. We will present our recent results from the fixed-node quantum Monte Carlo calculations of these systems. We will also report on recent progress in modeling the [4Mn-4O-Ca] cluster structural prototypes for the oxygen evolving center in green plants Photosystem II.

  4. Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides

    SciTech Connect

    Wei, Chunguang; Xu, Chengjun; Li, Baohua; Nan, Ding; Ma, Jun; Kang, Feiyu

    2012-07-15

    Highlights: ► Single-crystal γ-MnOOH was obtained via hydrothermal method. ► α-MnO{sub 2} was transformed to γ-MnOOH by a dissolution-growth-recrystallization process. ► α-MnO{sub 2} preferred growth on (111{sup ¯}) crystal plane of γ-MnOOH. ► γ-MnOOH was a useful precursor to prepare manganese oxide via calcination. -- Abstract: Formation and conversion mechanisms between single-crystal gamma-MnOOH and manganese oxides had investigated systematically. Without extra surfactant or template, α-MnO{sub 2} nanorods and prismatic single crystalline γ-MnOOH rods had been synthesized under hydrothermal treatment in this study. The formation and conversion mechanisms of prismatic γ-MnOOH rod were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). It was found that the formation process includes three evolution stages: (1) formation of α-MnO{sub 2} nanorods whiskers; (2) transformation from α-MnO{sub 2} nanorods to prismatic γ-MnOOH rods by a dissolution-growth-recrystallization process; and (3) preferred growth on (111{sup ¯}) crystal plane. In addition, β-MnO{sub 2}, Mn{sub 2}O{sub 3} or Mn{sub 3}O{sub 4} rods could be obtained by calcination of the γ-MnOOH rods at different temperatures, which indicated that γ-MnOOH is an important precursor for preparing manganese oxides. The morphology and dimension of γ-MnOOH rods remained unchanged after converted to β-MnO{sub 2}, Mn{sub 2}O{sub 3} and Mn{sub 3}O{sub 4}.

  5. Enhanced Removal of Biogenic Hydrocarbons in Power Plant Plumes Constrains the Dependence of Atmospheric Hydroxyl Concentrations on Nitrogen Oxides

    NASA Astrophysics Data System (ADS)

    De Gouw, J. A.; Trainer, M.; Parrish, D. D.; Brown, S. S.; Edwards, P.; Gilman, J.; Graus, M.; Hanisco, T. F.; Kaiser, J.; Keutsch, F. N.; Kim, S. W.; Lerner, B. M.; Neuman, J. A.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Veres, P. R.; Warneke, C.; Wolfe, G.

    2015-12-01

    Hydroxyl (OH) radicals in the atmosphere provide one of the main chemical mechanisms for the removal of trace gases. OH plays a central role in determining the atmospheric lifetime and radiative forcing of greenhouse gases like methane. OH also plays a major role in the oxidation of organic trace gases, which can lead to formation of secondary pollutants such as ozone and PM2.5. Due to its very short atmospheric lifetime of seconds or less, OH concentrations are extremely variable in space and time, which makes measurements and their interpretation very challenging. Several recent measurements have yielded higher than expected OH concentrations. To explain these would require the existence of unidentified, radical recycling processes, but issues with the measurements themselves are also still being discussed. During the NOAA airborne SENEX study in the Southeast U.S., the biogenic hydrocarbons isoprene and monoterpenes were consistently found to have lower mixing ratios in air masses with enhanced nitrogen oxides from power plants. We attribute this to faster oxidation rates of biogenic hydrocarbons due to increased concentrations of OH in the power plant plumes. Measurements at different downwind distances from the Scherer and Harllee Branch coal-fired power plants near Atlanta are used to constrain the dependence of OH on nitrogen oxides. It is found that OH concentrations were highest at nitrogen dioxide concentrations of 1-2 ppbv and decreased at higher and at lower concentrations. These findings agree with the expected dependence of OH on nitrogen oxide concentrations, but do not appear to be consistent with the reports in the literature that have shown high OH concentrations in regions of the atmosphere with high biogenic emissions and low NOx concentrations that would require unidentified radical recycling processes to be explained.

  6. Correlation between Mn oxidation state and magnetic behavior in Mn/ZnO multilayers prepared by sputtering

    SciTech Connect

    Cespedes, E.; Garcia-Lopez, J.; Garcia-Hernandez, M.; Andres, A. de; Prieto, C.

    2007-08-01

    Compositional, microstructural, and magnetic characterization of [ZnO(30 A )/Mn(x)]{sub n} multilayers prepared by sputtering is presented to study the observed ferromagnetism in the Mn-ZnO system. The nominal Mn layer thickness, x, is varied from 3 to 60 A , while the number of bilayers, n, is increased to maintain the total amount of Mn constant. Microstructure information was deduced from x-ray reflectivity, Mn oxidation state was determined by x-ray absorption spectroscopy, and magnetic properties were measured over a temperature range of 5-400 K. Magnetic behavior of these samples is found to be related to the Mn layer thickness (x). Multilayers with x{>=}30 A exhibit ferromagnetism with a Curie temperature above 400 K, while mostly paramagnetic behavior is obtained for x<15 A . Magnetic behavior is discussed in terms of electronic and structural parameters of samples. Mn-ZnO interface effect is related to the ferromagnetic order of the samples, but it is not a sufficient condition. The essential role of the Mn oxidation state in the magnetic behavior of this system is pointed out. It is shown a correlation between the obtained ferromagnetism and a Mn oxidation state close to 2+.

  7. Low-temperature magnetic properties of pelagic carbonates: Oxidation of biogenic magnetite and identification of magnetosome chains

    NASA Astrophysics Data System (ADS)

    Chang, Liao; Winklhofer, Michael; Roberts, Andrew P.; Heslop, David; Florindo, Fabio; Dekkers, Mark J.; Krijgsman, Wout; Kodama, Kazuto; Yamamoto, Yuhji

    2013-12-01

    marine carbonates provide important records of past environmental change. We carried out detailed low-temperature magnetic measurements on biogenic magnetite-bearing sediments from the Southern Ocean (Ocean Drilling Program (ODP) Holes 738B, 738C, 689D, and 690C) and on samples containing whole magnetotactic bacteria cells. We document a range of low-temperature magnetic properties, including reversible humped low-temperature cycling (LTC) curves. Different degrees of magnetite oxidation are considered to be responsible for the observed variable shapes of LTC curves. A dipole spring mechanism in magnetosome chains is introduced to explain reversible LTC curves. This dipole spring mechanism is proposed to result from the uniaxial anisotropy that originates from the chain arrangement of biogenic magnetite, similar to published results for uniaxial stable single domain (SD) particles. The dipole spring mechanism reversibly restores the remanence during warming in LTC measurements. This supports a previous idea that remanence of magnetosome chains is completely reversible during LTC experiments. We suggest that this magnetic fingerprint is a diagnostic indicator for intact magnetosome chains, although the presence of isolated uniaxial stable SD particles and magnetically interacting particles can complicate this test. Magnetic measurements through the Eocene section of ODP Hole 738B reveal an interval with distinct magnetic properties that we interpret to originate from less oxidized biogenic magnetite and enrichment of a biogenic "hard" component. Co-occurrence of these two magnetic fingerprints during the late Eocene in the Southern Ocean indicates less oxic conditions, probably due to increased oceanic primary productivity and organic carbon burial.

  8. Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

    PubMed

    Kim, Soon Sam; Bargar, John R; Nealson, Kenneth H; Flood, Beverly E; Kirschvink, Joseph L; Raub, Timothy D; Tebo, Bradley M; Villalobos, Mario

    2011-10-01

    Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

  9. Fertilizer impact on biogenic nitric oxide emissions from agricultural soils of the Taklimakan desert (Xinjiang, China)

    NASA Astrophysics Data System (ADS)

    Fechner, A. D.; Behrendt, T.; Bruse, M.; Mamtimin, B.; Andreae, M. O.; Meixner, F. X.

    2012-04-01

    It is known that soil microbial processes play a crucial role in the production and consumption of atmospheric trace gases worldwide. Soils are mostly a major source of biogenic nitric oxide (NO). The main influencing factors controlling soil NO emissions are soil moisture, soil temperature, as well as nutrient availability. Adding fertilizer to agricultural soils changes the pool of nutrients and impacts the net NO emission from these soils. Irrigated and fertilized oases around the great Central Asian Taklamakan desert form the backbone of the agricultural output (80% of the Chinese cotton production) of the Xinjiang Uygur Autonomous Region (NW-China). While nowadays 90% of the agricultural output is produced on just 4.3% of Xinjiang's total area, recent and future enlargement of farmland and intensification of agriculture will definitely impact the regional soil NO emission and consequently the budget of nitrogen oxides and ozone. We present a systematic laboratory study of the influence of urea (CH4N2O) and diammonium hydrogen phosphate ((NH4)2HPO4, DAP) fertilizer on NO emissions from Xinjiang soil samples. Urea is the most widely and excessively applied fertilizer in Xinjiang. Typically, about 600 kg ha-1 yr-1(in terms of mass of nitrogen) were applied to a cotton field in four separate events. In the laboratory, the fertilizer was applied accordingly, ranging from one quarter of the field amount within one of the four events (i.e. 37.5 kg ha-1 yr-1) to quadruple of that (150 kg ha-1 yr-1). Two different measurement series have been performed on six sub- samples (each out of a total of three soil samples taken in Xinjiang): the first series was conducted solely with urea fertilizer, the second one with a mixture of urea and DAP (2:1). All sub-samples were prepared in a standardized way: a fixed mass of soil (~0.06 kg, dried in field) was sieved (2 mm) and stored at 4° C. Then it was wetted up to a soil moisture tension of 1.8 pF. Subsequently, fertilizer was

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

    SciTech Connect

    Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho; Han, Jeong-Sik; Jeong, Byung-Hun; Park, Young-Kwon; Jeon, Jong-Ki

    2016-10-15

    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 of 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.

  11. Stability of beta MnOOH and manganese oxide deposition from springwater.

    USGS Publications Warehouse

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

    1982-01-01

    beta MnOOH is precipitated preferentially (with respect to Mn3O4) at T near 0oC when Mn2+ is oxidized in aerated aqueous solutions. Upon aging in solutions open to the atmosphere, a slurry of beta MnOOH 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+ + 1/4O2(aq) + 3/2H2O rt arrow beta MnOOH(c) + 2H+ and the disproportionation reaction 2beta MnOOH(c) + 2H+ rt arrow 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 028DELTA Gof of -129.8 + or - 0.6 kcal/mol was obtained for beta MnOOH from experimental data by assuming that the reaction affinity for the oxidation reaction is equal to that for the disproportionation, and a value of -129.8 + or - 0.5 kcal/mol was determined by measuring the redox potentials for the postulated half-reaction MnO2(c) + H+ + e- rt arrow beta MnOOH(c) at 0o, 5o, and 15oC and extrapolating to 25oC. Both these values are consistent with laboratory observations that beta MnOOH is less stable than gamma MnOOH or Mn3O4 at 25oC. Analytical data for Mn-depositing springwater samples are consistent with a non-equilibrium model involving disproportionation of either beta MnOOH or Mn3O4. (Authors' abstract)-T.R.

  12. Nano-sized Mn oxide/agglomerated silsesquioxane composite as a good catalyst for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Madadkhani, Sepideh

    2016-12-01

    Water splitting to hydrogen and oxygen is an important reaction to store sustainable energies, and water oxidation is identified as the bottleneck for water splitting because it requires the high activation energy to perform. Herein a nano-sized Mn oxide/agglomerated silsesquioxane composite was used to synthesize an efficient catalyst for water oxidation. The composite was synthesized by a straightforward and simple procedure and characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, dynamic light scattering, X-ray diffraction spectrometry, and electrochemical methods. Silsesquioxane causes good dispersion of Mn in the composite. The water-oxidizing activity of this composite was studied in the presence of cerium(IV) ammonium nitrate. The composite at the best calcination temperature (300 °C) shows a turnover frequency 0.3 (mmol O2/mol Mn.s). Regarding the low-cost, environmentally friendly precursors, simple synthesis, and efficiency for water oxidation, the composite is a promising catalyst that can be used in artificial photosynthetic systems for water splitting. We used Agglomerated silsesquioxane as a support for nano-sized Mn oxide to synthesize a good water-oxidizing catalyst.

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

    PubMed

    Andeer, Peter F; Learman, Deric R; McIlvin, Matt; Dunn, James A; Hansel, Colleen M

    2015-10-01

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

  14. Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO2 Using Quick X-ray Absorption Spectroscopy.

    PubMed

    Simanova, Anna A; Peña, Jasquelin

    2015-09-15

    Manganese oxides are important environmental oxidants that control the fate of many organic and inorganic species including cobalt. We applied ex situ quick X-ray absorption spectroscopy (QXAS) to determine the time evolution of Co(II) and Co(III) surface loadings and their respective average surface speciation in Mn(III)-rich δ-MnO2 samples at pH 6.5 and loadings of 0.01-0.20 mol Co mol(-1) Mn. In this Mn oxide, which contained few unoccupied vacancies but abundant Mn(III) at edge and interlayer sites, Co(II) sorption and oxidation started at the particle edges. We found no evidence for Co(II) oxidation by interlayer Mn(III) or Mn(III, IV) adjacent to vacancy sites at <10 min. After 10 min, basal surface sites were implicated due to slow Co oxidation by interlayer Mn(III) and reactive sites formed upon removal of interlayer Mn(III), such that 50-60% of the sorbed Co was incorporated into the MnO2 sheets or adsorbed at vacancy sites by 12 h. Our findings indicate that the redox reactivity of surface sites depends on Mn valence and crystallographic location, with Mn(III) at the edges being the most effective oxidant at short reaction times and Mn(III,IV) in the MnO2 sheet contributing at longer reaction times.

  15. 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.

  16. c-Type cytochromes and manganese oxidation in Pseudomonas putida MnB1

    SciTech Connect

    Caspi, R.; Tebo, B.M.; Haygood, M.G.

    1998-10-01

    Pseudomonas putida MnB1 is an isolate from an Mn oxide-encrusted pipeline that can oxidize Mn(II) to Mn oxides. The authors used transposon mutagenesis to construct mutants of strain MnB1 that are unable to oxidize manganese, and they characterized some of these mutants. The mutants were divided into three groups: mutants defective in the biogenesis of c-type cytochromes, mutants defective in genes that encode key enzymes of the tricarboxylic acid cycle, and mutants defective in the biosynthesis of tryptophan. The mutants in the first two groups were cytochrome c oxidase negative and did not contain c-type cytochromes. Mn(II) oxidation capability could be recovered in a c-type cytochrome biogenesis-defective mutant by complementation of the mutation.

  17. Origin of concretionary Mn-Fe-oxides in stream sediments of Maine, U.S.A.

    USGS Publications Warehouse

    Nowlan, G.A.; McHugh, J.B.; Hessin, T.D.

    1983-01-01

    Studies of stream and sediment-pore waters largely explain the genesis of concretionary Mn-Fe-oxides in Maine. Waters of two small streams near Jackman, Maine, were studied in terms of pH, Eh, dissolved oxygen, dissolved organic carbon, dissolved Mn, total dissolved Fe, and ferrous and ferric Fe. Pyrite Creek has profuse concretions and coatings of Mn-Fe-oxides, whereas West Pyrite Creek has only sparse Mn-Fe-oxide stains. Pyrite Creek drains boggy terrain and West Pyrite Creek drains well-drained terrain. In West Pyrite Creek, stream and subjacent pore waters have chemical characteristics that do not differ greatly. However, dissolved Mn, ferrous Fe, dissolved oxygen, and in situ Eh measurements show that a steep Eh gradient exists between stream and subjacent pore waters of Pyrite Creek. The steep Eh gradient is manifested by the common zonation of coatings and stains on rocks in stream sediment. The bottom zone has no deposition of oxides, the middle zone is red and consists mostly of Fe-oxides, and the upper zone is black or dark-brown and consists of Mn-oxides with varying amounts of Fe-oxides. The zonation agrees with theoretical predictions of oxide stability as one moves from a reducing to an oxidizing environment. At locations where concretionary Mn-Fe-oxides form, pore waters are depleted of oxygen because of abundant decaying organic material in the stream sediment. The pore waters are charged with dissolved Mn and Fe because mechanically deposited Mn-Fe-oxides are remobilized due to the low-Eh conditions. Groundwaters also contribute dissolved Mn and Fe. Stream waters, on the other hand, are oxygenated and the high-Eh conditions result in low concentrations of dissolved Mn and Fe in stream waters because of the insolubility of Mn-Fe-oxides in high-Eh environments. Therefore, concretionary Mn-Fe-oxides form at the interface between pore and stream waters because Mn- and Fe-rich pore waters, which are undersaturated with respect to Mn-Fe-oxides, mix with

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

    SciTech Connect

    Liu, Zhiqi; Biegalski, Michael D; Hsu, Mr. S. L.; Shang, Dr. Shunli; Marker, Cassie; Liu, Jian; Li, Li; Fan, Lisha; Meyer, Tricia L; Wong, Anthony T; Nichols, John A; Chen, Deyang; You, Long; Chen, Zuhuang; Wang, Kai; Wang, Kevin; Ward, Thomas Zac; Gai, Zheng; Lee, Ho Nyung; Sefat, Athena Safa; Lauter, Valeria; Liu, Zi-Kui; Christen, Hans M.

    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.

  19. Coupled Mn(II) Oxidation Pathways by a Planktonic Roseobacter-like Bacterium

    NASA Astrophysics Data System (ADS)

    Hansel, C. M.; Francis, C. A.

    2005-12-01

    Bacteria belonging to the Roseobacter clade of the alpha-Proteobacteria are numerically abundant in coastal waters, ecologically significant in the cycling of (in)organic sulfur, and occupy a wide range of environmental niches. Here we reveal that Roseobacter-like bacteria may play a previously unrecognized role in the oxidation and cycling of manganese (Mn) in coastal waters. A diverse array of Mn(II)-oxidizing Roseobacter-like species were isolated from Elkhorn Slough, a coastal estuary adjacent to Monterey Bay, California. One isolate (designated AzwK-3b), in particular, rapidly oxidizes Mn(II) to insoluble Mn(III, IV) oxides. Interestingly, AzwK-3b is 100% identical (at the 16S rRNA level) to a previously reported Pfiesteria-associated Roseobacter-like bacterium, which does not posses the ability to oxidize Mn(II). Manganese(II) oxidation rates by live cultures and cell-free filtrates are substantially higher when incubated in the presence of light. Rates of oxidation by washed cell extracts, however, are light independent, which are actually identical to rates by cell-free filtrates incubated in the dark. Thus, AwwK-3b induces two Mn(II) oxidation mechanisms when incubated in the presence of light as opposed to predominantly direct enzymatic oxidation in the dark. Within the light, production of photochemically-active metabolites is coupled with initial direct enzymatic Mn(II) oxidation, resulting in substantially accelerated Mn(II) oxidation rates. Thus, Roseobacter-like bacteria may not only greatly influence Mn(II) oxidation and cycling within coastal surface waters, but may also induce a novel photo-oxidation pathway providing an alternative means of Mn(II) oxidation within the photic zone.

  20. Stabilization of mercury over Mn-based oxides: Speciation and reactivity by temperature programmed desorption analysis.

    PubMed

    Xu, Haomiao; Ma, Yongpeng; Huang, Wenjun; Mei, Jian; Zhao, Songjian; Qu, Zan; Yan, Naiqiang

    2017-01-05

    Mercury temperature-programmed desorption (Hg-TPD) method was employed to clarify mercury species over Mn-based oxides. The elemental mercury (Hg(0)) removal mechanism over MnOx was ascribed to chemical-adsorption. HgO was the primary mercury chemical compound adsorbed on the surface of MnOx. Rare earth element (Ce), main group element (Sn) and transition metal elements (Zr and Fe) were chosen for the modification of MnOx. Hg-TPD results indicated that the binding strength of mercury on these binary oxides followed the order of Sn-MnOxMnOx∼MnOxOx. The activation energies for desorption were calculated and they were 64.34, 101.85, 46.32, 117.14, and 106.92eV corresponding to MnOx, Ce-MnOx, Sn-MnOx, Zr-MnOx and Fe-MnOx, respectively. Sn-MnOx had a weak bond of mercury (Hg-O), while Zr-MnOx had a strong bond (HgO). Ce-MnOx and Fe-MnOx had similar bonds compared with pure MnOx. Moreover, the effects of SO2 and NO were investigated based on Hg-TPD analysis. SO2 had a poison effect on Hg(0) removal, and the weak bond of mercury can be easily destroyed by SO2. NO was favorable for Hg(0) removal, and the bond strength of mercury was enhanced.

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

    SciTech Connect

    Hansel, C. M.; Zeiner, C. A.; Santelli, C. M.; Webb, S. M.

    2012-07-16

    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. Finally, 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.

  2. 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.

  3. Chemical and structural investigation of the role of both Mn and Mn oxide in the formation of manganese silicate barrier layers on SiO{sub 2}

    SciTech Connect

    Casey, P.; Bogan, J.; Hughes, G.; Lozano, J. G.; Nellist, P. D.

    2011-09-01

    In this study, Mn silicate (MnSiO{sub 3}) barrier layers were formed on thermally grown SiO{sub 2} using both metallic Mn and oxidized Mn films, in order to investigate the role of oxygen in determining the extent of the interaction between the deposited Mn and the SiO{sub 2} substrate. Using x-ray photoelectron spectroscopy, it has been shown that a metallic Mn film with an approximate thickness of 1 nm cannot be fully converted to Mn silicate following vacuum annealing to 500 deg. C. Transmission electron microscopy (TEM) analysis suggests the maximum MnSiO{sub 3} layer thickness obtainable using metallic Mn is {approx}1.7 nm. In contrast, a {approx}1 nm partially oxidized Mn film can be fully converted to Mn silicate following thermal annealing to 400 deg. C, forming a MnSiO{sub 3} layer with a measured thickness of 2.6 nm. TEM analysis also clearly shows that MnSiO{sub 3} growth results in a corresponding reduction in the SiO{sub 2} layer thickness. It has also been shown that a fully oxidized Mn oxide thin film can be converted to Mn silicate, in the absence of metallic Mn. Based on these results it is suggested that the presence of Mn oxide species at the Mn/SiO{sub 2} interface facilitates the conversion of SiO{sub 2} to MnSiO{sub 3}, in agreement with previously published studies.

  4. 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 (MnO2), 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 MnO2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO2 powder was a very pure - commercially available - natural MnO2 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 MnO2 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 MnO2 surface (at pH 7). Therefore it is concluded that just because MnO2 is present in a filter bed, it does not necessarily mean that MnO2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides.

  5. Fabrication of MnO 2-pillared layered manganese oxide through an exfoliation/reassembling and oxidation process

    NASA Astrophysics Data System (ADS)

    Yuan, Jiaqi; Liu, Zong-Huai; Qiao, Shanfeng; Ma, Xiangrong; Xu, Naicai

    MnO 2-pillared layered manganese oxide has been first fabricated by a delamination/reassembling process followed by oxidation reaction and then by heat treatment. The structural evolution of MnO 2-pillared layered manganese oxide has been characterized by XRD, SEM, DSC-GTA, IR and N 2 adsorption-desorption. MnO 2-pillared layered manganese oxide shows a relative high thermal stability and mesoporous characteristic. The layered structure with a basal spacing of 0.66 nm could be maintained up to 400 °C. The electrochemical properties of the synthesized MnO 2-pillared layered manganese oxide have been studied using cyclic voltammetry in a mild aqueous electrolyte. Sample MnO 2-BirMO (300 °C) shows good capacitive behavior and cycling stability, and the specific capacitance value is 206 F g -1.

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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.

  12. Anaerobic Oxidation of [1,2-14C]Dichloroethene under Mn(IV)-Reducing Conditions

    PubMed Central

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

    1998-01-01

    Anaerobic oxidation of [1,2-14C]dichloroethene to 14CO2 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. PMID:16349554

  13. Kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

    NASA Astrophysics Data System (ADS)

    Toyoda, Kazuhiro; Tebo, Bradley M.

    2016-09-01

    The kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1 was measured under controlled conditions of the initial Mn(II) concentration, spore concentration, chemical speciation, pH, O2, and temperature. Mn(II) oxidation experiments were performed with spore concentrations ranging from 0.7 to 11 × 109 spores/L, a pH range from 5.8 to 8.1, temperatures between 4 and 58 °C, a range of dissolved oxygen from 2 to 270 μM, and initial Mn(II) concentrations from 1 to 200 μM. The Mn(II) oxidation rates were directly proportional to the spore concentrations over these ranges of concentration. The Mn(II) oxidation rate increased with increasing initial Mn(II) concentration to a critical concentration, as described by the Michaelis-Menten model (Km = ca. 3 μM). Whereas with starting Mn(II) concentrations above the critical concentration, the rate was almost constant in low ionic solution (I = 0.05, 0.08). At high ionic solution (I = 0.53, 0.68), the rate was inversely correlated with Mn(II) concentration. Increase in the Mn(II) oxidation rate with the dissolved oxygen concentration followed the Michaelis-Menten model (Km = 12-19 μM DO) in both a HEPES-buffered commercial drinking (soft) water and in artificial and natural seawater. Overall, our results suggest that the mass transport limitations of Mn(II) ions due to secondary Mn oxide products accumulating on the spores cause a significant decrease of the oxidation rate at higher initial Mn(II) concentration on a spore basis, as well as in more concentrated ionic solutions. The optimum pH for Mn(II) oxidation was approximately 7.0 in low ionic solutions (I = 0.08). The high rates at the alkaline side (pH > 7.5) may suggest a contribution by heterogeneous reactions on manganese bio-oxides. The effect of temperature on the Mn(II) oxidation rate was studied in three solutions (500 mM NaCl, ASW, NSW solutions). Thermal denaturation occurred at 58 °C and spore germination was evident at 40 °C in all three

  14. Nanostructured Mn-based oxides for electrochemical energy storage and conversion.

    PubMed

    Zhang, Kai; Han, Xiaopeng; Hu, Zhe; Zhang, Xiaolong; Tao, Zhanliang; Chen, Jun

    2015-02-07

    Batteries and supercapacitors as electrochemical energy storage and conversion devices are continuously serving for human life. The electrochemical performance of batteries and supercapacitors depends in large part on the active materials in electrodes. As an important family, Mn-based oxides have shown versatile applications in primary batteries, secondary batteries, metal-air batteries, and pseudocapacitors due to their high activity, high abundance, low price, and environmental friendliness. In order to meet future market demand, it is essential and urgent to make further improvements in energy and power densities of Mn-based electrode materials with the consideration of multiple electron reaction and low molecular weight of the active materials. Meanwhile, nanomaterials are favourable to achieve high performance by means of shortening the ionic diffusion length and providing large surface areas for electrode reactions. This article reviews the recent efforts made to apply nanostructured Mn-based oxides for batteries and pseudocapacitors. The influence of structure, morphology, and composition on electrochemical performance has been systematically summarized. Compared to bulk materials and notable metal catalysts, nanostructured Mn-based oxides can promote the thermodynamics and kinetics of the electrochemical reactions occurring at the solid-liquid or the solid-liquid-gas interface. In particular, nanostructured Mn-based oxides such as one-dimensional MnO2 nanostructures, MnO2-conductive matrix nanocomposites, concentration-gradient structured layered Li-rich Mn-based oxides, porous LiNi0.5Mn1.5O4 nanorods, core-shell structured LiMnSiO4@C nanocomposites, spinel-type Co-Mn-O nanoparticles, and perovskite-type CaMnO3 with micro-nano structures all display superior electrochemical performance. This review should shed light on the sustainable development of advanced batteries and pseudocapacitors with nanostructured Mn-based oxides.

  15. Biogenic U(IV) oxidation by dissolved oxygen and nitrate in sediment after prolonged U(VI)/Fe(III)/SO42- reduction

    SciTech Connect

    Moon, H. S.; Komlos, J.; Jaffé, P. R.

    2009-02-01

    Sediment column experiments were performed to quantify the effect of biogenic iron sulfide precipitates on the stability of bioreduced uranium during and after a simulated bioremediation scenario. In particular, this study examined the effect of different oxidants (dissolved oxygen and nitrate) on biogenic U(IV) oxidation in sediment that experienced significant sulfate reduction in addition to Fe(III) and U(VI) reduction. The experimental set-up included five replicate columns (each 5 cm in diameter, 15 cm long and packed with background sediment from a site contaminated with uranium) that were bioreduced for 70 days by injecting a nutrient media containing 3 mM acetate and 6 mM sulfate prior to oxidation. Upon oxidation, iron sulfide precipitates formed during bioreduction acted as a buffer to partially prevent biogenic U(IV) oxidation. The iron sulfides were more effective at protecting biogenic U(IV) from oxidation when dissolved oxygen was the oxidant compared to nitrate. A constant supply of 0.25 mM and 1.6 mM nitrate over a 50 day period resulted in uranium resolubilization of 11% and 60%, respectively, while less than 1% of the uranium was resolubilized in the column supplied 0.27 mM dissolved oxygen during the same time period. Over time, oxidation increased pore water channeling, which was more pronounced during oxidation with nitrate. Finally, increased channeling with time of oxidation could affect the transport of an oxidant through the previously reduced zone, and hence the oxidation dynamics of the reduced species.

  16. Low-temperature synthesis of Mn-based mixed metal oxides with novel fluffy structures as efficient catalysts for selective reduction of nitrogen oxides by ammonia.

    PubMed

    Meng, Bo; Zhao, Zongbin; Chen, Yongsheng; Wang, Xuzhen; Li, Yong; Qiu, Jieshan

    2014-10-21

    A series of Mn-based mixed metal oxide catalysts (Co-Mn-O, Fe-Mn-O, Ni-Mn-O) with high surface areas were prepared via low temperature crystal splitting and exhibited extremely high catalytic activity for the low-temperature selective catalytic reduction of nitrogen oxides with ammonia.

  17. Kinetics of Mn(II) oxidation by Leptothrix discophora SS1

    NASA Astrophysics Data System (ADS)

    Zhang, Jinghao; Lion, Leonard W.; Nelson, Yarrow M.; Shuler, Michael L.; Ghiorse, William C.

    2002-03-01

    The kinetics of Mn(II) oxidation by the bacterium Leptothrix discophora SS1 was investigated in this research. Cells were grown in a minimal mineral salts medium in which chemical speciation was well defined. Mn(II) oxidation was observed in a bioreactor under controlled conditions with pH, O 2, and temperature regulation. Mn(II) oxidation experiments were performed at cell concentrations between 24 mg/L and 35 mg/L, over a pH range from 6 to 8.5, between temperatures of 10°C and 40°C, over a dissolved oxygen range of 0 to 8.05 mg/L, and with L. discophora SS1 cells that were grown in the presence of Cu concentrations ranging from zero to 0.1 μM. Mn(II) oxidation rates were determined when the cultures grew to stationary phase and were found to be directly proportional to O 2 and cell concentrations over the ranges investigated. The optimum pH for Mn(II) oxidation was approximately 7.5, and the optimum temperature was 30°C. A Cu level as low as 0.02 μM was found to inhibit the growth rate and yield of L. discophora SS1 observed in shake flasks, while Cu levels between 0.02 and 0.1 μM stimulated the Mn(II) oxidation rate observed in bioreactors. An overall rate law for Mn(II) oxidation by L. discophora as a function of pH, temperature, dissolved oxygen concentration (D.O.), and Cu concentration is proposed. At circumneutral pH, the rate of biologically mediated Mn(II) oxidation is likely to exceed homogeneous abiotic Mn(II) oxidation at relatively low (≈μg/L) concentrations of Mn oxidizing bacteria.

  18. Interactions of proteins with biogenic iron oxyhydroxides and a new culturing technique to increase biomass yields of neutrophilic, iron-oxidizing bacteria.

    PubMed

    Barco, Roman A; Edwards, Katrina J

    2014-01-01

    Neutrophilic, bacterial iron-oxidation remains one of the least understood energy-generating biological reactions to date. One of the reasons it remains under-studied is because there are inherent problems with working with iron-oxidizing bacteria (FeOB), including low biomass yields and interference from the iron oxides in the samples. In an effort to circumvent the problem of low biomass, a new large batch culturing technique was developed. Protein interactions with biogenic iron oxides were investigated confirming that such interactions are strong. Therefore, a protein extraction method is described to minimize binding of proteins to biogenic iron oxides. The combination of these two methods results in protein yields that are appropriate for activity assays in gels and for proteomic profiling.

  19. Interactions of proteins with biogenic iron oxyhydroxides and a new culturing technique to increase biomass yields of neutrophilic, iron-oxidizing bacteria

    PubMed Central

    Barco, Roman A.; Edwards, Katrina J.

    2014-01-01

    Neutrophilic, bacterial iron-oxidation remains one of the least understood energy-generating biological reactions to date. One of the reasons it remains under-studied is because there are inherent problems with working with iron-oxidizing bacteria (FeOB), including low biomass yields and interference from the iron oxides in the samples. In an effort to circumvent the problem of low biomass, a new large batch culturing technique was developed. Protein interactions with biogenic iron oxides were investigated confirming that such interactions are strong. Therefore, a protein extraction method is described to minimize binding of proteins to biogenic iron oxides. The combination of these two methods results in protein yields that are appropriate for activity assays in gels and for proteomic profiling. PMID:24910632

  20. The oxidation capacity of Mn3O4 nanoparticles is significantly enhanced by anchoring them onto reduced graphene oxide to facilitate regeneration of surface-associated Mn(III).

    PubMed

    Duan, Lin; Wang, Zhongyuan; Hou, Yan; Wang, Zepeng; Gao, Guandao; Chen, Wei; Alvarez, Pedro J J

    2016-10-15

    Metal oxides are often anchored to graphene materials to achieve greater contaminant removal efficiency. To date, the enhanced performance has mainly been attributed to the role of graphene materials as a conductor for electron transfer. Herein, we report a new mechanism via which graphene materials enhance oxidation of organic contaminants by metal oxides. Specifically, Mn3O4-rGO nanocomposites (Mn3O4 nanoparticles anchored to reduced graphene oxide (rGO) nanosheets) enhanced oxidation of 1-naphthylamine (used here as a reaction probe) compared to bare Mn3O4. Spectroscopic analyses (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) show that the rGO component of Mn3O4-rGO was further reduced during the oxidation of 1-naphthylamine, although rGO reduction was not the result of direct interaction with 1-naphthylamine. We postulate that rGO improved the oxidation efficiency of anchored Mn3O4 by re-oxidizing Mn(II) formed from the reaction between Mn3O4 and 1-naphthylamine, thereby regenerating the surface-associated oxidant Mn(III). The proposed role of rGO was verified by separate experiments demonstrating its ability to oxidize dissolved Mn(II) to Mn(III), which subsequently can oxidize 1-naphthylamine. The role of dissolved oxygen in re-oxidizing Mn(II) was ruled out by anoxic (N2-purged) control experiments showing similar results as O2-sparged tests. Opposite pH effects on the oxidation efficiency of Mn3O4-rGO versus bare Mn3O4 were also observed, corroborating the proposed mechanism because higher pH facilitates oxidation of surface-associated Mn(II) even though it lowers the oxidation potential of Mn3O4. Overall, these findings may guide the development of novel metal oxide-graphene nanocomposites for contaminant removal.

  1. 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.

  2. Mobilization of manganese by basalt associated Mn(II)-oxidizing bacteria from the Indian Ridge System.

    PubMed

    Sujith, P P; Mourya, B S; Krishnamurthi, S; Meena, R M; Loka Bharathi, P A

    2014-01-01

    The Indian Ridge System basalt bearing Mn-oxide coatings had todorokite as the major and birnesite as the minor mineral. We posit that microorganisms associated with these basalts participate in the oxidation of Mn and contribute to mineral deposition. We also hypothesized that, the Mn-oxidizing microbes may respond reversibly to pulses of fresh organic carbon introduced into the water column by mobilizing the Mn in Mn-oxides. To test these two hypotheses, we enumerated the number of Mn-oxidizers and -reducers and carried out studies on the mobilization of Mn by microbial communities associated with basalt. In medium containing 100 μM Mn(2+), 10(3) colony forming units (CFU) were recovered with undetectable number of reducers on Mn-oxide amended medium, suggesting that the community was more oxidative. Experiments were then conducted with basalt fragments at 4±2 °C in the presence 'G(+)' and absence 'G(-)' of glucose (0.1%). Controls included set-ups, some of which were poisoned with 15 mM azide and the others of which were heat-killed. The mobilization of Mn in the presence of glucose was 1.76 μg g(-1) d(-1) and in the absence, it was 0.17 μg g(-1) d(-1) after 150 d. Mn mobilization with and without added glucose was 13 and 4 times greater than the corresponding azide treated controls. However, rates in 'G(+)' were 16 times and 'G(-)' 24 times more than the respective heat killed controls. The corresponding total counts in the presence of added glucose increased from 1.63×10(6) to 6.71×10(7) cells g(-1) and from 1.41×10(7) to 3.52×10(7) cells g(-1) in its absence. Thus, the addition of glucose as a proxy for organic carbon changed the community's response from Mn(II)-oxidizing to Mn(IV)-reducing activity. The results confirm the participation of Mn oxidizing bacteria in the mobilization of Mn. Identification of culturable bacteria by 16S rRNA gene analysis showed taxonomic affiliations to Bacillus, Exiguobacterium, Staphylococcus, Brevibacterium and

  3. Crystal structure of the mixed Mn 4+/Mn 5+ 2H-perovskite-type Ba 4Mn 2NaO 9 oxide

    NASA Astrophysics Data System (ADS)

    Quarez, Eric; Roussel, Pascal; Pérez, Olivier; Leligny, Henri; Bendraoua, Abdelaziz; Mentré, Olivier

    2004-09-01

    Single crystals of the new Ba 4Mn 2NaO 9 have been prepared by electrosynthesis in molten NaOH. Its crystal structure has been solved from XRD data ( a=10.006(2), c=8.210(3), space group P321, Z=3, R=3.21%, wR=3.52%). It belongs to the wide family of 2H-related perovskite materials and shows columns of face-sharing MnO 6 octahedra and NaO 6 prisms according to the -(oct-oct-prism)- sequence isolated by Ba 2+ cations. The main characteristic of this new oxide is its mixed Mn 4+/Mn 5+ valence rarely reported up today. Help to the superspace formalism, Ba 4Mn 2NaO 9 (or Ba 1+ xNa xMn 1- xO 3 with x=1/3) can be regarded as composed of two interpenetrating sublattices [Ba 1+ x] and [Na 1/3Mn 2/3O 3] with their own period along the c axis. The ratio γ of these two periods is rational γ= c1/ c2=2/3. This composite structure approach which allows us, help to established rules, to predict the crystal structure from the γ-only knowledge has also been pointed out in this work.

  4. Aqueous ultracapacitors using amorphous MnO2 and reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Mery, Adrien; Ghamouss, Fouad; Autret, Cécile; Farhat, Douaa; Tran-Van, François

    2016-02-01

    Herein, synthesis and characterization of amorphous MnO2 and application in asymmetric aqueous ultracapacitors are reported. Different amorphous manganese oxide (MnO2) materials were synthesized from the reduction of KMnO4 in different media such as ethanol (EtOH) or dimethylformamide (DMF). The electrochemical behavior of amorphous MnO2, labeled MnO2-Et and MnO2-DMF, were studied by using cyclic voltammetry, impedance spectroscopy, and galvanostatic cycling in aqueous electrolyte. XRD, BET, TEM, and SEM characterizations highlighted the amorphous nature and the nanostructuration of these MnO2 materials. BET measurement established that these amorphous MnO2 are mesoporous. In addition, MnO2-Et exhibits a larger specific surface area (168 m2 g-1), a narrower pore diameters distribution with lower diameters compared to MnO2-DMF. These results are in agreement with the electrochemical results. Indeed, MnO2-Et shows a higher specific capacitance and lower impedance in aqueous K2SO4 electrolyte. Furthermore, aqueous asymmetric ultracapacitors were assembled and studied using amorphous MnO2 as positive electrode and reduced graphene oxide (rGO) as negative electrode. These asymmetric systems exhibit an electrochemical stability for more than 20,000 galvanostatic cycles at current density of 1 A g-1 with an operating voltage of 2 V.

  5. Interfacial strain and defects in asymmetric Fe-Mn oxide hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Mayence, Arnaud; Wéry, Madeleine; Tran, Dung Trung; Wetterskog, Erik; Svedlindh, Peter; Tai, Cheuk-Wai; Bergström, Lennart

    2016-07-01

    Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds.Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds. Electronic supplementary information (ESI) available: Materials characterization, powder X-ray diffraction, EFTEM images, EELS spectra, HAADF-STEM. See DOI: 10.1039/c6nr01373b

  6. Adsorption and oxidation of elemental mercury over Ce-MnOx/Ti-PILCs.

    PubMed

    He, Chuan; Shen, Boxiong; Chen, Jianhong; Cai, Ji

    2014-07-15

    A series of innovative Ce-Mn/Ti-pillared-clay (Ce-Mn/Ti-PILC) catalysts combining the advantages of PILCs and Ce-Mn were investigated for elemental mercury (Hg0) capture at 100-350 °C in the absence of HCl in the flue gas. The fresh and used catalysts were characterized by scanning electron microscopy (SEM), nitrogen adsorption-desorption, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The catalyst characterization indicated that the 6%Ce-6%MnOx/Ti-PILC catalyst possessed a large specific surface area and high dispersion of Ce and Mn on the surface. The experimental results indicated that the 6%Ce-6%MnOx/Ti-PILC catalyst exhibited high Hg0 capture (>90%) at 100-350 °C. During the first stage of the reaction, the main Hg0 capture mechanism for the catalyst was adsorption. As the reaction proceeded, the Hg0 oxidation ability was substantially enhanced. Both the hydroxyl oxygen and the lattice oxygen on the surface of the catalysts participated in Hg0 oxidation. At a low temperature (150 °C), the hydroxyl oxygen and lattice oxygen from Ce4+→Ce3+ and Mn3+→Mn2+ on the surface contributed to Hg0 oxidation. However, at a high temperature (250 °C), the hydroxyl oxygen and lattice oxygen from Mn4+→Mn3+ contributed to Hg0 oxidation. Hg0 oxidation was preferred at a high temperature. The 6%Ce-6%MnOx/Ti-PILC catalyst was demonstrated to a good Hg0 adsorbent and catalytic oxidant in the absence of HCl in the flue gas.

  7. Preliminary characterization and biological reduction of putative biogenic iron oxides (BIOS) from the Tonga-Kermadec Arc, southwest Pacific Ocean.

    PubMed

    Langley, S; Igric, P; Takahashi, Y; Sakai, Y; Fortin, D; Hannington, M D; Schwarz-Schampera, U

    2009-01-01

    Sediment samples were obtained from areas of diffuse hydrothermal venting along the seabed in the Tonga sector of the Tonga-Kermadec Arc, southwest Pacific Ocean. Sediments from Volcano 1 and Volcano 19 were analyzed by X-ray diffraction (XRD) and found to be composed primarily of the iron oxyhydroxide mineral, two-line ferrihydrite. XRD also suggested the possible presence of minor amounts of more ordered iron (hydr)oxides (including six-line ferrihydrite, goethite/lepidocrocite and magnetite) in the biogenic iron oxides (BIOS) from Volcano 1; however, Mössbauer spectroscopy failed to detect any mineral phases more crystalline than two-line ferrihydrite. The minerals were precipitated on the surfaces of abundant filamentous microbial structures. Morphologically, some of these structures were similar in appearance to the known iron-oxidizing genus Mariprofundus spp., suggesting that the sediments are composed of biogenic iron oxides. At Volcano 19, an areally extensive, active vent field, the microbial cells appeared to be responsible for the formation of cohesive chimney-like structures of iron oxyhydroxide, 2-3 m in height, whereas at Volcano 1, an older vent field, no chimney-like structures were apparent. Iron reduction of the sediment material (i.e. BIOS) by Shewanella putrefaciens CN32 was measured, in vitro, as the ratio of [total Fe(II)]:[total Fe]. From this parameter, reduction rates were calculated for Volcano 1 BIOS (0.0521 day(-1)), Volcano 19 BIOS (0.0473 day(-1)), and hydrous ferric oxide, a synthetic two-line ferrihydrite (0.0224 day(-1)). Sediments from both BIOS sites were more easily reduced than synthetic ferrihydrite, which suggests that the decrease in effective surface area of the minerals within the sediments (due to the presence of the organic component) does not inhibit subsequent microbial reduction. These results indicate that natural, marine BIOS are easily reduced in the presence of dissimilatory iron-reducing bacteria, and that the

  8. 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 H2O, SO2, 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 H2O, SO2, and NO. Furthermore, the extent of Hg(0) oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter kE-R, and the predicted result was consistent with the experimental result.

  9. 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.

  10. Oxide Transformation in Cr-Mn-Prealloyed Sintered Steels: Thermodynamic and Kinetic Aspects

    NASA Astrophysics Data System (ADS)

    Hryha, Eduard; Nyborg, Lars

    2014-04-01

    The main obstacle for utilization of Cr and Mn as alloying elements in powder metallurgy is their high oxygen affinity leading to oxidation risk during powder manufacturing, handling, and especially during further consolidation. Despite the high purity of the commercially available Cr- and Mn-prealloyed iron powder grades, the risk of stable oxide formation during the sintering process remains. Thermodynamic and kinetic simulation of the oxide formation/transformation on the former powder surface during heating and sintering stages using thermodynamic modeling tools (Thermo-Calc and HSC Chemistry) was performed. Simulation is based on the results from the analysis of amount, morphology, and composition of the oxide phases inside the inter-particle necks in the specimens from interrupted sintering trials utilizing advanced analysis tools (HRSEM + EDX and XPS). The effect of the processing parameters, such as sintering atmosphere composition, temperature profile as well as graphite addition on the possible scenarios of oxide reduction/formation/transformation for Fe-Cr-Mn-C powder systems, was evaluated. Results indicate that oxide transformation occurs in accordance with the thermodynamic stability of oxides as follows: Fe2O3 → FeO → Fe2MnO4 → Cr2FeO4 → Cr2O3 → MnCr2O4 → MnO/MnSiO x → SiO2. Spinel MnCr2O4 was identified as the most stable oxide phase at applied sintering conditions up to 1393 K (1120 °C). Controlled conditions during the heating stage minimize the formation of stable oxide products and produce oxide-free sintered parts.

  11. Seeded growth of ferrite nanoparticles from Mn oxides: observation of anomalies in magnetic transitions.

    PubMed

    Song, Hyon-Min; Zink, Jeffrey I; Khashab, Niveen M

    2015-07-28

    A series of magnetically active ferrite nanoparticles (NPs) are prepared by using Mn oxide NPs as seeds. A Verwey transition is identified in Fe3O4 NPs with an average diameter of 14.5 nm at 96 K, where a sharp drop of magnetic susceptibility occurs. In MnFe2O4 NPs, a spin glass-like state is observed with the decrease in magnetization below the blocking temperature due to the disordered spins during the freezing process. From these MnFe2O4 NPs, MnFe2O4@Mn(x)Fe(1-x)O core-shell NPs are prepared by seeded growth. The structure of the core is cubic spinel (Fd3¯m), and the shell is composed of iron-manganese oxide (Mn(x)Fe(1-x)O) with a rock salt structure (Fm3¯m). Moiré fringes appear perpendicular to the 〈110〉 directions on the cubic shape NPs through the plane-matched epitaxial growth. These fringes are due to the difference in the lattice spacings between MnFe2O4 and Mn(x)Fe(1-x)O. Exchange bias is observed in these MnFe2O4@Mn(x)Fe(1-x)O core-shell NPs with an enhanced coercivity, as well as the shift of hysteresis along the field direction.

  12. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene.

    PubMed

    Lu, Hanfeng; Kong, Xianxian; Huang, Haifeng; Zhou, Ying; Chen, Yinfei

    2015-06-01

    Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the CeO2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.

  13. Oxidation behavior of cubic phases formed by alloying Al3Ti with Cr and Mn

    NASA Technical Reports Server (NTRS)

    Parfitt, L. J.; Nic, J. P.; Mikkola, D. E.; Smialek, J. L.

    1991-01-01

    Gravimetric, SEM, and XRD data are presented which document the significant improvement obtainable in the oxidation resistance of Al3Ti-containing alloys through additions of Cr. The L1(2) Al(67)Cr(8)Ti25 alloy exhibited excellent cyclic oxidation resistance at 1473 K, with the primary oxide formed being the ideally protective alpha-Al2O3. The Al(67)Mn(8)Ti(25) alloy also tested for comparison exhibited poor cyclic oxidation resistance, with substantial occurrence of TiO2 in the protective scales. Catastrophic oxidation was also encountered in the quaternary alloy Al(67)Mn(8)Ti(22)V(3).

  14. Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation.

    PubMed

    Hinkle, Margaret A G; Dye, Katherine G; Catalano, Jeffrey G

    2017-03-01

    Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O6 octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO2, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presence of dissolved Mn(II).

  15. Electronic Structure and Oxidation State Changes in the Mn (4) Ca Cluster of Photosystem II

    SciTech Connect

    Yano, J.; Pushkar, Y.; Messinger, J.; Bergmann, U.; Glatzel, P.; Yachandra, V.K.; /SLAC

    2012-08-17

    Oxygen-evolving complex (Mn{sub 4}Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i = 0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn{sub 4}(III{sub 2},IV{sub 2}) and Mn{sub 4}(III,IV{sub 3}) for S{sub 1} and S{sub 2} states, while it is still controversial for the S{sub 0} and S{sub 3} states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn{sub 4}Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S{sub 0} to S{sub 1}, and S{sub 1} to S{sub 2} transitions is twice as large as that during the S{sub 2} to S{sub 3} transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.

  16. 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

  17. Cooperative Mn(II) oxidation between two bacterial strains in an aquatic environment.

    PubMed

    Liang, Jinsong; Bai, Yaohui; Hu, Chengzhi; Qu, Jiuhui

    2016-02-01

    In natural or engineered environments, diverse interspecific interactions among two or more microbial taxa may profoundly affect the transformation of organic compounds in the media. Little is known, however, about how these organisms and interactions affect the transformation of heavy metals. Recently, we found an interaction between two non-Mn(II)-oxidizing (when in monoculture) strains, Arthrobacter sp. QXT-31 and Sphingopyxis sp. QXT-31, which, when cultured in combination, resulted in Mn(II)-oxidizing activity in synthetic media. In order to study the occurrence likelihood of cooperative Mn(II) oxidation in natural water and discharged effluent, we initially identified an optimal ratio of the two strains in a combined culture, as well as the impacts of external factors on the cooperative oxidation. Once preferred initial conditions were established, we assessed the degree and rate of Mn(II) oxidation mediated by the combined QXT-31 strains (henceforth referred to as simply 'QXT-31') in three different water types: groundwater, domestic sewage and coking wastewater. Results showed that Mn(II) oxidation only occurred when the two strains were within a specific ratios range. When introduced to the test waters at the preferred ratio, QXT-31 demonstrated high Mn(II)-oxidizing activities, even when relative abundance of QXT-31 was very low (roughly 1.6%, calculated by 454 pyrosequencing events on 16S rcDNA). Interestingly, even under low relative abundance of QXT-31, removal of total organic carbon and total nitrogen in the test waters was significantly higher than the control treatments that were not inoculated with QXT-31. Data from our study indicate that cooperative Mn(II) oxidation is most likely to occur in natural aquatic ecosystems, and also suggests an alternative method to treat wastewater containing high concentrations of Mn(II).

  18. 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

  19. Decolorization of methylene blue by delta-MnO2-coated montmorillonite complexes: emphasizing redox reactivity of Mn-oxide coatings.

    PubMed

    Zhu, Mao-Xu; Wang, Zheng; Xu, Shao-Hui; Li, Tie

    2010-09-15

    Delta-MnO(2) coatings on clay substrates tend to be poorer in crystallinity as compared with their discrete counterparts, which may be of environmental significance for adsorption and oxidation of contaminants. Discrete delta-MnO(2) particles and three delta-MnO(2)-coated montmorillonite complexes with varying MnO(2) loadings (4.8-34.9%) were synthesized, and oxidative decolorization of methylene blue (MB) by the synthetic materials was investigated in batch systems. Results showed that oxidative decolorization of MB increased with increasing loading of Mn-oxide coatings, whereas oxidation capacity of the coatings, on the basis of unit mass of MnO(2), tended to decrease. Initial reaction rate of MB oxidation by both delta-MnO(2) coatings and their discrete counterpart increased linearly with increasing Mn-oxide loadings, but the rate of the former was higher than that of the latter. An increase in humic acid concentration displayed a progressively enhanced promotive effect on MB decolorization, whereas the promotive effect was greatly suppressed at lower pH.

  20. Effect of Oxygen Tension, Mn(II) Concentration, and Temperature on the Microbially Catalyzed Mn(II) Oxidation Rate in a Marine Fjord †

    PubMed Central

    Tebo, Bradley M.; Emerson, Steven

    1985-01-01

    We present evidence that the oxidation of Mn(II) in a zone above the O2/H2S interface in the water column of Saanich Inlet, British Columbia, Canada, is microbially catalyzed. We measured the uptake of 54Mn(II) in water samples under in situ conditions of pH and temperature and in the presence and absence of oxygen. Experiments in the absence of oxygen provided a measure of the exchange of the tracer between the dissolved and solid pools of Mn(II); we interpret the difference between experiments in the presence and absence of oxygen to be a measure of Mn(II) oxidation. Using this method we examined the effect of oxygen tension, Mn(II) concentration, and temperature on the initial in situ Mn(II) oxidation rate (V0). Mn(II) oxidation was almost twice as fast under conditions of 67% air saturation (V0=5.5 nM h−1) as with the in situ concentration of 15 μM (5% air saturation; V0=3.1 nM h−1). Additions of ca. 18 μM Mn(II) completely inhibited all Mn(II) oxidation at three different depths in the oxidizing zone, and there was a temperature optimum for Mn(II) oxidation of around 20°C. These results are consistent with biologically mediated Mn(II) oxidation and indicate that the rate is limited by both oxygen and the concentration of microbial binding sites in this environment. PMID:16346931

  1. Effect of palladium on the reducibility of Mn based materials: correlation with methane oxidation activity.

    PubMed

    Baylet, A; Royer, S; Labrugère, C; Valencia, H; Marécot, P; Tatibouët, J M; Duprez, D

    2008-10-21

    Mn-based oxide supports were synthesized using different procedures: (i) carbonate co-precipitation method, leading to the formation of a hexaaluminate crystallized solid (La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19)) and (ii) solid-solid diffusion method, leading to the formation of a doped theta-Al(2)O(3) crystallized solid (nominal composition: 60 wt% La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19) + 40 wt% Al(2)O(3)). Impregnation of 1.0 wt%Pd was carried out on both oxides. The solids were tested for the catalytic methane combustion up to 700 degrees C. It was observed that adding palladium resulted in an important increase in the catalytic activity. The combined use of H(2)-TPR and XPS techniques reveals that only Mn(3+)/Mn(2+) redox "couple" is present in the solids, whatever the synthesis procedure used. The fraction Mn(3+)/Mn is proportional to the total Mn content in the solid support, whatever the sample structure (hexaaluminate or doped theta-Al(2)O(3)) and its morphology (large crystals or aggregates of small particles, respectively). Pd impregnation and further calcination at 650 degrees C has no significant effect on the Mn(3+)/Mn fraction. However, some changes in Mn(3+) reduction profile are observed, depending on the solid structure. Indeed, palladium addition strongly affects the manganese reducibility with an important shift of the reduction process to lower temperatures (approximately 100 degrees C). On the basis of redox properties observed for the different catalysts, a Mars-van-Krevelen redox mechanism, with oxygen transfer from support oxides to palladium particles, is proposed to explain the difference in terms of catalytic conversion and stability with respect to a 1.0 wt%Pd/Al(2)O(3) reference sample.

  2. Electronic Structure and Oxidation State Changes in the Mn4Ca Cluster of Photosystem II

    SciTech Connect

    Yano, Junko; Pushkar, Yulia; Messinger, Johannes; Bergmann, Uwe; Glatzel, Pieter; Yachandra, Vittal K

    2007-08-03

    Oxygen-evolving complex (Mn4Ca cluster) of Photosystem II cycles through five intermediate states (Si-states, i =0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn4(III2,IV2) and Mn4(III,IV3) for S1 and S2 states, while it is still controversial for the S0 and S3 states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn4Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mncomplexes. The spectral changes in the Mn 1s2p3/2 RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S0 to S1, and S1 to S2 transitions is twice as large as that during the S2 to S3 transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.

  3. Photochemistry of biogenic gases

    NASA Technical Reports Server (NTRS)

    Levine, Joel S.

    1989-01-01

    The relationship between the biosphere and the atmosphere is examined, emphasizing the composition and photochemistry and chemistry of the troposphere and stratosphere. The reactions of oxygen, ozone, and hydroxyl are reviewed and the fate of the biogenic gases ammonia, methane, reduced sulfur species, reduced halogen species, carbon monoxide, nitric oxide, nitrous oxide, nitrogen, and carbon dioxide are described. A list is given of the concentration and sources of the various gases.

  4. Use of XPS to identify the oxidation state of Mn in solid surfaces of filtration media oxide samples from drinking water treatment plants.

    PubMed

    Cerrato, José M; Hochella, Michael F; Knocke, William R; Dietrich, Andrea M; Cromer, Thomas F

    2010-08-01

    X-ray photoelectron spectroscopy (XPS) was used to identify Mn(II), Mn(III), and Mn(IV) in the surfaces of pure oxide standards and filtration media samples from drinking water treatment plants through the determination of the magnitude of the Mn 3s multiplet splitting and the position and shape of the Mn 3p photo-line. The Mn 3p region has been widely studied by applied physicists and surface scientists, but its application to identify the oxidation state of Mn in heterogeneous oxide samples has been limited. This study shows that the use of both the Mn 3s multiplet splitting and the position and shape of the Mn 3p photo-line provides a feasible means of determining the oxidation state of manganese in complex heterogeneous, environmentally important samples. Surface analysis of filtration media samples from several drinking water treatment plants was conducted. While Mn(IV) was predominant in most samples, a mixture of Mn(III) and Mn(IV) was also identified in some of the filtration media samples studied. The predominance of Mn(IV) in the media samples was felt to be related to the maintenance of free chlorine (HOCl) at substantial concentrations (2-5 mg*L(-1) as Cl2) across these filters. XPS could be a useful tool to further understand the specific mechanisms affecting soluble Mn removal using MnOx-coated filtration media.

  5. Oxidation of CoCrFeMnNi High Entropy Alloys

    NASA Astrophysics Data System (ADS)

    Holcomb, Gordon R.; Tylczak, Joseph; Carney, Casey

    2015-06-01

    Eight model high entropy alloys (HEAs) in the CoCrFeMnNi family (including one alloy each in the CoCrFeNi and CoFeMnNi subfamilies) were made, prepared, and exposed to laboratory air for 1100 h at 650°C and 750°C. Two commercial alloys, nickel-base superalloy 230 (N06230) and austenitic stainless steel 304H (S30409), were simultaneously exposed for comparison. Mass change oxidation kinetics were measured and cross-sections of exposed samples were observed. Seven of these HEAs contained much more Mn (12-24 wt.%) than is found in commercial heat-resistant stainless steels and superalloys. The oxidation resistance of CoCrFeNi was excellent and comparable to 304H at 650°C and only slightly worse at 750°C. The thin oxide scale on CoCrFeNi was primarily Cr oxide (presumably Cr2O3) with some Mn oxide at the outer part of the scale. The CoCrFeMnNi HEAs all experienced more rapid oxidation than CoCrFeNi and, especially at 750°C, experienced oxide scale spallation. The addition of Y in the alloy to lower S improved the oxidation resistance of these HEAs. Alloy CoFeMnNi, without Cr, experienced much higher oxidation rates and scale spallation than the Cr-containing alloys. A linear regression analysis of the log of the parabolic rate constant, log(kp), as functions of wt.% Cr and Mn found a good correlation for the compositional dependence of the oxidation rate constant, especially at 650°C. Mn was found to be more detrimental increasing log(k p) than Cr was helpful reducing log(k p). If CoCrFeMnNi HEAs are to be used in high temperature oxidizing environments, then examining lower levels of Mn, while maintaining Cr levels, should be pursued.

  6. Revealing biogenic sulfuric acid corrosion in sludge digesters: detection of sulfur-oxidizing bacteria within full-scale digesters.

    PubMed

    Huber, B; Drewes, J E; Lin, K C; König, R; Müller, E

    2014-01-01

    Biogenic sulfuric acid corrosion (BSA) is a costly problem affecting both sewerage infrastructure and sludge handling facilities such as digesters. The aim of this study was to verify BSA in full-scale digesters by identifying the microorganisms involved in the concrete corrosion process, that is, sulfate-reducing (SRB) and sulfur-oxidizing bacteria (SOB). To investigate the SRB and SOB communities, digester sludge and biofilm samples were collected. SRB diversity within digester sludge was studied by applying polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) targeting the dsrB-gene (dissimilatory sulfite reductase beta subunit). To reveal SOB diversity, cultivation dependent and independent techniques were applied. The SRB diversity studies revealed different uncultured SRB, confirming SRB activity and H2S production. Comparable DGGE profiles were obtained from the different sludges, demonstrating the presence of similar SRB species. By cultivation, three pure SOB strains from the digester headspace were obtained including Acidithiobacillus thiooxidans, Thiomonas intermedia and Thiomonas perometabolis. These organisms were also detected with PCR-DGGE in addition to two new SOB: Thiobacillus thioparus and Paracoccus solventivorans. The SRB and SOB responsible for BSA were identified within five different digesters, demonstrating that BSA is a problem occurring not only in sewer systems but also in sludge digesters. In addition, the presence of different SOB species was successfully associated with the progression of microbial corrosion.

  7. Microbial Communities Associated with Biogenic Iron Oxide Mineralization in Circumneutral pH Environments

    NASA Astrophysics Data System (ADS)

    Chan, C. S.; Banfield, J. F.

    2002-12-01

    Lithotrophic growth on iron is a metabolism that has been found in a variety of neutral pH environments and is likely important in sustaining life in microaerophilic solutions, especially those low in organics. The composition of the microbial communities, especially the organisms that are responsible for iron oxidation, and carbon and nitrogen fixation, are not known, yet the ability to recognize these contributions is vital to our understanding of iron cycling in natural environments. Our approach has been to study the microbial community structure, mineralogy, and geochemistry of ~20 cm thick, 100's meters long, fluffy iron oxide-encrusted biological mats growing in the Piquette Mine tunnel, and to compare the results to those from geochemically similar environments. In situ measurements (Hydrolab) and geochemical characterization of bulk water samples and peepers (dialysis sampling vials) indicate that the environment is microaerobic, with micromolar levels of iron, high carbonate and sulfate, and typical groundwater nitrate and nitrite concentrations. 16S rDNA clone libraries show that the microbial mat and water contain communities with considerable diversity within the Bacterial domain, a large proportion of Nitrospira and Betaproteobacteria, and no Archaea. Because clone library data are not necessarily indicative of actual abundance, fluorescence in-situ hybridization (FISH) was performed on water, mat, and sediment samples from the Piquette mine and two circumneutral iron- and carbonate-rich springs in the Oregon Cascade Range. Domain- and phylum-level probes were chosen based on the clone library results (Nitrospira, Beta- and Gammaproteobacteria, Acidobacteria, Actinobacteria, Chloroflexi, and Planctomyces). FISH data reveal spatial associations between specific microbial groups and mineralized structures. The organisms responsible for making the mineralized sheaths that compose the bulk of the iron oxide mat are Betaproteobacteria (probably Leptothrix

  8. Structure-activity relationship of CuO/MnO2 catalysts in CO oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Kun; Qian, Zhaoxia; Hua, Qing; Jiang, Zhiquan; Huang, Weixin

    2013-05-01

    A series of CuO/MnO2 catalysts with different CuO loadings were synthesized by the incipient wetness impregnation method. The catalysts were characterized by N2 adsorption-desorption isotherms, powder X-ray diffraction, X-ray photoelectron spectroscopy, H2-temperature programmed reduction, CO-temperature programmed reduction and scanning electron microscope. The CuO/MnO2 catalysts with CuO loading of 1-40% exhibit almost the same catalytic performance toward CO oxidation while those with higher CuO loadings exhibit a much poorer catalytic activity. The structural characterization results demonstrate that the CuO-MnO2 interface is the active site for CO oxidation in CuO/MnO2 catalysts and CO oxidation over CuO/MnO2 probably follows the interfacial reaction mechanism in which CO chemisorbed on CuO reacts with oxygen species on MnO2 at the CuO-MnO2 interface.

  9. Crystal Structures at Atomic Resolution of the Perovskite-Related GdBaMnFeO5 and Its Oxidized GdBaMnFeO6.

    PubMed

    García-Martín, Susana; Manabe, Keisuke; Urones-Garrote, Esteban; Ávila-Brande, David; Ichikawa, Noriya; Shimakawa, Yuichi

    2017-02-06

    Perovskite-related GdBaMnFeO5 and the corresponding oxidized phase GdBaMnFeO6, with long-range layered-type ordering of the Ba and Gd atoms have been synthesized. Oxidation retains the cation ordering but drives a modulation of the crystal structure associated with the incorporation of the oxygen atoms between the Gd layers. Oxidation of GdBaMnFeO5 increases the oxidation state of Mn from 2+ to 4+, while the oxidation state of Fe remains 3+. Determination of the crystal structure of both GdBaMnFeO5 and GdBaMnFeO6 is carried out at atomic resolution by means of a combination of advanced transmission electron microscopy techniques. Crystal structure refinements from synchrotron X-ray diffraction data support the structural models proposed from the TEM data. The oxidation states of the Mn and Fe atoms are evaluated by means of EELS and Mössbauer spectroscopy, which also reveals the different magnetic behavior of these oxides.

  10. Contemporary and projected biogenic fluxes of methane and nitrous oxide in North American terrestrial ecosystems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The importance of methane (CH4) and nitrous oxide (N2O) in determining global climate change has been increasingly recognized, but terrestrial CH4 and N2O budgets and the underlying mechanisms remain far from certain. Accurate estimation of terrestrial CH4 and N2O budgets would be a critical step fo...

  11. Partial-Redox-Promoted Mn Cycling of Mn(II)-Doped Heterogeneous Catalyst for Efficient H2O2-Mediated Oxidation.

    PubMed

    Li, Hai-Tao; Gao, Qiang; Han, Bo; Ren, Zheng-Hui; Xia, Kai-Sheng; Zhou, Cheng-Gang

    2017-01-11

    The development of a heterogeneous catalyst with high catalytic activity and durability for H2O2-mediated oxidation is one of the most important industrial and environmental issues. In this study, a Mn(II)-doped TiO2 heterogeneous catalyst was developed for H2O2-mediated oxidation. The TiO2 substrate-dependent partial-redox behavior of Mn was identified on the basis of our density functional theory simulations. This unique redox cycle was induced by a moderate electron transfer from Ti to Mn, which compensated for the electron loss of Mn and finally resulted in a high-efficiency cycling of Mn between its oxidized and reduced forms. In light of the theoretical results, a Mn(II)-doped TiO2 composite with well-defined morphology and large surface area (153.3 m(2) g(-1)) was elaborately fabricated through incorporating Mn(II) ions into a TiO2 nanoflower, and further tested as the catalyst for oxidative degradation of organic pollutants in the presence of H2O2. Benefiting from the remarkable textural features and excellent Mn cycling property, this composite exhibited superior catalytic performance for organic pollutant degradation. Moreover, it could retain 98.40% of its initial activity even in the fifth cycle. Our study provides an effective strategy for designing heterogeneous catalytic systems for H2O2-mediated oxidations.

  12. 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

  13. Virus Removal by Biogenic Cerium

    SciTech Connect

    De Gusseme, B.; Du Laing, G; Hennebel, T; Renard, P; Chidambaram, D; Fitts, J; Bruneel, E; Van Driessche, I; Verbeken, K; et. al.

    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 of 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.

  14. Area integrated emission of biogenic nitric oxide by Lagrangian dispersion modeling (LASAT): Milan oasis, Taklimakan desert (Xinjiang, PR China)

    NASA Astrophysics Data System (ADS)

    Badawy, M.; Wu, Z.; Behrendt, T.; Fechner, A. D.; Meixner, F. X.; Andreae, M. O.; Mamtimin, B.

    2012-04-01

    Today's knowledge of soil biogenic NO emission rates from arid and hyper-arid land is based on a total of about 20 experimental studies. Nevertheless, biogenic NO emissions even from non-managed arid and hyper-arid soils are significant and may range between 1-10 ng m-2 s-1 (in terms of nitrogen, if conditions for soil NO production are favourable (optimum soil moisture, high soil temperatures). Irrigated and fertilized oases, ranging about 3000 km long around the great Central Asian Taklimakan desert form the backbone of the agricultural output (80% of the Chinese cotton production) of the Xinjiang Uygur Autonomous Region (NW-China). Recent and future development of farmland and intensification of agriculture will definitely impact the regional soil NO emission and consequently the budget of nitrogen oxides and ozone. Up to today, only a few studies have preliminarily addressed soil biogenic NO emissions from the Taklimakan desert. In our contribution, we will focus on the quantification of the area integrated NO emission from the Milan oasis located on the most southern fringe of the Takalimkan desert (39.26° N, 88.91° E). At a first step, the 3D distribution of ambient NO concentration is calculated using a state-of-the-art commercially available dispersion model (LASAT 3.2, Lagrange Simulation of Aerosol-Transport). Performing the dispersion simulation, transport and turbulent diffusion are simulated for a group of representative "simulation particles" by means of a stochastic process (Lagrange simulation). Surface sources (individual cotton fields, Jujube orchards) are known: their geographical location as well as their areal extent, their stage of vegetation growth as well as irrigation and fertilization events and amounts, soil temperatures and soil water contents. This information is used to up-scale our results of field specific potential net NO emission, which has been parameterized in terms of soil temperature, soil water content, and soil nutrient

  15. Chemical oxidative potential of secondary organic aerosol (SOA) generated from the photooxidation of biogenic and anthropogenic volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Tuet, Wing Y.; Chen, Yunle; Xu, Lu; Fok, Shierly; Gao, Dong; Weber, Rodney J.; Ng, Nga L.

    2017-01-01

    Particulate matter (PM), of which a significant fraction is comprised of secondary organic aerosols (SOA), has received considerable attention due to its health implications. In this study, the water-soluble oxidative potential (OPWS) of SOA generated from the photooxidation of biogenic and anthropogenic hydrocarbon precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different reaction conditions (RO2+ HO2 vs. RO2+ NO dominant, dry vs. humid) was characterized using dithiothreitol (DTT) consumption. The measured intrinsic OPWS-DTT values ranged from 9 to 205 pmol min-1 µg-1 and were highly dependent on the specific hydrocarbon precursor, with naphthalene and isoprene SOA generating the highest and lowest OPWS-DTT values, respectively. Humidity and RO2 fate affected OPWS-DTT in a hydrocarbon-specific manner, with naphthalene SOA exhibiting the most pronounced effects, likely due to the formation of nitroaromatics. Together, these results suggest that precursor identity may be more influential than reaction condition in determining SOA oxidative potential, demonstrating the importance of sources, such as incomplete combustion, to aerosol toxicity. In the context of other PM sources, all SOA systems, with the exception of naphthalene SOA, were less DTT active than ambient sources related to incomplete combustion, including diesel and gasoline combustion as well as biomass burning. Finally, naphthalene SOA was as DTT active as biomass burning aerosol, which was found to be the most DTT-active OA source in a previous ambient study. These results highlight a need to consider SOA contributions (particularly from anthropogenic hydrocarbons) to health effects in the context of hydrocarbon emissions, SOA yields, and other PM sources.

  16. Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

    PubMed

    Riccobono, Francesco; Schobesberger, Siegfried; Scott, Catherine E; Dommen, Josef; Ortega, Ismael K; Rondo, Linda; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; David, André; Downard, Andrew; Dunne, Eimear M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hansel, Armin; Junninen, Heikki; Kajos, Maija; Keskinen, Helmi; Kupc, Agnieszka; Kürten, Andreas; Kvashin, Alexander N; Laaksonen, Ari; Lehtipalo, Katrianne; Makhmutov, Vladimir; Mathot, Serge; Nieminen, Tuomo; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Santos, Filipe D; Schallhart, Simon; Seinfeld, John H; Sipilä, Mikko; Spracklen, Dominick V; Stozhkov, Yuri; Stratmann, Frank; Tomé, Antonio; Tsagkogeorgas, Georgios; Vaattovaara, Petri; Viisanen, Yrjö; Vrtala, Aron; Wagner, Paul E; Weingartner, Ernest; Wex, Heike; Wimmer, Daniela; Carslaw, Kenneth S; Curtius, Joachim; Donahue, Neil M; Kirkby, Jasper; Kulmala, Markku; Worsnop, Douglas R; Baltensperger, Urs

    2014-05-16

    Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

  17. Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring

    NASA Astrophysics Data System (ADS)

    Kristensen, Kasper; Glasius, Marianne

    2011-09-01

    Organosulfates of monoterpenes and isoprene, as well as their oxidation products have been identified in biogenic secondary organic aerosols (BSOA) from both laboratory and field studies. Organosulfates provide an interesting coupling between air pollution and formation of low-volatility BSOA. HPLC quadrupole time-of-flight mass spectrometry was used to study polar acidic monoterpene and isoprene oxidation products including pinic acid, pinonic and terpenylic acid along with organosulfates and nitrooxy organosulfates in aerosols from ambient air. The method was first validated by analysis of spiked quartz filters, which showed acceptable recoveries >74% for pinic acid, pinonic acid, camphor sulphonic acid and adipic acid. Acetonitrile was identified as a better solvent than methanol for extraction and analysis of pinonic acid and adipic acid, due to improved analytical sensitivity and prevention of methyl ester formation during sample extraction. PM 1 (i.e, aerosols with an aerodynamic diameter ≤1 μm) were collected during spring 2008 in a forest in Denmark with mixed deciduous and coniferous trees. Average concentrations of the most abundant compounds were: pinic acid: 1.5 ng m -3, pinonic acid: 3.0 ng m -3, terpenylic acid: 0.8 ng m -3 and 3-methyl-1,2,3-butanetricarboxylic acid: 3.0 ng m -3. Organosulfates and nitrooxy organosulfates were identified in a majority of the daily samples and the highest levels were observed during a warm period in late spring. As a first approach, due to the lack of authentic standards, organosulfates and nitrooxy organosulfates were tentatively quantified based on the analytical response of camphor sulphonic acid. Generally the concentrations of organosulfates and nitrooxy organosulfates were lower than first generation oxidation products. The maximum concentration of a total of 10 organosulfates and nitrooxy organosulfates were found to be about three times lower than pinonic acid with a maximum concentration of 8 ng m -3. A

  18. 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

  19. 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.

  20. Interactions in Ternary Mixtures of MnO2, Al2O3, and Natural Organic Matter (NOM) and the Impact on MnO2 Oxidative Reactivity.

    PubMed

    Taujale, Saru; Baratta, Laura R; Huang, Jianzhi; Zhang, Huichun

    2016-03-01

    Our previous work reported that Al2O3 inhibited the oxidative reactivity of MnO2 through heteroaggregation between oxide particles and surface complexation of the dissolved Al ions with MnO2 (S. Taujale and H. Zhang, "Impact of interactions between metal oxides to oxidative reactivity of manganese dioxide" Environ. Sci. Technol. 2012, 46, 2764-2771). The aim of the current work was to investigate interactions in ternary mixtures of MnO2, Al2O3, and NOM and how the interactions affect MnO2 oxidative reactivity. For the effect of Al ions, we examined ternary mixtures of MnO2, Al ions, and NOM. Our results indicated that an increase in the amount of humic acids (HAs) increasingly inhibited Al adsorption by forming soluble Al-HA complexes. As a consequence, there was less inhibition on MnO2 reactivity than by the sum of two binary mixtures (MnO2+Al ions and MnO2+HA). Alginate or pyromellitic acid (PA)-two model NOM compounds-did not affect Al adsorption, but Al ions increased alginate/PA adsorption by MnO2. The latter effect led to more inhibition on MnO2 reactivity than the sum of the two binary mixtures. In ternary mixtures of MnO2, Al2O3, and NOM, NOM inhibited dissolution of Al2O3. Zeta potential measurements, sedimentation experiments, TEM images, and modified DLVO calculations all indicated that HAs of up to 4 mg-C/L increased heteroaggregation between Al2O3 and MnO2, whereas higher amounts of HAs completely inhibited heteroaggregation. The effect of alginate is similar to that of HAs, although not as significant, while PA had negligible effects on heteroaggregation. Different from the effects of Al ions and NOMs on MnO2 reactivity, the MnO2 reactivity in ternary mixtures of Al2O3, MnO2, and NOM was mostly enhanced. This suggests MnO2 reactivity was mainly affected through heteroaggregation in the ternary mixtures because of the limited availability of Al ions.

  1. 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.

  2. Biogenic synthesis of zinc oxide nanoparticles using Ruta graveolens (L.) and their antibacterial and antioxidant activities

    NASA Astrophysics Data System (ADS)

    Lingaraju, K.; Raja Naika, H.; Manjunath, K.; Basavaraj, R. B.; Nagabhushana, H.; Nagaraju, G.; Suresh, D.

    2016-06-01

    In the present investigation, green synthesis of zinc oxide nanoparticles were successfully synthesized by biological method using aqueous stem extract of Ruta graveolens act as reducing agent. Formation of ZnO nanoparticles were characterized by powder X-ray diffraction (PXRD), UV-visible spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. Zinc oxide nanoparticles were subjected to biological properties such as antibacterial and antioxidant studies. The PXRD pattern reveals that ZnO sample belongs to hexagonal phase with Wurtzite structure. The UV-vis absorption spectrum shows an absorption band at 355 nm due to ZnO nanoparticles. SEM images show that the particles have spherical like structure with large surface area and the average crystallite sizes were found to be in the range ~28 nm. These observations were confirmed by TEM analysis. The ZnO nanoparticles are found to inhibit the antioxidant activity of 1,1-diphenyl-2-picrylhydrazyl free radicals effectively. ZnO Nps exhibit significant bactericidal activity against Gram -ve bacterial strains such as Klebsiella aerogenes, Pseudomonas aeruginosa, Escherichia coli and Gram +ve Staphylococcus aureus by agar well diffusion method.

  3. Oxidation of a new Biogenic VOC: Chamber Studies of the Atmospheric Chemistry of Methyl Chavicol

    NASA Astrophysics Data System (ADS)

    Bloss, William; Alam, Mohammed; Adbul Raheem, Modinah; Rickard, Andrew; Hamilton, Jacqui; Pereira, Kelly; Camredon, Marie; Munoz, Amalia; Vazquez, Monica; Vera, Teresa; Rodenas, Mila

    2013-04-01

    The oxidation of volatile organic compounds (VOCs) leads to formation of ozone and SOA, with consequences for air quality, health, crop yields, atmospheric chemistry and radiative transfer. Recent observations have identified Methyl Chavicol ("MC": Estragole; 1-allyl-4-methoxybenzene, C10H12O) as a major BVOC above pine forests in the USA, and oil palm plantations in Malaysian Borneo. Palm oil cultivation, and hence MC emissions, may be expected to increase with societal food and bio fuel demand. We present the results of a series of simulation chamber experiments to assess the atmospheric fate of MC. Experiments were performed in the EUPHORE facility, monitoring stable product species, radical intermediates, and aerosol production and composition. We determine rate constants for reaction of MC with OH and O3, and ozonolysis radical yields. Stable product measurements (FTIR, PTRMS, GC-SPME) are used to determine the yields of stable products formed from OH- and O3- initiated oxidation, and to develop an understanding of the initial stages of the MC degradation chemistry. A surrogate mechanism approach is used to simulate MC degradation within the MCM, evaluated in terms of ozone production measured in the chamber experiments, and applied to quantify the role of MC in the real atmosphere.

  4. Thermodynamic Modeling of Oxide Phases in the Mn-O System

    NASA Astrophysics Data System (ADS)

    Kang, Youn-Bae; Jung, In-Ho

    2016-09-01

    A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Mn-O system 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 temperature at compositions covering from MnO to MnO2, and oxygen partial pressure from 10-15 to 102 (bar). The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Two spinel phases (α - and β -Mn3O4) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. Valence states of the spinels are interpreted based on the available thermopower measurement, for which Mn4+ was considered in the cubic spinel (β -Mn3O4). The present Mn3O4 spinel solutions can be integrated into a larger spinel solution database, which has been already developed. 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 sections and thermodynamic properties.

  5. Seasonal variation of nitrogen oxides, ozone and biogenic volatile organic compound concentrations and fluxes at Norway spruce forest

    NASA Astrophysics Data System (ADS)

    Juran, Stanislav; Vecerova, Kristyna; Holisova, Petra; Zapletal, Milos; Pallozzi, Emanuele; Guidolotti, Gabriele; Calfapietra, Carlo; Vecera, Zbynek; Cudlin, Pavel; Urban, Otmar

    2015-04-01

    Dynamics of nitrogen oxides (NOx) and ozone concentration and their depositions were investigated on the Norway spruce forest at Bily Kriz experimental station at the Silesian Beskydy Mountains (north-eastern part of the Czech Republic). Both NOx and ozone concentration and fluxes were modelled for the whole season and covering thus different climate conditions. Data were recorded for three consecutive years and therefore deeper analyses were performed. During the summer 2014 BVOC field campaign was carried out using proton-transfer-reaction-time-of-flight-mass-spectrometry (PTR-TOF, Ionicon Analytik GmbH, Innsbruck, Austria) and volatile organic compound of biogenic origin (BVOC) were measured at the different levels of tree canopies. By the same time BVOC were trapped into the Tenax tubes (Markes International Ltd., UK) and put afterwards for thermal desorption (Markes Unity System 2, Markes International Ltd., UK) to GS-MS analysis (TSQ Quntum XLS triple Quadrupole, Thermo Scientific, USA). Thus data of different levels of canopies together with different spectra of monoterpenes were obtained. Interesting comparison of both methods will be shown. It was the first BVOC field campaign using PTR technique at any of the forest in the Czech Republic. Highest fluxes and concentrations were recorded around the noon hours, represented particularly by monoterpenes, especially α-pinen and limonene. Other BVOCs than monoterpenes were negligible. Variation of fluxes between different canopies levels was observed, highlighting difference in shaded and sun exposed leaves. Sun leaves emitted up to 2.4 nmol m-2 s-1 of monoterpenes, while shaded leaves emitted only up to 0.6 nmol m-2 s-1 when measured under standard conditions (irradiance 1000 µmol m-2 s-1; temperature 30°C). We discuss here the importance of the most common Norway spruce tree forests in the Czech Republic in bi-directional exchanges of important secondary pollutant such as ozone and nitrogen oxides, their

  6. 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. 

  7. Development of bioinspired Mn4O4-cubane water oxidation catalysts: lessons from photosynthesis.

    PubMed

    Dismukes, G Charles; Brimblecombe, Robin; Felton, Greg A N; Pryadun, Ruslan S; Sheats, John E; Spiccia, Leone; Swiegers, Gerhard F

    2009-12-21

    Hydrogen is the most promising fuel of the future owing to its carbon-free, high-energy content and potential to be efficiently converted into either electrical or thermal energy. The greatest technical barrier to accessing this renewable resource remains the inability to create inexpensive catalysts for the solar-driven oxidation of water. To date, the most efficient system that uses solar energy to oxidize water is the photosystem II water-oxidizing complex (PSII-WOC), which is found within naturally occurring photosynthetic organisms. The catalytic core of this enzyme is a CaMn(4)O(x) cluster, which is present in all known species of oxygenic phototrophs and has been conserved since the emergence of this type of photosynthesis about 2.5 billion years ago. The key features that facilitate the catalytic success of the PSII-WOC offer important lessons for the design of abiological water oxidation catalysts. In this Account, we examine the chemical principles that may govern the PSII-WOC by comparing the water oxidation capabilities of structurally related synthetic manganese-oxo complexes, particularly those with a cubical Mn(4)O(4) core ("cubanes"). We summarize this research, from the self-assembly of the first such clusters, through the elucidation of their mechanism of photoinduced rearrangement to release O(2), to recent advances highlighting their capability to catalyze sustained light-activated electrolysis of water. The [Mn(4)O(4)](6+) cubane core assembles spontaneously in solution from monomeric precursors or from [Mn(2)O(2)](3+) core complexes in the presence of metrically appropriate bidentate chelates, for example, diarylphosphinates (ligands of Ph(2)PO(2)(-) and 4-phenyl-substituted derivatives), which bridge pairs of Mn atoms on each cube face (Mn(4)O(4)L(6)). The [Mn(4)O(4)](6+) core is enlarged relative to the [Mn(2)O(2)](3+) core, resulting in considerably weaker Mn-O bonds. Cubanes are ferocious oxidizing agents, stronger than analogous complexes

  8. Manganese mineral formation by bacterial spores of the marine Bacillus , strain SG-1: Evidence for the direct oxidation of Mn(II) to Mn(IV)

    NASA Astrophysics Data System (ADS)

    Mandernack, Kevin W.; Post, Jeffrey; Tebo, Bradley M.

    1995-11-01

    The spores of a marine Bacillus bacterium, strain SG-1, are able to oxidize Mn (H) over a wide range of temperatures (0-80°C) and Mn (II) concentrations (25 mM), in both low ionic strength N- (2-hydroxyethyl) piperazine- N'-ethanesulfonic acid (HEPES) buffer (HB) and in HEPES-buffered seawater (SW). Using SG-1 spores as a catalyst for manganese mineral formation, and by varying the temperature and Mn (II) concentration at pH 7.4-8.0, a variety of manganese oxide and manganate minerals were formed under environmentally relevant conditions in HB and SW. In general, mixed phases of lower valence state minerals (hausmannite, Mn 30 4; feitknechtite, βMnOOH; and manganite, γMnOOH) formed in HB and SW at high Mn (II) concentrations (10 mM initial), or at high temperatures (70°C), by two weeks. βMnOOH was favored at low temperatures (3°C) and Mn 3O 4 at higher temperatures (55-70°C). After 1 year of aging, yMnOOH became the dominant or only mineral present at 25 and 55°C. At lower Mn (II) concentrations (initial concentrations ≤100 μM in HB and ≤1 MM in SW), Mn(IV) minerals precipitated. In HB the Mn(IV) minerals most often resembled sodium buserite, evidenced by collapse of a 10 to 7 Å phase with air drying at room temperature. In SW both buserite and Mg-rich noncollapsible 10 Å manganates were formed. The Mg-rich 10 Å manganates did not collapse to 7 Å even with baking at 100°C. The oxidation state of the minerals were generally higher in SW (as high as 3.7) than in HB (3.2). Mn (IV) minerals also formed at higher Mn (II) concentrations in SW than in HB. These observed differences between SW and HB may have resulted from differences in the chemical milieu, or because of the marine adapted physiology of the bacterial spores. Under a variety of conditions (HB and SW, 3-55δC) Mn (IV) mineral formation often occurred at pH and Mn (II) concentrations too high to be favorable for the disproportionation of Mn 30 4, or βMnOOH to Mn (IV). The results

  9. Biogenic concrete protection driven by the formate oxidation by Methylocystis parvus OBBP

    PubMed Central

    Ganendra, Giovanni; Wang, Jianyun; Ramos, Jose A.; Derluyn, Hannelore; Rahier, Hubert; Cnudde, Veerle; Ho, Adrian; Boon, Nico

    2015-01-01

    The effectiveness of Microbiologically Induced Carbonate Precipitation (MICP) from the formate oxidation by Methylocystis parvus OBBP as an alternative process for concrete protection was investigated. MICP was induced on Autoclaved Aerated Concrete (AAC), the model material, by immersing the material in 109 M. parvus cells mL−1 containing 5 g L−1 of calcium formate. A 2 days immersion of the material gave the maximum weight increase of the specimens (38 ± 19 mg) and this was likely due to the deposition of calcium carbonate, biomass, and unconverted calcium formate. The solid deposition mainly occurred in the micropores of the specimen, close to the outer surface. A significantly lower water absorption was observed in the bacterially treated specimens compared to the non-treated ones (up to 2.92 ± 0.91 kg m−2) and this could be attributed to the solid deposition. However, the sonication test demonstrated that the bacterial treatment did not give a consolidating effect to the material. Overall, compared to the currently employed urea hydrolysis process, the formate-based MICP by M. parvus offers a more environmentally friendly approach for the biotechnological application to protect concrete. PMID:26284061

  10. Biogenic concrete protection driven by the formate oxidation by Methylocystis parvus OBBP.

    PubMed

    Ganendra, Giovanni; Wang, Jianyun; Ramos, Jose A; Derluyn, Hannelore; Rahier, Hubert; Cnudde, Veerle; Ho, Adrian; Boon, Nico

    2015-01-01

    The effectiveness of Microbiologically Induced Carbonate Precipitation (MICP) from the formate oxidation by Methylocystis parvus OBBP as an alternative process for concrete protection was investigated. MICP was induced on Autoclaved Aerated Concrete (AAC), the model material, by immersing the material in 10(9) M. parvus cells mL(-1) containing 5 g L(-1) of calcium formate. A 2 days immersion of the material gave the maximum weight increase of the specimens (38 ± 19 mg) and this was likely due to the deposition of calcium carbonate, biomass, and unconverted calcium formate. The solid deposition mainly occurred in the micropores of the specimen, close to the outer surface. A significantly lower water absorption was observed in the bacterially treated specimens compared to the non-treated ones (up to 2.92 ± 0.91 kg m(-2)) and this could be attributed to the solid deposition. However, the sonication test demonstrated that the bacterial treatment did not give a consolidating effect to the material. Overall, compared to the currently employed urea hydrolysis process, the formate-based MICP by M. parvus offers a more environmentally friendly approach for the biotechnological application to protect concrete.

  11. Reductive dissolution of Mn oxides in river-recharged aquifers: a laboratory column study

    NASA Astrophysics Data System (ADS)

    Petrunic, B. M.; MacQuarrie, K. T. B.; Al, T. A.

    2005-01-01

    River-recharged aquifers are developed for drinking water supplies in many parts of the world. Often, however, dissolved organic carbon (DOC) present in the infiltrating river water causes biogeochemical reactions to occur in the adjacent aquifer that create elevated Mn and Fe. Mn concentrations in groundwater from some of the production wells installed in the aquifer at Fredericton, New Brunswick exceed the Canadian Drinking Water Guideline of 9.1×10 -4 mmol/l by up to 5.5×10 -2 mmol/l. It has previously been hypothesized that the influx of DOC from the Saint John River is causing bacterially mediated reductive dissolution of Mn oxides in the aquifer system, leading to elevated aqueous Mn concentrations. Previous work was limited to the collection of water samples from production wells and several observation wells installed in the glacial outwash aquifer. The objective of this study was to investigate the biogeochemical controls on Mn concentrations using sand-filled columns. One column was inoculated with bacteria while a second column was treated with ethanol in order to decrease the microbial population initially present in the system. Both columns received the same influent solution that contained acetate as a source of DOC. The results of the experiments suggested that the two main controls on Mn concentrations in the columns were microbially mediated reductive dissolution of Mn oxides and cation exchange. The conceptual model that was developed based on the experimental data was supported by the results obtained using a one-dimensional reactive-transport model. The reductive dissolution of Mn oxides in the aquifer sands could be adequately simulated using dual-Monod kinetics. Similar trends are observed in the experimental data and field data collected from Production Well 5, located in the Fredericton Aquifer. From the experiments, it is evident that cation-exchange reactions may be an important geochemical control on Mn concentrations during the initial

  12. 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.

  13. Thallium Isotopes Tracking Mn-Oxide Burial - A Proxy for Deoxygenation During Oceanic Anoxic Event 2

    NASA Astrophysics Data System (ADS)

    Ostrander, C.; Owens, J. D.; Nielsen, S.

    2015-12-01

    Thallium (Tl) is proving to be a useful paleoredox proxy given that the Tl isotope composition of seawater is highly dependent on the magnitude of manganese (Mn) oxide burial in the ocean. In turn, Mn oxides require oxygen at the sediment-water interface to precipitate, linking the Tl isotope cycle to ocean oxygenation. Currently, the marine residence time of Tl is ~20kyrs and the Tl isotope composition of seawater is invariant, which suggests Tl isotopes could be a global tracer of marine Mn-oxide burial. Importantly, recent research suggests sediments deposited under a euxinic water column faithfully record the Tl isotope value of the overlying oxic water column (e.g. Black Sea and Cariaco Basin). Therefore, analysis of organic-rich black shales may prove useful in evaluating the seawater Tl isotope composition of past oceans and, hence, large-scale burial of Mn-oxides and the extent of bottom water ocean oxygenation. A logical test for this proxy is during the well-studied Cenomanian-Turonian boundary event termed Oceanic Anoxic Event 2 (OAE-2) at ~94 Ma. It is known that the global extent of anoxia and euxinia increased during this event, however, to what extent global bottom water deoxygenation occured is unconstrained. If deep water deoxygenation occurred, it would be hypothesized that Mn-oxide precipitation would decrease, resulting in a positive Tl isotope excursion during OAE-2. We have analyzed the Tl isotope composition of organic-rich black shales from Site 1258 of the Ocean Drilling Program (ODP) spanning the period before, during, and after OAE-2. Based on Fe redox proxies, the entire section is euxinic and thus no Mn-oxides are present (i.e. no local redox changes). Before the event, Tl isotope compositions are similar or slightly heavier than modern seawater values. Just prior to the onset of OAE-2, a positive shift occurs and is maintained until recovery, slightly before the termination of the event. The shift to heavier values and subsequent

  14. Peroxynitrite formation in nitric oxide-exposed submitochondrial particles: Detection, oxidative damage and catalytic removal by Mn-porphyrins

    PubMed Central

    Valez, Valeria; Cassina, Adriana; Batinic-Haberle, Ines; Kalyanaraman, Balaraman; Ferrer-Sueta, Gerardo; Radi, Rafael

    2012-01-01

    Peroxynitrite (ONOO−) formation in mitochondria may be favored due to the constant supply of superoxide radical (O2•−) by the electron transport chain plus the facile diffusion of nitric oxide (•NO) to this organelle. Herein, a model system of submitochondrial particles (SMP) in the presence of succinate plus the respiratory inhibitor antimycin A (to increase O2•− rates) and the •NO-donor NOC-7 was studied to directly establish and quantitate peroxynitrite by a multiplicity of methods including chemiluminescence, fluorescence and immunochemical analysis. While all the tested probes revealed peroxynitrite at near stoichiometric levels with respect to its precursor radicals, coumarin boronic acid (a probe that directly reacts with peroxynitrite) had the more straightforward oxidation profile from O2•−-forming SMP as a function of the •NO flux. Interestingly, immunospintrapping studies verified protein radical generation in SMP by peroxynitrite. Substrate-supplemented SMP also reduced Mn(III)porphyrins (MnP) to Mn(II)P under physiologically-relevant oxygen levels (3–30 μM); then, Mn(II)P were capable to reduce peroxynitrite and protect SMP from the inhibition of complex I-dependent oxygen consumption and protein radical formation and nitration of membranes. The data directly support the formation of peroxynitrite in mitochondria and demonstrate that MnP can undergo a catalytic redox cycle to neutralize peroxynitrite-dependent mitochondrial oxidative damage. PMID:23142682

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

    SciTech Connect

    Prasankumar, T.; Jose, Sujin P.; Ilangovan, R.; Venkatesh, K. S.

    2015-06-24

    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 in 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.

  16. Endolithic Mn-oxidizing bacteria commonly associated with basalts at active Seamounts

    NASA Astrophysics Data System (ADS)

    Templeton, A.; Haucke, L.; Bailey, B.; Staudigel, H.; Tebo, B.

    2005-12-01

    Mn is a trace component of volcanic rocks that is commonly enriched by 1-2 orders of magnitude within the secondary mineral assemblages associated with submarine basalts. Our analysis of relatively young basalts recovered from active seamounts such as Loihi Seamount (Hawaii) and Vailulu'u Seamount (American Samoa) shows that Mn(IV)-oxides readily form during short time-periods (10 years) of low-temperature (~2C) alteration, although the abiotic kinetics of Mn(II)-oxidation are slow at this temperatures and pH. We suggest that the formation of these secondary minerals are likely due to the common presence of heterotrophic bacteria with the functional capability of Mn(II)-oxidation, which accelerate the rates of oxidation several orders of magnitude faster than predicted for water-rock interaction alone. To identify and isolate endolithic Mn(II)-oxidizing microorganisms from naturally-weathered basalt surfaces, samples were recovered from the cold outer-flanks of Loihi and Vailulu'u Seamount via submersible with a sealable biobox. Using a variety of oligotrophic to organic-rich seawater-based media, we have isolated over 40 strains of Mn(II)-oxidizing bacteria. These isolates are primarily alpha- and gamma-Proteobacteria that can grow on low concentrations of simple to complex organics, but not Mn(II) as a sole energy source. None of the isolates, nor their closest relatively, were previously recognized as Mn(II)-oxidizing bacteria. In particular, we have found that there are several strains that are common to the basalts recovered from Loihi & Vailulu'u Seamount, as well as from basalts collected at the East Pacific Rise, particularly Pseudoalteromonas and Sulfitobacter sp. The 16S rRNA gene sequences of the Pseudoalteromonas isolates are also observed in T-RFLP data and 16S clone libraries for microbial mats at Loihi, indicating that these isolates are environmentally-relevant and abundant in-situ. The ubiquitous distribution of these isolates also suggests that

  17. Design and Preparation of MnO2/CeO2-MnO2 Double-Shelled Binary Oxide Hollow Spheres and Their Application in CO Oxidation.

    PubMed

    Zhang, Jian; Cao, Yidan; Wang, Chang-An; Ran, Rui

    2016-04-06

    Herein, we designed an extremely facile method to prepare well-defined MnO2@CeO2-MnO2 ball-in-ball binary oxide hollow spheres by employing carbon spheres (CSs) as sacrificial templates. The synthesis process involves a novel self-assembled approach to prepare core-shell CSs@CeO2 precursor, which would directly react with KMnO4 aqueous solution to form yolk-shell CSs@MnO2/CeO2-MnO2 precursor in the following step. Well-dispersed Ce-Mn binary oxide with double-shelled hollow sphere structure could be achieved after annealing the precursor in air. The evolution process and formation mechanism of this novel structure were thoroughly studied in this paper. Especially the as-prepared double-shell MnO2/CeO2-MnO2 hollow spheres exhibited enhanced catalytic activity for CO oxidation compared with the pure MnO2 hollow spheres and pure CeO2 hollow spheres. We believe the high surface area, hierarchical porous structures, and strong synergistic interaction between CeO2 and MnO2 contribute to the excellent catalytic activity. Most importantly, this method could be extended to prepare other transition metal oxides. As an example, triple-shelled Co-Mn composite hollow spheres assembled by ultrathin nanoplates were successfully prepared.

  18. Manganese carbonates as possible biogenic relics in Archean settings

    NASA Astrophysics Data System (ADS)

    Rincón-Tomás, Blanca; Khonsari, Bahar; Mühlen, Dominik; Wickbold, Christian; Schäfer, Nadine; Hause-Reitner, Dorothea; Hoppert, Michael; Reitner, Joachim

    2016-07-01

    Carbonate minerals such as dolomite, kutnahorite or rhodochrosite are frequently, but not exclusively generated by microbial processes. In recent anoxic sediments, Mn(II)carbonate minerals (e.g. rhodochrosite, kutnahorite) derive mainly from the reduction of Mn(IV) compounds by anaerobic respiration. The formation of huge manganese-rich (carbonate) deposits requires effective manganese redox cycling in an oxygenated atmosphere. However, putative anaerobic pathways such as microbial nitrate-dependent manganese oxidation, anoxygenic photosynthesis and oxidation in ultraviolet light may facilitate manganese cycling even in an early Archean environment, without the availability of oxygen. In addition, manganese carbonates precipitate by microbially induced processes without change of the oxidation state, e.g. by pH shift. Hence, there are several ways how these minerals could have been formed biogenically and deposited in Precambrian sediments. We will summarize microbially induced manganese carbonate deposition in the presence and absence of atmospheric oxygen and we will make some considerations about the biogenic deposition of manganese carbonates in early Archean settings.

  19. 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.

  20. Manganese Oxide Biomineralization by Spores of the Marine Bacillus sp. Strain SG-1

    NASA Astrophysics Data System (ADS)

    Bargar, J. R.; Tebo, B. M.; Pecher, K. H.; McCubbery, D.; Chiu, V.; Tonner, B. P.

    2001-12-01

    Biogenic Mn oxides are ubiquitous in natural waters, have high sorptive capacities for metal ions, and oxidize organic and inorganic substances such as aromatic hydrocarbons, Cr(III), and hydrogen sulfide. In this fashion, Mn(II)-oxidizing bacteria impact the biogeochemical cycling of essential nutrients and toxic trace constituents of natural waters. In spite of their importance, the molecular mechanisms, intermediates, and products of Mn oxide biomineralization are poorly understood. Similarly, the relationship between biotic and abiotic Mn oxidation mechanisms is not well documented. We have studied Mn oxide biomineralization by spores of the marine Bacillus sp. strain SG-1 as functions of reaction time (10 min to 77 d), Mn(II) concentration (0.01 to 1 mM), major ion composition (50 mM NaCl to sea water), O2 partial pressure, and temperature. SG-1 spores are an ideal subject because they are dormant, Mn-oxidation is not inactivated by the x-rays utilized, and they previously have been extensively studied. Reaction products and Mn oxidation state evolution were directly observed in order to infer mechanisms and phase dominance. To obtain this information, a combination of Mn(II) uptake measurements, K-edge x-ray absorption spectroscopy (XAS), L-edge scanning transmission x-ray microspectroscopy (STXM, 60 nm nominal spot size), and synchrotron-based x-ray diffraction measurements were performed. All samples were measured under fully hydrated conditions to prevent dehydration of reaction products. This set of techniques provides chemical and structural information on Mn in amorphous and crystalline states in the samples. Mn oxide biomineralization products were sensitive to [Mn(II)]. At 0.01 mM [Mn(II)], biogenic Mn oxides were found to contain highly oxidized Mn (80-85% Mn(IV)) as observed after 48 hr. reaction. The dominant phase is identified as an amorphous Mn(IV) oxide similar to d-MnO2. K-edge XAS measurements suggest this phase forms within minutes of

  1. A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean.

    PubMed

    Sauer, Kenneth; Yachandra, Vittal K

    2002-06-25

    The photosynthetic water oxidation complex consists of a cluster of four Mn atoms bridged by O atoms, associated with Ca2+ and Cl-, and incorporated into protein. The structure is similar in higher plants and algae, as well as in cyanobacteria of more ancient lineage, dating back more than 2.5 billion years ago on Earth. It has been proposed that the proto-enzyme derived from a component of a natural early marine manganese precipitate that contained a CaMn4O9 cluster. A variety of MnO2 minerals are found in nature. Three major classes are spinels, sheet-like layered structures, and three-dimensional networks that contain parallel tunnels. These relatively open structures readily incorporate cations (Na+, Li+, Mg2+, Ca2+, Ba2+, H+, and even Mn2+) and water. The minerals have different ratios of Mn(III) and Mn(IV) octahedrally coordinated to oxygens. Using x-ray spectroscopy we compare the chemical structures of Mn in the minerals with what is known about the arrangement in the water oxidation complex to define the parameters of a structural model for the photosynthetic catalytic site. This comparison provides for the structural model a set of candidate Mn(4) clusters-some previously proposed and considered and others entirely novel.

  2. A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean

    SciTech Connect

    Sauer, Kenneth; Yachandra, Vittal K.

    2002-04-30

    The photosynthetic water oxidation complex consists of a cluster of 4 Mn atoms bridged by O atoms, associated with Ca2+ and Cl- and incorporated into protein. The structure is similar in higher plants and algae, as well as in cyanobacteria of more ancient lineage, dating back more than 2.5 Ga on Earth. It has been proposed that the proto-enzyme derived from a component of a natural early marine manganese precipitate that contained a CaMn4O9 cluster. A variety of MnO2 minerals is found in nature. Three major classes are spinels, sheet-like layered structures and 3-dimensional networks that contain parallel tunnels. These relatively open structures readily incorporate cations (Na+, Li+, Mg2+, Ca2+, Ba2+, H+ and even Mn2+) and water. The minerals have different ratios of Mn(III) and Mn(IV) octahedrally coordinated to oxygens. Using X-ray spectroscopy we compare the chemical structures of Mn in the minerals with what is known about the arrangement in the water-oxidation complex to define the parameters of a structural model for the photosynthetic catalytic site. This comparison provides for the structural model a set of candidate Mn4 clusters -- some previously proposed and considered and others entirely novel.

  3. Oxidation Characteristics of Fe–18Cr–18Mn-Stainless Steel Alloys

    SciTech Connect

    Rawers, James

    2010-10-01

    Air oxidation studies of Fe-18Cr-18Mn stainless steels were conducted at 525°C, 625°C, and 725°C. Alloys were evaluated with respect to changes in oxidation properties as a result of interstitial additions of nitrogen and carbon and of minor solute additions of silicon, molybdenum, and nickel. Interstitial concentrations possibly had a small, positive effect on oxidation resistance. Minor solute additions significantly improved oxidation resistance but could also reduce interstitial solubility resulting in formation of chromium carbides. Loss of solute chromium resulted in a slight reduction in oxidation protection. Oxidation lasting over 500 hours produced a manganese rich, duplex oxide structure: an outer sesquioxide and an inner spinel oxide.

  4. Preparation of a novel graphene oxide/Fe-Mn composite and its application for aqueous Hg(II) removal.

    PubMed

    Tang, Jingchun; Huang, Yao; Gong, Yanyan; Lyu, Honghong; Wang, Qilin; Ma, Jianli

    2016-10-05

    A novel graphene oxide/Fe-Mn (GO/Fe-Mn) composite was synthesized (molar ratio of Fe/Mn=3/1 and mass ratio of Fe/GO=1/7.5) and investigated for the sorption characteristics and mechanisms of aqueous mercury (Hg(2+)) as well as the biological effects to wheat and rice. Characterization tests showed that Fe-Mn oxides were impregnated onto GO sheets in an amorphous form through oxygen-containing functional groups (i.e., CO, epoxy COC, carboxyl OCO, and CO) and π-π interactions. GO/Fe-Mn possessed large surface area, surface enhanced Raman scattering with more sp(3) defects, and greater thermal stability than GO. XPS analysis revealed that Fe2O3, FeOOH, MnO2, MnOOH, and MnO were the dominant metal oxides in GO/Fe-Mn. Pseudo-second-order kinetic model and Sips isotherm model fitted well with the sorption kinetic and isotherm data. The maximum sorption capacity for mercury was 32.9mg/g. Ligand exchange and surface complexation were the dominant mechanisms for mercury removal. GO/Fe-Mn greatly reduced the bioavailability of mercury to wheat and rice, even promoted the seedling growth. This work suggests that GO/Fe-Mn can be used as an effective and environmental-friendly adsorbent in heavy metal remediation.

  5. Arsenic(V) Incorporation in Vivianite during Microbial Reduction of Arsenic(V)-Bearing Biogenic Fe(III) (Oxyhydr)oxides.

    PubMed

    Muehe, E Marie; Morin, Guillaume; Scheer, Lukas; Pape, Pierre Le; Esteve, Imène; Daus, Birgit; Kappler, Andreas

    2016-03-01

    The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.

  6. New structural types and different oxidation levels in the family of Mn6-oxime single-molecule magnets.

    PubMed

    Jones, Leigh F; Inglis, Ross; Cochrane, Martyn E; Mason, Kevin; Collins, Anna; Parsons, Simon; Perlepes, Spyros P; Brechin, Euan K

    2008-11-28

    The synthesis and magnetic properties of three new members of a family of salicyaldoxime based [Mn6] single-molecule magnets possessing new structural types, core topologies and Mn oxidation state distributions are reported. The isostructural complexes [MnIII6O2(R-sao)6(X)2(EtOH)6] (R = Et, X = Br (1); R = Me, X = I (2)) exhibit single-molecule magnet behaviour with spin Hamiltonian parameters S = 12, g = 1.98 and D = -0.36 cm(-1) in both cases. The hexametallic cluster [MnIII4MnIV2O2(OMe)(4-)(Et-sao)6(MeOH)2].MeOH (3.MeOH) possesses a planar rod-like topology and a mixed valent [MnIV4MnIII2] core, which is unprecedented in this family of [Mn6] SMMs.

  7. Intense turquoise and green colors in brownmillerite-type oxides based on Mn5+ in Ba2In(2-x)Mn(x)O(5+x).

    PubMed

    Jiang, Peng; Li, Jun; Ozarowski, A; Sleight, Arthur W; Subramanian, M A

    2013-02-04

    Brownmillerite-type oxides Ba(2)In(2-x)Mn(x)O(5+x) (x = 0.1-0.7) have been prepared and characterized. Magnetic measurements indicate that manganese in as-prepared samples is substituting predominantly as Mn(5+) for all values of x with observed paramagnetic spin-only moments close to values expected for two unpaired electrons. Electron paramagnetic resonance measurements indicate that this Mn(5+) is present in a highly distorted tetrahedral environment. Neutron diffraction structure refinements show that Mn(5+) occupies tetrahedral sites for orthorhombic (x = 0.1) and tetragonal (x = 0.2) phases. For Mn ≥ 0.3 samples, neutron refinements show that the phases are cubic with disordered cations and oxygen vacancies. The colors of the phases change from light yellow (x = 0) to intense turquoise (x = 0.1) to green (x = 0.2, 0.3) or to dark green (x ≥ 0.4). Under reducing conditions, Mn(5+) is reduced to Mn(3+), and Ba(2)In(2-x)Mn(x)O(5+x) phases become black Ba(2)In(2-x)Mn(x)O(5) phases still with the brownmillerite structure.

  8. Removal of Mn2+ from water by "aged" biofilter media: the role of catalytic oxides layers.

    PubMed

    Sahabi, Danladi Mahuta; Takeda, Minoru; Suzuki, Ichiro; Koizumi, Jun-ichi

    2009-02-01

    The present work was aimed at evaluating the surface coatings characteristics and autocatalytic manganese oxidation potentials of two groups of "aged" biofilter media. This refers to the anthracite filter media of a biological water treatment plant on which metal oxides and a biofilm have deposited on the surface of the filter media over long time of filtration. Duplicate samples of anthracite filter media were collected from each of the six filter wells in the plant and classified into two groups, based on their duration of operation, as 3-years filter media and 15-years filter media. Batch experiments showed that the 15-years filter media exhibited very high manganese sorption capacity and were less dependent on the microbial activity than the 3-years filter media. Results of the surface coatings analyses indicated that the biofilter materials is predominantly composed of variable layers of manganese and iron oxides, with microbial biomass contributing only about 3.5 and 1.4% of the dry weight of the surface coatings on the 3- and 15-years filter media respectively. Investigations onto the Mn2+ sorption by the lyophilized biofilter media showed that, the sorption kinetics on the catalytic oxides layers followed the pseudo-second-order kinetics model, thus suggesting chemisorption as the dominant mechanism of Mn2+ removal. This implied that manganese removal by these biofilters is mainly by adsorption of Mn2+ onto the iron and manganese (catalytic) oxides layers and autocatalytic oxidation. The present study has clearly linked Mn2+ oxidation to the catalytic oxides layers on the aged biofilter media.

  9. Dimers and organosulfates derived from biogenic oxidation products in aerosols during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in California 2007 and 2009 (Invited)

    NASA Astrophysics Data System (ADS)

    Glasius, M.; Worton, D. R.; Kristensen, K.; Nguyen, Q.; Surratt, J.; Enggrob, K. L.; Bouvier-Brown, N. C.; Farmer, D.; Docherty, K. S.; Platt, S.; Bilde, M.; Nøjgaard, J. K.; Seinfeld, J.; Jimenez, J. L.; Goldstein, A.

    2010-12-01

    Oxidation products of biogenic volatile organic compounds, such as monoterpenes and isoprene, contribute to biogenic secondary organic aerosol (BSOA). The organosulfate derivatives of these compounds are formed through heterogeneous reactions involving sulphur compounds, with a considerable contribution from anthropogenic sources. Organosulfate derivatives of biogenic oxidation products thus belong to a new group of anthropogenic enhanced biogenic SOA (ABSOA). The Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) during summers of 2007 and 2009 provided an excellent platform at Blodgett Forest, California (a ponderosa pine plantation) for studying ABSOA. Typically, polluted air masses were transported upslope from the California Central Valley during day, while night conditions were influenced by downslope transport of air masses, low local atmospheric mixing and formation of a shallow boundary layer. We collected particle samples (PM2.5) as one nighttime and two daytime samples per day. After extraction of filters in polar organic solvents (i.e. acetonitrile or methanol), organic aerosol constituents were analyzed by HPLC coupled through an electrospray inlet to a quadrupole time-of-flight mass spectrometer (qTOF-MS). Organosulfates and nitrooxy organosulfates derived from oxidation products of α-pinene, β-pinene, limonene and isoprene were identified based on their molecular mass and MS fragmentation patterns. Measurements by High Resolution Time of Flight Aerosol Mass Spectrometry (HR-ToF-AMS) show high mass loadings of nitrate in the night and morning samples with highest levels of the nitrooxy organosulfates with MW 295 and MW 297. This may indicate that elevated levels of nitrate and nitrooxy organosulfates are formed in the same polluted air mass, probably through nitrate radical reactions. Terpenylic acid, diterpenylic acid acetate, and methylbutane tricarboxylic acid were found at concentrations comparable to pinic acid. A dimer of

  10. Reconsidering the possibility of room temperature ferromagnetism in Mn-doped zirconium oxide

    NASA Astrophysics Data System (ADS)

    Chakraborty, Akash; Bouzerar, Georges

    2013-12-01

    The possibility to induce long-range ferromagnetic order by doping oxides with transition metal ions has become a very exciting challenge in the last decade. Theoretically, it has been claimed that Mn-doped ZrO2 could be a very promising spintronic candidate and that high critical temperatures could be already achieved even for a low Mn concentration. Some experiments have reported room temperature ferromagnetism (RT-FM) whilst some others only paramagnetism. When observed, the nature of RT-FM appears to be controversial and not clearly understood. In this study, we propose to clarify and shed light on some of theses existing issues. A detailed study of the critical temperatures and low-energy magnetic excitations in Mn-doped ZrO2 is performed. We show that the Curie temperatures were largely overestimated previously, due to the inadequate treatment of both thermal and transverse fluctuations, and disorder. It appears that the Mn-Mn couplings cannot explain the observed RT-FM. We argue, that this can be attributed to the interaction between large moments induced in the vicinity of the manganese. This is similar to the non-magnetic defect-induced ferromagnetism reported in oxides, semiconductors and graphene/graphite.

  11. Effects of Mn Doping on Zinc Oxide Films Prepared by Spray Pyrolysis Technique

    NASA Astrophysics Data System (ADS)

    Singh, Bhavana; Shrivastava, S. B.; Ganesan, V.

    The work deals with the preparation of Zinc Oxide (ZnO) thin films on microscopic glass substrate by spray pyrolysis technique. The systematic study on the influence of Mn doping up to 15% has been performed. The structural studies revealed that pure and doped film has hexagonal structure. In order to reduce the internal strain due to Mn doping, the crystallite size decreases. The atomic force microscopy (AFM) measurement shows the decrease in grain size and roughness with doping. The resistivity curve shows a clear hump corresponding to smaller Mn doping (x=0.5-4%) around T˜340-365 K. This hump was found to reduce with the increase in Mn concentration and for x≥7.5, beyond which it vanishes completely. This is attributed to critical behavior of resistivity and may be due to the scattering of carriers by magnetic spin fluctuation via exchange interaction. The optical measurement shows the shift in absorption edge of Mn doped ZnO films toward the longer wavelength side. This correlates the reduction in grain size as a function of Mn concentration. The optical bandgap goes down, whereas refractive index increases with dopant concentration.

  12. Activation of Manganese Oxidants with Bisulfite for Enhanced Oxidation of Organic Contaminants: The Involvement of Mn(III).

    PubMed

    Sun, Bo; Guan, Xiaohong; Fang, Jingyun; Tratnyek, Paul G

    2015-10-20

    MnO4(-) was activated by HSO3(-), resulting in a process that oxidizes organic contaminants at extraordinarily high rates. The permanganate/bisulfite (PM/BS) process oxidized phenol, ciprofloxacin, and methyl blue at pHini 5.0 with rates (kobs ≈ 60-150 s(-1)) that were 5-6 orders of magnitude faster than those measured for permanganate alone, and ∼5 to 7 orders of magnitude faster than conventional advanced oxidation processes for water treatment. Oxidation of phenol was fastest at pH 4.0, but still effective at pH 7.0, and only slightly slower when performed in tap water. A smaller, but still considerable (∼3 orders of magnitude) increase in oxidation rates of methyl blue was observed with MnO2 activated by HSO3(-) (MO/BS). The above results, time-resolved spectroscopy of manganese species under various conditions, stoichiometric analysis of pH changes, and the effect of pyrophosphate on UV absorbance spectra suggest that the reactive intermediate(s) responsible for the extremely rapid oxidation of organic contaminants in the PM/BS process involve manganese(III) species with minimal stabilization by complexation. The PM/BS process may lead to a new category of advanced oxidation technologies based on contaminant oxidation by reactive manganese(III) species, rather than hydroxyl and sulfate radicals.

  13. The extrinsic PsbO protein modulates the oxidation/reduction rate of the exogenous Mn cation at the high-affinity Mn-binding site of Mn-depleted PSII membranes.

    PubMed

    Semin, Boris K; Podkovirina, Tatiana E; Davletshina, Lira N; Timofeev, Kirill N; Ivanov, Il'ya I; Rubin, Andrei B

    2015-08-01

    The oxidation of exogenous Mn(II) cations at the high-affinity (HA) Mn-binding site in Mn-depleted photosystem II (PSII) membranes with or without the presence of the extrinsic PsbO polypeptide was studied by EPR. The six-lines EPR spectrum of Mn(II) cation disappears in the absence of the PsbO protein in membranes under illumination, but there was no effect when PSII preparations bound the PsbO protein. Our study demonstrates that such effect is determined by significant influence of the PsbO protein on the ratio between the rates of Mn oxidation and reduction at the HA site when the membranes are illuminated.

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

    SciTech Connect

    Semin, Boris K.; Seibert, Michael

    2016-02-04

    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.

  15. Mechanistic studies of mercury adsorption and oxidation by oxygen over spinel-type MnFe2O4.

    PubMed

    Yang, Yingju; Liu, Jing; Zhang, Bingkai; Liu, Feng

    2017-01-05

    MnFe2O4 has been regarded as a very promising sorbent for mercury emission control in coal-fired power plants because of its high adsorption capacity, magnetic, recyclable and regenerable properties. First-principle calculations based on density functional theory (DFT) were used to elucidate the mercury adsorption and oxidation mechanisms on MnFe2O4 surface. DFT calculations show that Mn-terminated MnFe2O4 (1 0 0) surface is much more stable than Fe-terminated surface. Hg(0) is physically adsorbed on Fe-terminated MnFe2O4 (1 0 0) surface. Hg(0) adsorption on Mn-terminated MnFe2O4 (1 0 0) surface is a chemisorption process. The partial density of states (PDOS) analysis indicates that Hg atom interacts strongly with surface Mn atoms through the orbital hybridization. HgO is adsorbed on the MnFe2O4 surface in a chemical adsorption manner. The small HOMO-LUMO energy gap implies that HgO molecular shows high chemical reactivity for HgO adsorption on MnFe2O4 surface. The energy barriers of Hg(0) oxidation by oxygen on Fe- and Mn-terminated MnFe2O4 surfaces are 206.37 and 76.07kJ/mol, respectively. Mn-terminated surface is much more favorable for Hg(0) oxidation than Fe-terminated surface. In the whole Hg(0) oxidation process, the reaction between adsorbed mercury and surface oxygen is the rate-determining step.

  16. 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.

  17. Structural transformations in cubic structure of Mn/Co perovskites in reducing and oxidizing atmospheres

    NASA Astrophysics Data System (ADS)

    Koponen, Markus J.; Suvanto, Mika; Kallinen, Kauko; Kinnunen, Toni-J. J.; Härkönen, Matti; Pakkanen, Tapani A.

    2006-05-01

    ABO ( A=La, Pr; B=Mn, Co), ABBx'O ( A=La, Pr; B=Mn, Co; B=Co, Pd), and ABCoPdO ( A=La, Pr; B=Fe, Mn) ( x=0.05, 0.37; y=0.38) perovskites were synthesized via malic acid complexation. O 2-TPD, O 2-TPO, and H 2-TPR treatments were carried out to study the oxidation and reduction behavior of the synthesized perovskites. LaCo 0.95Pd 0.05O 3, PrCo 0.95Pd 0.05O 3, and PrCoO 3 perovskites had the highest desorption, oxidation, and reduction activity within the studied perovskite series. Powder XRD studies revealed structural transformation of the cubic structure of all synthesized perovskites except LaFe 0.57Co 0.38Pd 0.05O 3 in H 2/Ar atmosphere when the temperature was over 400 °C. The decomposed structure reverted to the original perovskite structure under oxidizing atmosphere. This reversion was accompanied by increased oxygen desorption activity. It was noticed that the Co and Mn combinations in the B-site of the perovskites structure decreased the thermal stability of the synthesized perovskites.

  18. Catalytic combustion of benzene over nanosized LaMnO3 perovskite oxides.

    PubMed

    Jung, Won Young; Lim, Kwon Taek; Lee, Gun Dae; Lee, Man Sig; Hong, Seong-Soo

    2013-09-01

    In this study, LaMnO3 perovskite type oxides were successfully prepared using the malic acid method. The oxides were characterized by TG/DTA, XRD, XPS, TEM and H2-TPR and their catalytic activities for the combustion of benzene were determined. Almost all of the catalysts showed perovskite crystalline phase and had a particle size of 15-60 nm. The LaMnO3 catalysts prepared with more than 1.0 mol of malic acid showed the highest activity and the conversion reached almost 100% at 310 degrees C. The catalysts were modified to enhance the activity by substituting the metal at the A or B site of the perovskite oxides. In the LaMnO3-type catalyst, the partial substitution of Sr into site A enhanced the catalytic activity during benzene combustion. In addition, the partial substitution of Co into site B also increased the catalytic activity and the catalytic activity was in the following order: Co > Cu > Fe in the LaMn1_xBxO3(B = Co, Fe, Cu) type catalysts.

  19. 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.

  20. Olefin oxidation by zeolite-encapsulated Mn(salen) sup + complexes under ambient conditions

    SciTech Connect

    Bowers, C.; Dutta, P.K. )

    1990-04-01

    Zeolite-encapsulated manganese complex of the salen ligand (N,N{prime}-ethylenebis(salicylideneaminato)) was synthesized, and its catalytic activity toward various olefins was examined. Iodosylbenzene was chosen to be the terminal oxidant. Oxidation products, which included the epoxide, alcohol, and aldehyde, are formed from cyclohexene, styrene, and trans- and cis-stilbene. In comparison with catalysis by Mn(salen){sup +} complexes in solution, encapsulation lowers the rate of reaction considerably, but provides for selective oxidation based on olefin size and ability to penetrate the zeolite cages.

  1. Sputtering and native oxide formation on (110) surfaces of Cd(1-x)Mn(x)Te

    NASA Technical Reports Server (NTRS)

    Neff, H.; Lay, K. Y.; Abid, B.; Lange, P.; Lucovsky, G.

    1986-01-01

    Native oxides on the surface of Cd(1-x)Mn(x)Te (X between 0 and 0.7) have been analyzed on the basis of X-ray photoemission spectroscopy measurements. Depth profile analysis revealed a significant increase in the thickness at higher Mn concentrations and a strong Mn segregation to the surface, respectively. Sputter-induced damage on cleaved (110)-oriented surfaces was analyzed by photoreflectance and photoluminescence measurements. The damage was found to be larger on CdTe than on the alloy. Thermal annealing showed nearly complete restoration for the surface of the alloy, while CdTe revealed irreversible modifications in the near-surface regime upon sputtering and post annealing.

  2. Elemental mercury oxidation and adsorption on magnesite powder modified by Mn at low temperature.

    PubMed

    Xu, Yalin; Zhong, Qin; Liu, Xinya

    2015-01-01

    Mn modified the commercial magnesite powder prepared by wet impregnation method has been shown to be effective for gas-phase elemental mercury (Hg(0)) removal at low temperatures. The prepared samples are characterized in detail across multiform techniques: XRF, BET, SEM-EDX, XRD, H2-TPR, and XPS, and all the results show that the amorphous MnO2 impregnated on magnesite powder improves the removal efficiency of Hg(0). Through further analysis by TG and in situ FTIR, the reasonable removal mechanism is also speculated. The results indicate that chemisorbed oxygen is an important reactant in the heterogeneous reaction, and gas-phase Hg(0) is adsorbed and then oxidized to solid MnHgO3 on the surface of the adsorbent.

  3. Electrochemical oxidation of methanol on Pt nanoparticles composited MnO 2 nanowire arrayed electrode

    NASA Astrophysics Data System (ADS)

    Zhao, Guang-Yu; Li, Hu-Lin

    2008-03-01

    By use of the membrane-template synthesis route, MnO 2 nanowire arrayed electrodes are successfully synthesized by means of the anodic deposition technique. The Pt nanoparticles composited MnO 2 nanowire arrayed electrodes (PME) are obtained through depositing Pt on MnO 2 nanowire arrayed electrode by cathode deposition technique. For comparison of electrochemical performance, Pt nanowire arrayed electrodes which have the same amount of Pt with PME are also prepared. The electro-oxidation of methanol on PME and Pt nanowire arrayed electrodes is investigated at room temperature by cyclic voltammetry, which show that about 110 mV decreased overpotential and 2.1-fold enhanced votammetric current are achieved on PME. The chronoamperometry result demonstrates that the resistance to carbon monoxide for PME is improved.

  4. Shell Model for Atomistic Simulation of Lithium Diffusion in Mixed Mn/Ti Oxides

    SciTech Connect

    Kerisit, Sebastien N.; Chaka, Anne M.; Droubay, Timothy C.; Ilton, Eugene S.

    2014-10-23

    Mixed Mn/Ti oxides present attractive physicochemical properties such as their ability to accommodate Li for application in Li-ion batteries. In this work, atomic parameters for Mn were developed to extend an existing shell model of the Li-Ti-O system and allow simulations of pure and lithiated Mn and mixed Mn/Ti oxide polymorphs. The shell model yielded good agreement with experimentally-derived structures (i.e. lattice parameters and inter-atomic distances) and represented an improvement over existing potential models. The shell model was employed in molecular dynamics (MD) simulations of Li diffusion in the 1×1 c direction channels of LixMn1 yTiyO2 with the rutile structure, where 0 ≤ x ≤ 0.25 and 0 ≤ y ≤ 1. In the infinite dilution limit, the arrangement of Mn and Ti ions in the lattice was found to have a significant effect on the activation energy for Li diffusion in the c channels due to the destabilization of half of the interstitial octahedral sites. Anomalous diffusion was demonstrated for Li concentrations as low as x = 0.125, with a single Li ion positioned in every other c channel. Further increase in Li concentration showed not only the substantial effect of Li-Li repulsive interactions on Li mobility but also their influence on the time dependence of Li diffusion. The results of the MD simulations can inform intrinsic structure-property relationships for the rational design of improved electrode materials for Li-ion batteries.

  5. 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.

  6. On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

    SciTech Connect

    Kwon, K.D.; Refson, K.; Sposito, G.

    2009-06-01

    Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO{sub 2} and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).

  7. Mesoporous MnCeOx 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 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%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganesemore » 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.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  9. 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

  10. 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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  11. Synthesis of ultrasmall Li-Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties.

    PubMed

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-10-12

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li-Mn spinel oxides by tuning the hydration of Li(+) ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m(2) g(-1). They exhibited unique properties such as unusual topotactic Li(+)/H(+) ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li-Mn spinel oxides obtained by conventional solid-state methods.

  12. Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    PubMed Central

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-01-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li–Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g−1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li–Mn spinel oxides obtained by conventional solid-state methods. PMID:26456216

  13. Biogenic VOC measurements during the Oxidant and Particle Photochemical Processes (OP3) above a South-East Asian tropical rainforest Campaign

    NASA Astrophysics Data System (ADS)

    Jones, Charlotte; Hopkins, James; Lee, James; Lewis, Alastair; Hamilton, Jacqueline

    2010-05-01

    We present the first ambient air speciated monoterpene measurements from the UK FGAM (Facility for Ground based Atmospheric Measrements) - York dual channel gas chromatograph system with flame ionisation detectors, alongside measurements of other biogenic volatile organic compounds (BVOCs) such as isoprene, which were made during the Oxidant and Particle Photochemical Processes above a South-East Asian tropical rainforest (OP3) campaign in Danum Valley, Borneo, in 2008. The monoterpenes measured were alpha-pinene, camphene, 3-carene, gamma-terpinene and limonene. We compare the relative concentrations and diurnal profiles of the different monoterpene species and other BVOCs such as isoprene, and analyse variability in their concentrations in light of various environmental conditions, in order to gain insight into factors which influence their emission rates, and therefore regulate their potential impact upon photochemical processes within the boundary layer. We also present regional BVOC measurements made onboard the FAAM BAE 146 aircraft over both the natural rainforest and oil palm plantations.

  14. Oxidative transformation of levofloxacin by δ-MnO2: products, pathways and toxicity assessment.

    PubMed

    Li, Yuan; Wei, Dongbin; Du, Yuguo

    2015-01-01

    The characteristics of the oxidative transformation of the antibiotic levofloxacin (abbreviated as LEV) by manganese oxide were investigated. Up to 91% of LEV were removed with an equivalent of 200 units (abbreviated as equiv) of manganese oxide within a 35-day treatment period. A total of ten transformation products were identified, and five of them were newly reported. A tentative transformation pathway of LEV in the manganese oxide system involving oxidation and dealkylation was proposed. In addition, the variation in the genotoxicity and antibacterial activity along with the treatment by manganese oxide were traced using a SOS/umu assay and Escherichia coli growth inhibition assay, respectively. The results indicated that the genotoxicity significantly decreased in response to treatment with manganese oxide, while the antibacterial activity was not markedly affected until 160-equiv of δ-MnO2 were added. This study suggests that the oxidative degradation of LEV by manganese oxide can play an important role in the natural attenuation of LEV in sediment or soil matrices. The transformation reaction may be further optimized for removing quinolone antibiotics from wastewater or other environmental matrices to reduce the potential risk.

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

    PubMed Central

    2016-01-01

    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. PMID:26645454

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

    SciTech Connect

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

    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. 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.

  17. Design of Mn porphyrins for treating oxidative stress injuries and their redox-based regulation of cellular transcriptional activities

    PubMed Central

    Spasojevic, Ivan; Tse, Hubert M.; Tovmasyan, Artak; Rajic, Zrinka; St. Clair, Daret K.; Vujaskovic, Zeljko; Dewhirst, Mark W.; Piganelli, Jon D.

    2010-01-01

    The most efficacious Mn(III) porphyrinic (MnPs) scavengers of reactive species have positive charges close to the Mn site, whereby they afford thermodynamic and electrostatic facilitation for the reaction with negatively charged species such as O2•− and ONOO−. Those are Mn(III) meso tetrakis(N-alkylpyridinium-2-yl)porphyrins, more specifically MnTE-2-PyP5+ (AEOL10113) and MnTnHex-2-PyP5+ (where alkyls are ethyl and n-hexyl, respectively), and their imidazolium analog, MnTDE-2-ImP5+ (AEOL10150, Mn(III) meso tetrakis(N,N′-diethylimidazolium-2-yl) porphyrin). The efficacy of MnPs in vivo is determined not only by the compound antioxidant potency, but also by its bio-availability. The former is greatly affected by the lipophilicity, size, structure, and overall shape of the compound. These porphyrins have the ability to both eliminate reactive oxygen species and impact the progression of oxidative stress-dependent signaling events. This will effectively lead to the regulation of redox-dependent transcription factors and the suppression of secondary inflammatory- and oxidative stress-mediated immune responses. We have reported on the inhibition of major transcription factors HIF-1α, AP-1, SP-1, and NF-κB by Mn porphyrins. While the prevailing mechanistic view of the suppression of transcription factors activation is via antioxidative action (presumably in cytosol), the pro-oxidative action of MnPs in suppressing NF-κB activation in nucleus has been substantiated. The magnitude of the effect is dependent upon the electrostatic (porphyrin charges) and thermodynamic factors (porphyrin redox ability). The pro-oxidative action of MnPs has been suggested to contribute at least in part to the in vitro anticancer action of MnTE-2-PyP5+ in the presence of ascorbate, and in vivo when combined with chemotherapy of lymphoma. Given the remarkable therapeutic potential of metalloporphyrins, future studies are warranted to further our understanding of in vivo action/s of Mn

  18. Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

    DOE PAGES

    Nguyen, T. B.; Crounse, J. D.; Schwantes, R. H.; ...

    2014-12-19

    The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech.more » During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark- and photo-induced oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models.« less

  19. Adsorption and Catalytic Oxidation of Gaseous Elemental Mercury in Flue Gas over MnOx/Alumina

    SciTech Connect

    Qiao, S.H.; Chen, J.; Li, J.F.; Qu, Z.; Liu, P.; Yan, N.Q.; Jia, J.Q.

    2009-04-15

    MnOx/Al{sub 2}O{sub 3} catalysts (i.e., impregnating manganese oxide on alumina) were employed to remove elemental mercury (Hg{sup 0}) from flue gas. MnOx/Al{sub 2}O{sub 3} was found to have significant adsorption performance on capturing Hg{sup 0} in the absence of hydrogen chloride (HCl), and its favorable adsorption temperature was about 600 K. However, the catalytic oxidation of Hg{sup 0} became dominant when HCl or chlorine (Cl{sub 2}) was present in flue gas, and the removal efficiency of Hg{sup 0} was up to 90% with 20 ppm of HCl or 2 ppm of Cl{sub 2}. In addition, the catalysts with adsorbed mercury could be chemically regenerated by rinsing with HCl gas to strip off the adsorbed mercury in the form of HgCl{sub 2}. Sulfur dioxide displayed inhibition to the adsorption of Hg{sup 0} on the catalysts, but the inhibition was less to the catalytic oxidation of Hg{sup 0}, especially in the presence of Cl{sub 2}. The analysis results of XPS and pyrolysis-AAS indicated that the adsorbed mercury was mainly in the forms of mercuric oxide (Hg{sup 0}) and the weakly bonded speciation, and the ratio of them varied with the adsorption amount and manganese content on catalysts. The multifunctional performances of MnOx/Al{sub 2}O{sub 3} on the removal of Hg{sup 0} appeared to the promising in the industrial applications.

  20. Frenkel-Defect-Mediated Chemical Ordering Transition in a Li-Mn-Ni Spinel Oxide.

    PubMed

    Ryoo, Hyewon; Bae, Hyung Bin; Kim, Young-Min; Kim, Jin-Gyu; Lee, Seongsu; Chung, Sung-Yoon

    2015-06-26

    Using spinel-type Li(Mn(1.5)Ni(0.5) )O4 with two different cations, Mn and Ni, in the oxygen octahedra as a model system, we show that a cation ordering transition takes place through the formation of Frenkel-type point defects. A series of experimental results based on atomic-scale observations and in situ powder diffractions along with ab initio calculations consistently support such defect-mediated transition behavior. In addition to providing a precise suggestion of the intermediate transient states and the resulting kinetic pathway during the transition between two phases, our findings emphasize the significant role of point defects in ordering transformation of complex oxides.

  1. Electronic properties and native point defects of high efficient NO oxidation catalysts SmMn2O5

    NASA Astrophysics Data System (ADS)

    Li, Hao-Bo; Yang, Zhi; Liu, Jieyu; Yao, Xiaolong; Xiong, Ka; Liu, Hui; Wang, Wei-Hua; Lu, Feng; Wang, Weichao

    2016-11-01

    Mn-based oxide SmMn2O5 exhibits great catalytic performance in NO oxidation [Wang et al., Science 337, 832 (2012)]. Nevertheless, the fundamental understanding of SmMn2O5 properties is so far not fully accessible. Here, the SmMn2O5 nanoparticles are synthesized through hydrothermal methods, and the pure phase of triclinic SmMn2O5 is characterized by high-resolution tunneling electron microscope and X-ray diffraction. Furthermore, the X-ray photoelectron spectroscopy, absorption, photoluminescence spectra (PL), and density functional theory based first-principles calculations are employed to explore the fundamental electronic structures of pristine and defective SmMn2O5. Combined with band structure calculations, light absorption, and PL spectra, we first show that SmMn2O5 presents an insulating behavior with an indirect band gap of ˜1.0 eV. Between the two types of crystal fields, i.e., octahedral and tetrahedral, the later one contributes to the dz2 of the valence band edge, resulting in superior catalytic performance of NO oxidation. Furthermore, the native point defects in SmMn2O5 are first reported. Among the various native point defects, we demonstrate that oxygen vacancy (VO) shows the lowest formation energy in oxygen poor conditions, while the oxygen interstitial (Oi) and Mn vacancies are energetically favorable in oxygen rich situations. In other words, SmMn2O5 could be potentially utilized as an oxygen storage material.

  2. Temporal and spatial distribution of tropospheric NO2 over arid areas of Central Asia by OMI Satellite observations: Evidence for a strong contribution of soil biogenic nitric oxide

    NASA Astrophysics Data System (ADS)

    Mamtimin, Buhalqem; Qi, Yue; Beirle, Steffen; Wagner, Thomas; Meixner, Franz X.

    2013-04-01

    We present results observations of tropospheric NO2 carried out by Ozone Monitoring Instrument (OMI) over the Central Asian arid areas from 2005 to 2011. We selected 8 oases (Ruoqiang, Milan, Waxxari, Qiemo, Minfeng, Shache, Awati and Kuche) in Taklimakan desert (part of the great Central Asian deserts). For these, spatial distributions, seasonal variations, and trends of tropospheric NO2 Vertical Column Densities (VCDs) retrieved are discussed. In the Taklimakan desert, oases are the centers of all human activities and the economy of the selected oases are dominated by oasis agriculture. Irrigation and fertilization favor the microbial production of nitric oxide in soils, which after emission is converted to NO2 by ozone. Consequently, tropospheric NO2-VCDs are a good proxy for biogenic NO emissions from soils. For contrast, we examined also the NO2-VCDs in the area of the growing megacity Urumqi (43.85°N, 87.62°E), which is known as an anthropogenic highly polluted city in the Central Asian deserts. For 2005-2011, all selected oases are hot spots of NO/NO2 in the Taklimakan desert. Higher NO2-VCDs were observed during growing seasons over all 8 oases. NO2-VCDs observed in summer generally increased from 2005 to 2011. NO2-VCDs over Urumqi were generally at least 1 order of magnitude higher than those over the oases. In contrast to the oases, wintertime NO2-VCDs over Urumqi are higher than in summer. We evaluated governmental statistical agricultural data of the 8 oasis, and compared the trends with corresponding summertime NO2-VCDs. Inter-annual trends of NO2-VCDs over the oases show similar patterns to those of N-fertilizer application and sown (and irrigated) areas. Highest NO2-VCDs observed in summer for agriculturally dominated oases are a strong indication that soil biogenic NO emission is the main contributor to the tropospheric NO2 over all 8 oases, while in Urumqi fossil fuel combustion, particularly during winter, is the main source for NO/NO2. With

  3. Superior lithium storage performance using sequentially stacked MnO2/reduced graphene oxide composite electrodes.

    PubMed

    Kim, Sue Jin; Yun, Young Jun; Kim, Ki Woong; Chae, Changju; Jeong, Sunho; Kang, Yongku; Choi, Si-Young; Lee, Sun Sook; Choi, Sungho

    2015-04-24

    Hybrid nanostructures based on graphene and metal oxides hold great potential for use in high-performance electrode materials for next-generation lithium-ion batteries. Herein, a new strategy to fabricate sequentially stacked α-MnO2 /reduced graphene oxide composites driven by surface-charge-induced mutual electrostatic interactions is proposed. The resultant composite anode exhibits an excellent reversible charge/discharge capacity as high as 1100 mA h g(-1) without any traceable capacity fading, even after 100 cycles, which leads to a high rate capability electrode performance for lithium ion batteries. Thus, the proposed synthetic procedures guarantee a synergistic effect of multidimensional nanoscale media between one (metal oxide nanowire) and two dimensions (graphene sheet) for superior energy-storage electrodes.

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

    NASA Astrophysics Data System (ADS)

    Yu, Changxun; Drake, Henrik; Mathurin, Frédéric A.; Åström, Mats E.

    2017-02-01

    This study focuses on the mechanisms of Ce sequestration and accumulation in the fracture network of the upper kilometer of the granitoid bedrock of the Baltic Shield in southeast Sweden (Laxemar area, Sweden). The material includes 81 specimens of bulk secondary mineral precipitates (;fracture coatings;) collected on fracture walls identified in 17 drill cores, and 66 groundwater samples collected from 21 deep boreholes with equipment designed for retrieval of representative groundwater at controlled depths. The concentrations of Ce in the fracture coatings, although varying considerably (10-90th percentiles: 67-438 mg kg-1), were frequently higher than those of the wall rock (10-90th percentiles: 70-118 mg kg-1). Linear combination fitting analysis of Ce LIII-edge X-ray absorption near-edge structure (XANES) spectra, obtained for 19 fracture coatings with relatively high Ce concentrations (⩾145 mg kg-1) and a wide range of Ce-anomaly values, revealed that Ce(IV) occurs frequently in the upper 10 m of the fracture network (Ce(IV)/Cetotal = 0.06-1.00 in 8 out of 11 specimens) and is mainly associated with Mn oxides (modeled as Ce oxidatively scavenged by birnessite). These features are in line with the strong oxidative and sorptive capacities of Mn oxide as demonstrated by previous studies, and abundant todorokite and birnessite-like Mn oxides identified in 3 out of 4 specimens analyzed by Mn K-edge X-ray absorption spectroscopy (XAS) in the upper parts of the fracture network (down to 5 m). For a specimen with very high Ce concentration (1430 mg kg-1) and NASC-normalized Ce anomaly (3.63), the analysis of Ce XANES and Mn XAS data revealed (i) a predominance of Ce oxide in addition to Ce scavenged by Mn oxide; and (ii) a large fraction of poorly-crystalline hexagonal birnessite and aqueous Mn2+, suggesting a recent or on-going oxidation of Mn2+ in this fracture. In addition, the Ce oxide precipitates on this fracture observed by in situ SEM-EDS contained

  5. Preparation and application of Mn-substituted δ-FeOOH for oxidative adsorption of As(III)

    NASA Astrophysics Data System (ADS)

    Chon, C.; Yang, H.; Cho, D.; Kim, Y.; Schwartz, F.; Lee, E.; Jeon, B.; Song, H.

    2013-12-01

    Iron oxides are one of the commonly used media for arsenic treatment, but they have significantly low adsorption capacity for As(III) than As(V), rendering limited applicability to treat groundwater possessing relatively high level of As(III). In this study, we prepared a Mn-substituted iron oxyhydroxide and demonstrated its applicability for enhancing As(III) removal. Four synthetic samples of Mn-substituted δ-FeOOH (MSF) with different ratios of Mn:Fe (0, 10, 30, and 50%) were prepared by oxidative hydrolysis of Fe(II) and Mn(II) salts with very rapid oxidation using H2O2. X-ray diffraction and Rietveld refinement analysis revealed that the crystal structures of MSFs resembles those of feroxyhyte (δ'-FeOOH), with the c unit cell parameter proportionally decreasing with increasing Mn-substitution, resulting in formation of δ-(Fe1-x, Mnx)OOH like structure. Adsorption batch experiments with MSF revealed that As(III) was oxidized into As(V) by surface oxidation of MSF, suggesting Mn-mediated oxidative adsorption of As(III). This oxidative removal of As(III) is consistent with previous studies that reported removal of As(III) by iron minerals containing MnOOH or reduced species of Mn. However, the adsorption capacities decreased from 20.0 to 10.8 mg/g with increasing Mn ratio from 0 to 50%. This indicates the loss of available adsorption sites by increased occupancy of Mn on the surface sites. Arsenic removal by iron oxides has been reported to occur via co-precipitation of As(III) and an inner-sphere complexation of As(V) that involves Fe atoms on the surface. Therefore, it appears Mn-substitution on Fe is for the decrease of arsenic sorption.. The adsorption of arsenic on MSF containing 10% Mn exhibited 93.8 % removal within the first 70 min and reaching sorption equilibrium after 530 min for initial As(III) concentration of 19.5 mg/L. Adsorption capacities of MSF were 18.3, 44.5, and 55.3 mg/g for the initial concentrations of 19.5, 52.7 and 96.7 mg

  6. Thermodynamic modeling of oxide phases in the Fe-Mn-O system

    NASA Astrophysics Data System (ADS)

    Kang, Youn-Bae; Jung, In-Ho

    2016-11-01

    A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-O system 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 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. Two spinel phases (cubic and tetragonal) were modeled using Compound Energy Formalism (CEF) with the use of physically meaningful parameters. The present Fe-Mn spinel solutions can be integrated into a larger spinel solution database, which has been already developed. 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.

  7. Mn K-edge XANES and Kbeta XES studies of two Mn-oxo binuclear complexes: investigation of three different oxidation states relevant to the oxygen-evolving complex of photosystem II.

    PubMed

    Visser, H; Anxolabéhère-Mallart, E; Bergmann, U; Glatzel, P; Robblee, J H; Cramer, S P; Girerd, J J; Sauer, K; Klein, M P; Yachandra, V K

    2001-07-25

    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 Kbeta X-ray emission spectroscopy (Kbeta XES). The two manganese compounds are the di-mu-oxo compound [L'2Mn(III)O2Mn(IV)L'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-mu-oxo compound [LMn(III)OMn(III)L](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 Mn(IV)Mn(IV) species for the di-mu-oxo compound and the Mn(III)Mn(IV) and Mn(IV)Mn(IV) species for the mono-mu-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-mu-oxo and linear mono-mu-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, Kbeta XES spectra show less dependence on ligand environment. The Kbeta1,3 peak energies are comparable for the di-mu-oxo and mono

  8. 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.

  9. Synthesis and Comparative Catalytic Study of Zirconia–MnCO3 or –Mn2O3 for the Oxidation of Benzylic Alcohols

    PubMed Central

    Assal, Mohamed E.; Kuniyil, Mufsir; Khan, Mujeeb; Al‐Warthan, Abdulrahman; Siddiqui, Mohammed Rafiq H.; Tremel, Wolfgang

    2016-01-01

    Abstract We report on the synthesis of the zirconia–manganese carbonate ZrO x (x  %)–MnCO3 catalyst (where x=1–7) that, upon calcination at 500 °C, is converted to zirconia–manganese oxide ZrO x (x  %)–Mn2O3. We also present a comparative study of the catalytic performance of the both catalysts for the oxidation of benzylic alcohol to corresponding aldehydes by using molecular oxygen as the oxidizing agent. ZrO x (x  %)–MnCO3 was prepared through co‐precipitation by varying the amounts of Zr(NO3)4 (w/w %) in Mn(NO3)2. The morphology, composition, and crystallinity of the as‐synthesized product and the catalysts prepared upon calcination were studied by using scanning electron microscopy, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, and powder X‐ray diffraction. The surface areas of the catalysts [133.58 m2 g−1 for ZrO x (1 %)–MnCO3 and 17.48 m2 g−1 for ZrO x (1 %)–Mn2O3] were determined by using the Brunauer–Emmett–Teller method, and the thermal stability was assessed by using thermal gravimetric analysis. The catalyst with composition ZrO x (1 %)–MnCO3 pre‐calcined at 300 °C exhibited excellent specific activity (48.00 mmolg−1 h−1) with complete conversion within approximately 5 min and catalyst cyclability up to six times without any significant loss in activity. The specific activity, turnover number and turnover frequency achieved is the highest so far (to the best of our knowledge) compared to the previously reported catalysts used for the oxidation of benzyl alcohol. The catalyst showed selectivity for aromatic alcohols over aliphatic alcohols. PMID:28168156

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

    SciTech Connect

    Glaser, Mathias; Peisert, Heiko Adler, Hilmar; Aygül, Umut; Ivanovic, Milutin; Chassé, Thomas; Nagel, Peter; Merz, Michael; Schuppler, Stefan

    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 charge 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.

  11. Stable Isotope Fractionation during Chromium(III) Oxidation by δ-MnO2

    NASA Astrophysics Data System (ADS)

    Wang, D. T.; Fregoso, D. C.; Ellis, A. S.; Johnson, T. M.; Bullen, T. D.

    2010-12-01

    Hexavalent chromium is a highly mobile anthropogenic pollutant, and reduction of Cr(VI) to the less-soluble Cr(III) is the most important natural process involved in contamination attenuation. Earlier work has shown a preferential reduction of lighter Cr stable isotopes attributed to a kinetically-controlled mechanism, and isotope ratio measurements may be used as indicators of Cr(VI) reduction [1]. Recent work has detected no significant isotope exchange between dissolved Cr(III) and Cr(VI) over a period of days to weeks, and has suggested that complex bidirectional reactions control fractionation during Cr(III) oxidation by H2O2 [2]. Previous studies on oxidation by pyrolusite (β-MnO2) have reported δ53/52Cr up to approximately +1.1‰ in the Cr(VI) product [3]. However, laboratory investigations of fractionation during Cr(III) oxidation by birnessite (δ-MnO2) have been inconclusive, and oxidation mechanisms remain unclear [4]. In order to fully exploit stable isotope fractionation during redox reactions of Cr in groundwater as an indicator of Cr attenuation, the effect of Cr(III) oxidation on isotope ratios must be better understood. We will report the latest measurements of isotope fractionation during oxidation on birnessite under varying pH and MnO2 and Cr(III) concentrations. Our preliminary findings (at initial Cr(III) and δ-MnO2 concentrations of 10 mg/L and 100 mg/L, respectively) show the Cr(VI) product shifted by -0.5‰ to +0.0‰ relative to the reactant at pH ≈ 4.5. The reaction is incomplete and plateaus within 60 min. Unlike that observed with pyrolusite, fractionation during Cr oxidation on birnessite is much smaller or absent. These initial results suggest that kinetic effects are either very small or are negated by back reaction or equilibration in the multi-step oxidation mechanism. Alternatively, in our experiments, a step involving little isotope fractionation may be rate-limiting; thus, the final magnitude of isotope fractionation

  12. High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn{sub 3}O{sub 4} nanoparticles

    SciTech Connect

    Laffont, L.; Gibot, P.

    2010-11-15

    Manganese oxides particularly Mn{sub 3}O{sub 4} Hausmannite are currently used in many industrial applications such as catalysis, magnetism, electrochemistry or air contamination. The downsizing of the particle size of such material permits an improvement of its intrinsic properties and a consequent increase in its performances compared to a classical micron-sized material. Here, we report a novel synthesis of hydrophilic nano-sized Mn{sub 3}O{sub 4}, a bivalent oxide, for which a precise characterization is necessary and for which the determination of the valency proves to be essential. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and particularly High Resolution Electron Energy Loss Spectroscopy (HREELS) allow us to perform these measurements on the nanometer scale. Well crystallized 10-20 nm sized Mn{sub 3}O{sub 4} particles with sphere-shaped morphology were thus successfully synthesized. Meticulous EELS investigations allowed the determination of a Mn{sup 3+}/Mn{sup 2+} ratio of 1.5, i.e. slightly lower than the theoretical value of 2 for the bulk Hausmannite manganese oxide. This result emphasizes the presence of vacancies on the tetrahedral sites in the structure of the as-synthesized nanomaterial. - Research Highlights: {yields}Mn{sub 3}O{sub 4} bulk and nano were studied by XRD, TEM and EELS. {yields}XRD and TEM determine the degree of crystallinity and the narrow grain size. {yields}HREELS gave access to the Mn{sup 3+}/Mn{sup 2+} ratio. {yields}Mn{sub 3}O{sub 4} nano have vacancies on the tetrahedral sites.

  13. Susceptibility of dry-cured tuna to oxidative deterioration and biogenic amines generation: I. Effect of NaCl content, antioxidant type and ageing.

    PubMed

    Roseiro, L C; Santos, C; Gonçalves, H; Serrano, C; Aleixo, C; Partidário, A; Lourenço, A R; Dias, M Abreu; da Ponte, D J B

    2017-08-01

    This study aimed to assess lipid oxidation and biogenic amine (BA) development in "muxama", a dry-cured tuna muscle product, as affected by salt content, antioxidant type and ageing time. Overall, BA contents decreased with NaCl level (2785.1mgkg(-1), 1148.1mgkg(-1) and 307.7mgkg(-1)) and increased with ageing time (366.2mgkg(-1), 1711.8mgkg(-1) and 2959.2mgkg(-1) in the final product (T0), and after 1 (T1) and 3 (T3) months of ageing, respectively). Regardless of the test conditions, the most concentrated BA was always tyramine. For the ageing periods considered in the present study, malondialdehyde formation was affected by the NaCl level, with the saltiest samples exhibiting lower content. Rosemary and sage extracts represented promising technological options for preserving muxama from oxidation and to minimize the presence of a fishy flavour and odour, but this treatment may cause the colour to lose some of its redness and become less appealing.

  14. A chromatographic method to analyze products from photo-oxidation of anthropogenic and biogenic mixtures of volatile organic compounds in smog chambers.

    PubMed

    Pindado Jiménez, Oscar; Pérez Pastor, Rosa M; Vivanco, Marta G; Santiago Aladro, Manuel

    2013-03-15

    A method for quantifying secondary organic aerosol compounds (SOA) and water soluble secondary organic aerosol compounds (WSOA) produced from photo-oxidation of complex mixtures of volatile organic compounds (VOCs) in smog chambers by gas chromatography/mass spectrometry (GC/MS) has been developed. This method employs a double extraction with water and methanol jointly to a double derivatization with N,O-bis (trimethylsilil) trifluoroacetamide (BSTFA) and O-(2,3,4,5,6)-pentafluorobenzyl-hydroxylamine hydrochloride (PFBHA) followed by an analysis performed by GC/MS. The analytical procedure complements other methodologies because it can analyze SOA and WSOA compounds simultaneously at trace levels. As application, the methodology was employed to quantify the organic composition of aerosols formed in a smog chamber as a result of photo-oxidation of two different mixtures of volatile organic compounds: an anthropogenic mixture and a biogenic mixture. The analytical method allowed us to quantify up to 17 SOA compounds at levels higher than 20 ng m(-3) with reasonable recovery and a precision below 11%. Values found for applicability, selectivity, linearity, precision, recovery, detection limit, quantification limit and sensitivity demonstrated that the methodology can be satisfactorily applied to quantify SOA and WSOA.

  15. Guanine Oxidation in Double-stranded DNA by MnTMPyP/KHSO(5): At Least Three Independent Reaction Pathways.

    PubMed

    Lapi, A; Pratviel, G; Meunier, B

    2001-01-01

    In order to better define the mechanism and the products of guanine oxidation within DNA, we investigated the details of the mechanism of guanine oxidation by a metalloporphyrin, Mn-TMPyP, associated to KHSO(5) on oligonucleotides. We found that the three major products of guanine oxidation are formed by independent reaction routes. The oxidized guanidinohydantoin (1) and the proposed spiro compound 3 derivatives are not precursors of imidazolone lesion (Iz). These guanine lesions as well as their degradation products, may account for non-detected guanine oxidation products on oxidatively damaged DNA.

  16. 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.

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

    NASA Astrophysics Data System (ADS)

    Toyoda, Kazuhiro; Tebo, Bradley M.

    2013-01-01

    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 10 mM 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 (0-2000 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 environment

  18. Decoration of the layered manganese oxide birnessite with Mn(II/III) gives a new water oxidation catalyst with fifty-fold turnover number enhancement.

    PubMed

    McKendry, Ian G; Kondaveeti, Sandeep K; Shumlas, Samantha L; Strongin, Daniel R; Zdilla, Michael J

    2015-08-07

    The role of the manganese average oxidation state (AOS) in water oxidation catalysis by birnessite was investigated. Low AOS samples were most active, generating O2 immediately. Samples with a relatively high AOS showed an initial induction period and decreased turnover. Mn(ii- and iii)-enriched samples gave a 10-50 fold enhancement in turnover number.

  19. Mn(II) Binding and Subsequent Oxidation by the Multicopper Oxidase MnxG Investigated by Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Tao, Lizhi; Stich, Troy A; Butterfield, Cristina N; Romano, Christine A; Spiro, Thomas G; Tebo, Bradley M; Casey, William H; Britt, R David

    2015-08-26

    The dynamics of manganese solid formation (as MnOx) by the multicopper oxidase (MCO)-containing Mnx protein complex were examined by electron paramagnetic resonance (EPR) spectroscopy. Continuous-wave (CW) EPR spectra of samples of Mnx, prepared in atmosphere and then reacted with Mn(II) for times ranging from 7 to 600 s, indicate rapid oxidation of the substrate manganese (with two-phase pseudo-first-order kinetics modeled using rate coefficients of: k(1obs) = 0.205 ± 0.001 s(-1) and k(2obs) = 0.019 ± 0.001 s(-1)). This process occurs on approximately the same time scale as in vitro solid MnOx formation when there is a large excess of Mn(II). We also found CW and pulse EPR spectroscopic evidence for at least three classes of Mn(II)-containing species in the reaction mixtures: (i) aqueous Mn(II), (ii) a specifically bound mononuclear Mn(II) ion coordinated to the Mnx complex by one nitrogenous ligand, and (iii) a weakly exchange-coupled dimeric Mn(II) species. These findings provide new insights into the molecular mechanism of manganese mineralization.

  20. Removal of trace mercury(II) from aqueous solution by in situ formed Mn-Fe (hydr)oxides.

    PubMed

    Lu, Xixin; Huangfu, Xiaoliu; Ma, Jun

    2014-09-15

    The efficiency and mechanism of trace mercury (Hg(II)) removal by in situ formed manganese-ferric (hydr)oxides (in situ Mn-Fe) were investigated by reacting KMnO4 with Fe(II) in simulated solutions and natural water. In the simulated solutions, the impact of coagulant dosage, pH, and temperature on mercury removal was studied. Experimental results showed that in situ Mn-Fe more effectively removed mercury compared with polyaluminum chloride (PAC) and iron(III) chloride (FeCl3), and that mercury existed in the form of uncharged species, namely Hg(OH)2, HgClOH(aq), and HgCl2(aq). Fourier transform infrared spectroscopy demonstrated that in situ Mn-Fe contained hydroxyl groups as the surface active sites, while X-ray photoelectron spectroscopy (XPS) measurements revealed that MnO2 or MnOOH and FeOOH were the dominant species in the precipitates. XPS analysis indicated that an Hg-Mn-Fe mixture was formed in the precipitates, suggesting that mercury was removed from solutions via transfer from the liquid phase to solid phase. These results indicated that the primary mercury removal mechanisms in in situ Mn-Fe were surface complexation and flocculation-precipitation processes. Satisfactory removal efficiency of mercury was also observed following in situ Mn-Fe in natural waters.

  1. 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

  2. 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

    2016-12-09

    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.

  3. Effects of synthesis conditions on structure and surface properties of SmMn2O5 mullite-type oxide

    NASA Astrophysics Data System (ADS)

    Thampy, Sampreetha; Ibarra, Venessa; Lee, Yun-Ju; McCool, Geoffrey; Cho, Kyeongjae; Hsu, Julia W. P.

    2016-11-01

    A mixed-phase compound that contains SmMn2O5 mullite-type oxides has been reported to display excellent catalytic activity for nitric oxide (NO) oxidation. Here we investigate the effects of calcination temperature and precipitation pH on structural, physical, chemical, and surface properties of SmMn2O5. As the calcination temperature increases from 750 °C to 1000 °C, mullite phase purity increases from 74% to 100%, while specific surface area (SSA) decreases from 23.6 m2/g to 5.1 m2/g with particle size increases correspondingly. Mullite phase purity (87%) is independent of pH between 8.5-10.4, whereas SSA monotonically increases from 12.5 m2/g at pH 8.1 to 27.4 m2/g at pH 13. X-ray photoelectron spectroscopy (XPS) studies reveal that the surface Mn/Sm ratio is similar to the bulk value and is unaffected by calcination temperature and pH values up to 10.4, whereas sample precipitated at pH 13 is surface-rich in Sm. NO chemisorption studies show that the SSA and surface Mn/Sm ratio determine NO uptake by SmMn2O5 mullite oxides.

  4. Sn-Mn binary metal oxides as non-carbon sorbent for mercury removal in a wide-temperature window.

    PubMed

    Xie, Jiangkun; Xu, Haomiao; Qu, Zan; Huang, Wenjun; Chen, Wanmiao; Ma, Yongpeng; Zhao, Songjian; Liu, Ping; Yan, Naiqiang

    2014-08-15

    A series of Sn-Mn binary metal oxides were prepared through co-precipitation method. The sorbents were characterized by powder X-ray diffraction (powder XRD), transmission electronic microscopy (TEM), H2-temperature-programmed reduction (H2-TPR) and NH3-temperature-programmed desorption (NH3-TPD) methods. The capability of the prepared sorbents for mercury adsorption from simulated flue gas was investigated by fixed-bed experiments. Results showed that mercury adsorption on pure SnO2 particles was negligible in the test temperature range, comparatively, mercury capacity on MnOx at low temperature was relative high, but the capacity would decrease significantly when the temperature was elevated. Interestingly, for Sn-Mn binary metal oxide, mercury capacity increased not only at low temperature but also at high temperature. Furthermore, the impact of SO2 on mercury adsorption capability of Sn-Mn binary metal oxides was also investigated and it was noted that the effect at low temperature was different comparing with that of high temperature. The mechanism was investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs). Moreover, a mathematic model was built to calculate mercury desorption activation energy from Sn to Mn binary metal oxides.

  5. Mn porphyrin in combination with ascorbate acts as a pro-oxidant and mediates caspase-independent cancer cell death.

    PubMed

    Evans, Myron K; Tovmasyan, Artak; Batinic-Haberle, Ines; Devi, Gayathri R

    2014-03-01

    Resistance to therapy-mediated apoptosis in inflammatory breast cancer, an aggressive and distinct subtype of breast cancer, was recently attributed to increased superoxide dismutase (SOD) expression, glutathione (GSH) content, and decreased accumulation of reactive species. In this study, we demonstrate the unique ability of two Mn(III) N-substituted pyridylporphyrin (MnP)-based SOD mimics (MnTE-2-PyP(5+) and MnTnBuOE-2-PyP(5+)) to catalyze oxidation of ascorbate, leading to the production of excessive levels of peroxide, and in turn cell death. The accumulation of peroxide, as a consequence of MnP+ascorbate treatment, was fully reversed by the administration of exogenous catalase, showing that hydrogen peroxide is essential for cell death. Cell death as a consequence of the action of MnP+ascorbate corresponded to decreases in GSH levels, prosurvival signaling (p-NF-κB, p-ERK1/2), and in expression of X-linked inhibitor of apoptosis protein, the most potent caspase inhibitor. Although markers of classical apoptosis were observed, including PARP cleavage and annexin V staining, administration of a pan-caspase inhibitor, Q-VD-OPh, did not reverse the observed cytotoxicity. MnP+ascorbate-treated cells showed nuclear translocation of apoptosis-inducing factor, suggesting the possibility of a mechanism of caspase-independent cell death. Pharmacological ascorbate has already shown promise in recently completed phase I clinical trials, in which its oxidation and subsequent peroxide formation was catalyzed by endogenous metalloproteins. The catalysis of ascorbate oxidation by an optimized metal-based catalyst (such as MnP) carries a large therapeutic potential as an anticancer agent by itself or in combination with other modalities such as radio- and chemotherapy.

  6. Diversity of Methane-Oxidizing Bacteria in Soils from “Hot Lands of Medolla” (Italy) Featured by Anomalous High-Temperatures and Biogenic CO2 Emission

    PubMed Central

    Cappelletti, Martina; Ghezzi, Daniele; Zannoni, Davide; Capaccioni, Bruno; Fedi, Stefano

    2016-01-01

    “Terre Calde di Medolla” (TCM) (literally, “Hot Lands of Medolla”) refers to a farming area in Italy with anomalously high temperatures and diffuse emissions of biogenic CO2, which has been linked to CH4 oxidation processes from a depth of 0.7 m to the surface. We herein assessed the composition of the total bacterial community and diversity of methane-oxidizing bacteria (MOB) in soil samples collected at a depth at which the peak temperature was detected (0.6 m). Cultivation-independent methods were used, such as: i) a clone library analysis of the 16S rRNA gene and pmoA (coding for the α-subunit of the particulate methane monooxygenase) gene, and ii) Terminal Restriction Fragment Length Polymorphism (T-RFLP) fingerprinting. The 16S rRNA gene analysis assessed the predominance of Actinobacteria, Acidobacteria, Proteobacteria, and Bacillus in TCM samples collected at a depth of 0.6 m along with the presence of methanotrophs (Methylocaldum and Methylobacter) and methylotrophs (Methylobacillus). The phylogenetic analysis of pmoA sequences showed the presence of MOB affiliated with Methylomonas, Methylocystis, Methylococcus, and Methylocaldum in addition to as yet uncultivated and uncharacterized methanotrophs. Jaccard’s analysis of T-RFLP profiles at different ground depths revealed a similar MOB composition in soil samples at depths of 0.6 m and 0.7 m, while this similarity was weaker between these samples and those taken at a depth of 2.5 m, in which the genus Methylocaldum was absent. These results correlate the anomalously high temperatures of the farming area of “Terre Calde di Medolla” with the presence of microbial methane-oxidizing bacteria. PMID:27645100

  7. Diversity of Methane-Oxidizing Bacteria in Soils from "Hot Lands of Medolla" (Italy) Featured by Anomalous High-Temperatures and Biogenic CO2 Emission.

    PubMed

    Cappelletti, Martina; Ghezzi, Daniele; Zannoni, Davide; Capaccioni, Bruno; Fedi, Stefano

    2016-12-23

    "Terre Calde di Medolla" (TCM) (literally, "Hot Lands of Medolla") refers to a farming area in Italy with anomalously high temperatures and diffuse emissions of biogenic CO2, which has been linked to CH4 oxidation processes from a depth of 0.7 m to the surface. We herein assessed the composition of the total bacterial community and diversity of methane-oxidizing bacteria (MOB) in soil samples collected at a depth at which the peak temperature was detected (0.6 m). Cultivation-independent methods were used, such as: i) a clone library analysis of the 16S rRNA gene and pmoA (coding for the α-subunit of the particulate methane monooxygenase) gene, and ii) Terminal Restriction Fragment Length Polymorphism (T-RFLP) fingerprinting. The 16S rRNA gene analysis assessed the predominance of Actinobacteria, Acidobacteria, Proteobacteria, and Bacillus in TCM samples collected at a depth of 0.6 m along with the presence of methanotrophs (Methylocaldum and Methylobacter) and methylotrophs (Methylobacillus). The phylogenetic analysis of pmoA sequences showed the presence of MOB affiliated with Methylomonas, Methylocystis, Methylococcus, and Methylocaldum in addition to as yet uncultivated and uncharacterized methanotrophs. Jaccard's analysis of T-RFLP profiles at different ground depths revealed a similar MOB composition in soil samples at depths of 0.6 m and 0.7 m, while this similarity was weaker between these samples and those taken at a depth of 2.5 m, in which the genus Methylocaldum was absent. These results correlate the anomalously high temperatures of the farming area of "Terre Calde di Medolla" with the presence of microbial methane-oxidizing bacteria.

  8. Ca cofactor of the water-oxidation complex: Evidence for a Mn/Ca heteronuclear cluster

    SciTech Connect

    Cinco, Roehl M.; Robblee, John H.; Messinger, Johannes; Fernandez, Carmen; McFarlane, Karen L.; Pizarro, Shelly A.; Sauer, Ken; Yachandra, Vittal K.

    2001-07-25

    Calcium and chloride are necessary cofactors for the proper function of the oxygen-evolving complex (OEC) of Photosystem II (PS II). Located in the thylakoid membranes of green plants, cyanobacteria and algae, PS II and the OEC catalyze the light-driven oxidation of water into dioxygen (released into the biosphere), protons and electrons for carbon fixation. The actual chemistry of water oxidation is performed by a cluster of four manganese atoms, along with the requisite cofactors Ca{sup 2+} and Cl{sup -}. While the Mn complex has been extensively studied by X-ray absorption techniques, comparatively less is known about the Ca{sup 2+} cofactor. The fewer number of studies on the Ca{sup 2+} cofactor have sometimes relied on substituting the native cofactor with strontium or other metals, and have stirred some debate about the structure of the binding site. past efforts using Mn EXAFS on Sr-substituted PSII are suggestive of a close link between the Mn cluster and Sr, within 3.5 {angstrom}. The most recent published study using Sr EXAFS on similar samples confirms this finding of a 3.5 {angstrom} distance between Mn and Sr. This finding was base3d on a second Fourier peak (R {approx} 3 {angstrom}) in the Sr EXAFS from functional samples, but is absent from inactive, hydroxylamine-treated PS II. This Fourier peak II was found to fit best to two Mn at 3.5 {angstrom} rather than lighter atoms (carbon). Nevertheless, other experiments have given contrary results. They wanted to extend the technique by using polarized Sr EXAFS on layered Sr-substituted samples, to provide important angle information. Polarized EXAFS involves collecting spectra for different incident angles ({theta}) between the membrane normal of the layered sample and the X-ray electric field vector. Dichroism in the EXAFS can occur, depending on how the particular absorber-backscatterer (A-B) vector is aligned with the electric field. Through analysis of the dichroism, they extract the average number

  9. An analysis of the effects of Mn{sup 2+} on oxidative phosphorylation in liver, brain, and heart mitochondria using state 3 oxidation rate assays

    SciTech Connect

    Gunter, Thomas E.; Gerstner, Brent; Lester, Tobias; Wojtovich, Andrew P.; Malecki, Jon; Swarts, Steven G.; Brookes, Paul S.; Gavin, Claire E. Gunter, Karlene K.

    2010-11-15

    Manganese (Mn) toxicity is partially mediated by reduced ATP production. We have used oxidation rate assays-a measure of ATP production-under rapid phosphorylation conditions to explore sites of Mn{sup 2+} inhibition of ATP production in isolated liver, brain, and heart mitochondria. This approach has several advantages. First, the target tissue for Mn toxicity in the basal ganglia is energetically active and should be studied under rapid phosphorylation conditions. Second, Mn may inhibit metabolic steps which do not affect ATP production rate. This approach allows identification of inhibitions that decrease this rate. Third, mitochondria from different tissues contain different amounts of the components of the metabolic pathways potentially resulting in different patterns of ATP inhibition. Our results indicate that Mn{sup 2+} inhibits ATP production with very different patterns in liver, brain, and heart mitochondria. The primary Mn{sup 2+} inhibition site in liver and heart mitochondria, but not in brain mitochondria, is the F{sub 1}F{sub 0} ATP synthase. In mitochondria fueled by either succinate or glutamate + malate, ATP production is much more strongly inhibited in brain than in liver or heart mitochondria; moreover, Mn{sup 2+} inhibits two independent sites in brain mitochondria. The primary site of Mn-induced inhibition of ATP production in brain mitochondria when succinate is substrate is either fumarase or complex II, while the likely site of the primary inhibition when glutamate plus malate are the substrates is either the glutamate/aspartate exchanger or aspartate aminotransferase.

  10. 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 MnS2/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 MnS2 nanoparticles and MnS2/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 MnS2 and MnS2/r-GO hybrids, respectively. Carbophenothion as an insecticide photodegradation was used to estimate the photocatalytic activity of the MnS2/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 MnS2/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.

  11. 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.

  12. 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.

  13. Biogenic synthesis of Zinc oxide nanostructures from Nigella sativa seed: Prospective role as food packaging material inhibiting broad-spectrum quorum sensing and biofilm.

    PubMed

    Al-Shabib, Nasser A; Husain, Fohad Mabood; Ahmed, Faheem; Khan, Rais Ahmad; Ahmad, Iqbal; Alsharaeh, Edreese; Khan, Mohd Shahnawaz; Hussain, Afzal; Rehman, Md Tabish; Yusuf, Mohammad; Hassan, Iftekhar; Khan, Javed Masood; Ashraf, Ghulam Md; Alsalme, Ali Mohammed; Al-Ajmi, Mohamed F; Tarasov, Vadim V; Aliev, Gjumrakch

    2016-12-05

    Bacterial spoilage of food products is regulated by density dependent communication system called quorum sensing (QS). QS control biofilm formation in numerous food pathogens and Biofilms formed on food surfaces act as carriers of bacterial contamination leading to spoilage of food and health hazards. Agents inhibiting or interfering with bacterial QS and biofilm are gaining importance as a novel class of next-generation food preservatives/packaging material. In the present study, Zinc nanostructures were synthesised using Nigella sativa seed extract (NS-ZnNPs). Synthesized nanostructures were characterized hexagonal wurtzite structure of size ~24 nm by UV-visible, XRD, FTIR and TEM. NS-ZnNPs demonstrated broad-spectrum QS inhibition in C. violaceum and P. aeruginosa biosensor strains. Synthesized nanostructures inhibited QS regulated functions of C. violaceum CVO26 (violacein) and elastase, protease, pyocyanin and alginate production in PAO1 significantly. NS-ZnNPs at sub-inhibitory concentrations inhibited the biofilm formation of four-food pathogens viz. C. violaceum 12472, PAO1, L. monocytogenes, E. coli. Moreover, NS-ZnNPs was found effective in inhibiting pre-formed mature biofilms of the four pathogens. Therefore, the broad-spectrum inhibition of QS and biofilm by biogenic Zinc oxide nanoparticles and it is envisaged that these nontoxic bioactive nanostructures can be used as food packaging material and/or as food preservative.

  14. Biogenic synthesis of Zinc oxide nanostructures from Nigella sativa seed: Prospective role as food packaging material inhibiting broad-spectrum quorum sensing and biofilm

    PubMed Central

    Al-Shabib, Nasser A.; Husain, Fohad Mabood; Ahmed, Faheem; Khan, Rais Ahmad; Ahmad, Iqbal; Alsharaeh, Edreese; Khan, Mohd Shahnawaz; Hussain, Afzal; Rehman, Md Tabish; Yusuf, Mohammad; Hassan, Iftekhar; Khan, Javed Masood; Ashraf, Ghulam Md; Alsalme, Ali Mohammed; Al-Ajmi, Mohamed F.; Tarasov, Vadim V.; Aliev, Gjumrakch

    2016-01-01

    Bacterial spoilage of food products is regulated by density dependent communication system called quorum sensing (QS). QS control biofilm formation in numerous food pathogens and Biofilms formed on food surfaces act as carriers of bacterial contamination leading to spoilage of food and health hazards. Agents inhibiting or interfering with bacterial QS and biofilm are gaining importance as a novel class of next-generation food preservatives/packaging material. In the present study, Zinc nanostructures were synthesised using Nigella sativa seed extract (NS-ZnNPs). Synthesized nanostructures were characterized hexagonal wurtzite structure of size ~24 nm by UV-visible, XRD, FTIR and TEM. NS-ZnNPs demonstrated broad-spectrum QS inhibition in C. violaceum and P. aeruginosa biosensor strains. Synthesized nanostructures inhibited QS regulated functions of C. violaceum CVO26 (violacein) and elastase, protease, pyocyanin and alginate production in PAO1 significantly. NS-ZnNPs at sub-inhibitory concentrations inhibited the biofilm formation of four-food pathogens viz. C. violaceum 12472, PAO1, L. monocytogenes, E. coli. Moreover, NS-ZnNPs was found effective in inhibiting pre-formed mature biofilms of the four pathogens. Therefore, the broad-spectrum inhibition of QS and biofilm by biogenic Zinc oxide nanoparticles and it is envisaged that these nontoxic bioactive nanostructures can be used as food packaging material and/or as food preservative. PMID:27917856

  15. Laser flash photolysis generation and kinetic studies of porphyrin-manganese-oxo intermediates. Rate constants for oxidations effected by porphyrin-Mn(V)-oxo species and apparent disproportionation equilibrium constants for porphyrin-Mn(IV)-oxo species.

    PubMed

    Zhang, Rui; Horner, John H; Newcomb, Martin

    2005-05-11

    Porphyrin-manganese(V)-oxo and porphyrin-manganese(IV)-oxo species were produced in organic solvents by laser flash photolysis (LFP) of the corresponding porphyrin-manganese(III) perchlorate and chlorate complexes, respectively, permitting direct kinetic studies. The porphyrin systems studied were 5,10,15,20-tetraphenylporphyrin (TPP), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPFPP), and 5,10,15,20-tetrakis(4-methylpyridinium)porphyrin (TMPyP). The order of reactivity for (porphyrin)Mn(V)(O) derivatives in self-decay reactions in acetonitrile and in oxidations of substrates was (TPFPP) > (TMPyP) > (TPP). Representative rate constants for reaction of (TPFPP)Mn(V)(O) in acetonitrile are k = 6.1 x 10(5) M(-1) s(-1) for cis-stilbene and k = 1.4 x 10(5) M(-1) s(-1) for diphenylmethane, and the kinetic isotope effect in oxidation of ethylbenzene and ethylbenzene-d(10) is k(H)/k(D) = 2.3. Competitive oxidation reactions conducted under catalytic conditions display approximately the same relative rate constants as were found in the LFP studies of (porphyrin)Mn(V)(O) derivatives. The apparent rate constants for reactions of (porphyrin)Mn(IV)(O) species show inverted reactivity order with (TPFPP) < (TMPyP) < (TPP) in reactions with cis-stilbene, triphenylamine, and triphenylphosphine. The inverted reactivity results because (porphyrin)Mn(IV)(O) disproportionates to (porphyrin)Mn(III)X and (porphyrin)Mn(V)(O), which is the primary oxidant, and the equilibrium constants for disproportionation of (porphyrin)Mn(IV)(O) are in the order (TPFPP) < (TMPyP) < (TPP). The fast comproportionation reaction of (TPFPP)Mn(V)(O) with (TPFPP)Mn(III)Cl to give (TPFPP)Mn(IV)(O) (k = 5 x 10(8) M(-1) s(-1)) and disproportionation reaction of (TPP)Mn(IV)(O) to give (TPP)Mn(V)(O) and (TPP)Mn(III)X (k approximately 2.5 x 10(9) M(-1) s(-1)) were observed. The relative populations of (porphyrin)Mn(V)(O) and (porphyrin)Mn(IV)(O) were determined from the ratios of observed rate constants for

  16. Manganese hexacyanoferrate derived Mn3O4 nanocubes-reduced graphene oxide nanocomposites and their charge storage characteristics in supercapacitors.

    PubMed

    Subramani, K; Jeyakumar, D; Sathish, M

    2014-03-14

    Mn3O4-reduced graphene oxide (RGO) nanocomposites were prepared by chemical decomposition of the manganese hexacyanoferrate (MnHCF) complex directly on the graphene surface. XRD studies revealed the formation of crystalline hausmannite Mn3O4 nanocubes in the as-prepared nanocomposites without any heat treatment. The FE-SEM images showed the formation of Mn3O4 nanocubes on the graphene surface in the as-prepared nanocomposites. HR-TEM studies confirmed the homogeneous dispersion of ∼25 nm Mn3O4 nanocubes on graphene nanosheets. The amount of Mn3O4 nanocubes and graphene in the nanocomposites was estimated using TGA analysis from room temperature to 800 °C in air. The FT-IR and Raman spectroscopic analysis confirmed the functional groups in the nanocomposites and defects in graphene nanosheets in the nanocomposites. Cyclic voltammetry and galvanostatic charge-discharge experiments demonstrated a high specific capacitance of 131 F g(-1) in 1 M Na2SO4 electrolyte at a current density of 0.5 A g(-1) for the RGM-0.5 nanocomposite. A capacitance retention of 99% was observed for 500 charge-discharge cycles at a current density of 5 A g(-1), which conformed the excellent stability of the RGM electrodes. The prepared Mn3O4-RGO nanocomposites are promising for electrochemical energy storage.

  17. Mn-catalase (Alr0998) protects the photosynthetic, nitrogen-fixing cyanobacterium Anabaena PCC7120 from oxidative stress.

    PubMed

    Banerjee, Manisha; Ballal, Anand; Apte, Shree Kumar

    2012-11-01

    Role of the non-haem, manganese catalase (Mn-catalase) in oxidative stress tolerance is unknown in cyanobacteria. The ORF alr0998 from the Anabaena PCC7120, which encodes a putative Mn-catalase, was constitutively overexpressed in Anabaena PCC7120 to generate a recombinant strain, AnKat(+). The Alr0998 protein could be immunodetected in AnKat(+) cells and zymographic analysis showed a distinct thermostable catalase activity in the cytosol of AnKat(+) cells but not in the wild-type Anabaena PCC7120. The observed catalase activity was insensitive to inhibition by azide indicating that Alr0998 protein is indeed a Mn-catalase. In response to oxidative stress, the AnKat(+) showed reduced levels of intracellular ROS which was also corroborated by decreased production of an oxidative stress-inducible 2-Cys-Prx protein. Treatment of wild-type Anabaena PCC7120 with H(2)O(2) caused (i) RNA degradation in vivo, (ii) severe reduction of photosynthetic pigments and CO(2) fixation, (iii) fragmentation and lysis of filaments and (iv) loss of viability. In contrast, the AnKat(+) strain was protected from all the aforesaid deleterious effect under oxidative stress. This is the first report on protection of an organism from oxidative stress by overexpression of a Mn-catalase.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    Boumaiza, Hella; Coustel, Romain; Medjahdi, Ghouti; Ruby, Christian; Bergaoui, Latifa

    2017-04-01

    Birnessite was synthetized through redox reaction by mixing MnO4-, Mn2+ and OH- 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 of birnessite and hausmannite and shows the ways to obtain pure birnessite. The role of counter-ion ie. Na+ or K+ was also examined.

  20. Biogenic emissions modeling for Southeastern Texas

    SciTech Connect

    Estes, M.; Jacob, D.; Jarvie, J.

    1996-12-31

    The Texas Natural Resource Conservation Commission (TNRCC) modeling staff performed biogenic hydrocarbon emissions modeling in support of gridded photochemical modeling for ozone episodes in 1992 and 1993 for the Coastal Oxidant Assessment for Southeast Texas (COAST) modeling domain. This paper summarizes the results of the biogenic emissions modeling and compares preliminary photochemical modeling results to ambient air monitoring data collected during the 1993 COAST study. Biogenic emissions were estimated using BIOME, a gridded biogenic emissions model that uses region-specific land use and biomass density data, and plant species-specific emission factor data. Ambient air monitoring data were obtained by continuous automated gas chromatography at two sites, one-hour canister samples at 5 sites, and 24-hour canister samples at 13 other sites. The concentrations of Carbon Bond-IV species (as determined from urban airshed modeling) were compared to measured hydrocarbon concentrations. In this paper, we examined diurnal and seasonal variations, as well as spatial variations.

  1. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation.

    PubMed

    Liang, Xiaoliang; Liu, Peng; He, Hongping; Wei, Gaoling; Chen, Tianhu; Tan, Wei; Tan, Fuding; Zhu, Jianxi; Zhu, Runliang

    2016-04-05

    In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H2 temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200-600°C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300-600°C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400°C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn(4+) species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites.

  2. 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.

  3. 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.

  4. 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

  5. Thermal stability of the prototypical Mn porphyrin-based superoxide dismutase mimic and potent oxidative-stress redox modulator Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin chloride, MnTE-2-PyP5+

    PubMed Central

    Pinto, Victor H. A.; CarvalhoDa-Silva, Dayse; Santos, Jonas L. M. S.; Weitner, Tin; Fonseca, Maria Gardênnia; Yoshida, Maria Irene; Idemori, Ynara M.; Batinić-Haberle, Ines; Rebouças, Júlio S.

    2012-01-01

    Cationic Mn porphyrins are among the most potent catalytic antioxidants and/or cellular redox modulators. Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin chloride (MnTE-2-PyPCl5) is the Mn porphyrin most studied in vivo and has successfully rescued animal models of a variety of oxidative stress-related diseases. The stability of an authentic MnTE-2-PyPCl5 sample was investigated hereon by thermogravimetric, derivative thermogravimetric, and differential thermal analyses (TG/DTG/DTA), under dynamic air, followed by studies at selected temperatures to evaluate the decomposition path and appropriate conditions for storage and handling of these materials. All residues were analyzed by thin-layer chromatography (TLC) and UV-vis spectroscopy. Three thermal processes were observed by TG/DTG. The first event (endothermic) corresponded to dehydration, and did not alter the MnTE-2-PyPCl5 moiety. The second event (endothermic) corresponded to the loss of EtCl (dealkylation), which was characterized by gas chromatography-mass spectrometry. The residue at 279 °C had UV-vis and TLC data consistent with those of the authentic, completely dealkylated analogue, MnT-2-PyPCl. The final, multi-step event corresponded to the loss of the remaining organic matter to yield Mn3O4 which was characterized by IR spectroscopy. Isothermal treatment at 188 °C under static air for 3 h yielded a mixture of partially dealkylated MnPs and traces of the free-base, dealkylated ligand, H2T-2-PyP, which reveals that dealkylation is accompanied by thermal demetallation under static air conditions. Dealkylation was not observed if the sample was heated as a solid or in aqueous solution up to ∼100 °C. Whereas moderate heating changes sample composition by loss of H2O, the dehydrated sample is indistinguishable from the original sample upon dissolution in water, which indicates that catalytic activity (on Mn basis) remains unaltered. Evidently, dealkylation at high temperature compromises sample

  6. 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.

  7. Ab initio and experimental pre-edge investigations of the Mn K -edge XANES in oxide-type materials

    NASA Astrophysics Data System (ADS)

    Farges, François

    2005-04-01

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the Td symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the Oh symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the “true pre-edge,” making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

  8. Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials

    SciTech Connect

    Farges, Francois

    2005-04-15

    Mn K edge ab initio FEFF8.2 calculations of the pre-edge features of the x-ray-absorption near-edge structure (XANES) region were undertaken for a series of Mn-bearing oxide-type compounds. The aim of the study is to provide a reliable method for determining quantitative and accurate redox and symmetry information for manganese. In agreement with multiplet calculations by Glatzel and co-workers, FEFF8.2 predicts a doublet and a triplet for Mn(II) and Mn(III) in octahedral symmetry, respectively, in agreement with high-resolution XANES experiments. Site distortion increases notably the contribution from dipolar transitions and, consequently, the pre-edge feature integrated area. An even more intense pre-edge feature is calculated and measured for the T{sub d} symmetry (singletlike). For Mn(IV), a triplet is predicted and measured for the O{sub h} symmetry. However, additional transitions are found in Mn(IV)-rich compounds, that are related to metal-metal transitions. These transitions overlap strongly with the 'true pre-edge', making extraction of redox and symmetry information for Mn(IV) more challenging. However, a model of the pre-edge with pseudo-Voigt functions of fixed calculated width (based on core-hole lifetime and experimental resolution) helps to separate the contributions related to first-neighbor symmetry from those of the metal-metal pairs. Application to multivalent defective manganese oxide materials suggests that the pre-edge information varies linearly as a function of Mn redox state or symmetry but varies nonlinearly as a function of both parameters. Finally, the polymerization of the manganese networks can be estimated from the metal-metal transitions found in the pre-edge region.

  9. 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

    2017-01-18

    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 analyzed. 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.

  10. Magnetoelasticity in ACr2O4 spinel oxides (A= Mn, Fe, Co, Ni, and Cu)

    NASA Astrophysics Data System (ADS)

    Kocsis, V.; Bordács, S.; Varjas, D.; Penc, K.; Abouelsayed, A.; Kuntscher, C. A.; Ohgushi, K.; Tokura, Y.; Kézsmárki, I.

    2013-02-01

    Dynamical properties of the lattice structure were studied by optical spectroscopy in ACr2O4 chromium spinel oxide magnetic semiconductors over a broad temperature region of T=10-335 K. The systematic change of the A-site ions (A= Mn, Fe, Co, Ni and Cu) showed that the occupancy of 3d orbitals on the A site has strong impact on the lattice dynamics. For compounds with orbital degeneracy (FeCr2O4, NiCr2O4, and CuCr2O4), clear splitting of infrared-active phonon modes and/or activation of silent vibrational modes have been observed upon the Jahn-Teller transition and at the onset of the subsequent long-range magnetic order. Although MnCr2O4 and CoCr2O4 show multiferroic and magnetoelectric character, no considerable magnetoelasticity was found in spinel compounds without orbital degeneracy as they closely preserve the high-temperature cubic spinel structure even in their magnetic ground state. Aside from lattice vibrations, intra-atomic 3d-3d transitions of the A2+ ions were also investigated to determine the crystal field and Racah parameters and the strength of the spin-orbit coupling.

  11. Immobilization of selenite in soil and groundwater using stabilized Fe-Mn binary oxide nanoparticles.

    PubMed

    Xie, Wenbo; Liang, Qiqi; Qian, Tianwei; Zhao, Dongye

    2015-03-01

    Stabilized Fe-Mn binary oxide nanoparticles were synthesized and tested for removal and in-situ immobilization of Se(IV) in groundwater and soil. A water-soluble starch or food-grade carboxymethyl cellulose (CMC) was used as a stabilizer to facilitate in-situ delivery of the particles into contaminated soil. While bare and stabilized nanoparticles showed rapid sorption kinetics, starch-stabilized Fe-Mn offered the greatest capacity for Se(IV). The Langmuir maximum capacity was determined to be 109 and 95 mg-Se/g-Fe for starch- and CMC-stabilized nanoparticles, respectively, and the high Se(IV) uptake was observed over the typical groundwater pH range of 5-8. Column breakthrough tests indicated that the stabilized nanoparticles were deliverable in a model sandy soil while non-stabilized particles were not. When a Se(IV)-spiked soil was treated in situ with the nanoparticles, >90% water leachable Se(IV) was transferred to the nanoparticle phase, and thereby immobilized as the particles were retained in the downstream soil matrix. The nanoparticle amendment reduced the TCLP (toxicity characteristic leaching procedure) leachability and the California WET (waste extraction test) leachability of Se(IV) by 76% and 71%, respectively. The technology holds the potential to fill a major technology gap in remediation of metals-contaminated soil and groundwater.

  12. Absence of Mn-Centered Oxidation in the S2 → S3 Transition: Implications for the Mechanism of Photosynthetic Water Oxidation

    PubMed Central

    Messinger, Johannes; Robblee, John H.; Bergmann, Uwe; Fernandez, Carmen; Glatzel, Pieter; Visser, Hendrik; Cinco, Roehl M.; McFarlane, Karen L.; Bellacchio, Emanuele; Pizarro, Shelly A.; Cramer, Stephen P.; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

    2014-01-01

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen-evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S3 → [S4] → S0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kβ XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S2 → S3 transition, in contrast to the S0 → S1 and S1 → S2 transitions, does not involve a Mn-centered oxidation. On the basis of new structural data from the S3-state, manganese μ-oxo bridge radical formation is proposed for the S2 → S3 transition, and three possible mechanisms for the O–O bond formation are presented. PMID:11493054

  13. Distributed microbially- and chemically-mediated redox processes controlling arsenic dynamics within Mn-/Fe-oxide constructed aggregates

    NASA Astrophysics Data System (ADS)

    Ying, Samantha C.; Masue-Slowey, Yoko; Kocar, Benjamin D.; Griffis, Sarah D.; Webb, Samuel; Marcus, Matthew A.; Francis, Christopher A.; Fendorf, Scott

    2013-03-01

    The aggregate-based structure of soils imparts physical heterogeneity that gives rise to variation in microbial and chemical processes which influence the speciation and retention of trace elements such as As. To examine the impact of distributed redox conditions on the fate of As in soils, we imposed various redox treatments upon constructed soil aggregates composed of ferrihydrite- and birnessite-coated sands presorbed with As(V) and inoculation with the dissimilatory metal reducing bacterium Shewanella sp. ANA-3. Aeration of the advecting solution surrounding the aggregates was varied to simulate environmental conditions. We find that diffusion-limited transport within high dissolved organic carbon environments allows reducing conditions to persist in the interior of aggregates despite aerated advecting external solutes, causing As, Mn, and Fe to migrate from the reduced aggregate interiors to the aerated exterior region. Upon transitioning to anoxic conditions in the external solutes, pulses of As, Mn and Fe are released into the advecting solution, while, conversely, a transition to aerated conditions in the exterior resulted in a cessation of As, Mn, and Fe release. Importantly, we find that As(III) oxidation by birnessite is appreciable only in the presence of O2; oxidation of As(III) to As(V) by Mn-oxides ceases under anaerobic conditions apparently as a result of microbially mediated Mn(IV/III) reduction. Our results demonstrate the importance of considering redox conditions and the physical complexity of soils in determining As dynamics, where redox transitions can either enhance or inhibit As release due to speciation shifts in both sorbents (solubilization versus precipitation of Fe and Mn oxides) and sorbates (As).

  14. Characterization, catalyzed water oxidation and anticancer activities of a NIR BODIPY-Mn polymer

    NASA Astrophysics Data System (ADS)

    Lan, Ya-Quan; Xiao, Ke-Jing; Wu, Yun-Jie; Chen, Qiu-Yun

    2017-04-01

    To obtain near-IR absorbing biomaterials as fluorescence cellular imaging and anticancer agents for hypoxic cancer cell, a nano NIR fluorescence Mn(III/IV) polymer (PMnD) was spectroscopically characterized. The PMnD shows strong emission at 661 nm when excited with 643 nm. Furthermore, PMnD can catalyze water oxidation to generate dioxygen when irradiated by red LED light (10 W). In particular, the PMnD can enter into HepG-2 cells and mitochondria. Both anticancer activity and the inhibition of the expression of HIF-1α for PMnD were concentration dependent. Our results demonstrate that PMnD can be developed as mitochondria targeted imaging agents and new inhibitors for HIF-1 in hypoxic cancer cells.

  15. Photoluminescence and Raman Spectroscopy of Jurassic Fe-Mn Oxide Rocks Forming Chimney Systems, Hungary

    NASA Astrophysics Data System (ADS)

    Vigh, T.; Polgári, M.; Hein, J. R.; Gucsik, A.; Koós, M.; Veres, M.; Tóth, S.; Tóth, A. L.; Bíró, L.

    2009-08-01

    Three ore samples were collected from an inferred hydrothermal vent site at the Úrkút-Csárdahegy open pit mine. The samples are black with a brown rind, blocky or mound-like with stromatolitic texture, cryptocrystalline, and often with vugs infilled by spherulites. Fe-Mn-oxide stromatolitic mounds grew at the sediment/water interface burying preexisting chimneys containing fluid-flow microchannels. The occurrence of amorphous carbon phases in the samples is variable and their distribution is inhomogeneous, and suggests a possible microbial origin. The occurrence of gypsum may reflect a Fe-S precursor phase. These results provide additional evidence for the existence of a local vent system at Csárdahegy.

  16. Why MnIn{sub 2}O{sub 4} spinel is not a transparent conducting oxide?

    SciTech Connect

    Martinez-Lope, M.J.; Retuerto, M.; Calle, C. de la; Porcher, Florence

    2012-03-15

    The title compound has been synthesized by a citrate technique. The crystal structure has been investigated at room temperature from high-resolution neutron powder diffraction (NPD) data. It crystallizes in a cubic spinel structure, space group Fd3-bar m, Z=8, with a=9.0008(1) A at 295 K. It exhibits a crystallographic formula (Mn{sub 0.924(2)}In{sub 0.076(2)}){sub 8a}(In{sub 1.804(2)}Mn{sub 0.196(2)}){sub 16d}O{sub 4}, where 8a and 16d stand for the tetrahedral and octahedral sites of the spinel structure, respectively, with a slight degree of inversion, {lambda}=0.08. MnIn{sub 2}O{sub 4} shows antiferromagnetic interactions below T{sub N} Almost-Equal-To 40 K, due to the statistical distribution of Mn ions over the two available sites. Unlike the related MgIn{sub 2}O{sub 4} and CdIn{sub 2}O{sub 4} spinels, well known as transparent conducting oxides, MnIn{sub 2}O{sub 4} is not transparent and shows a poor conductivity ({sigma}=0.38 S cm{sup -1} at 1123 K): the presence of Mn ions, able to adopt mixed valence states, localizes the charges that, otherwise, would be delocalized in the spinel conduction band. - Graphical Abstract: From NPD data the crystallographic formula (Mn{sub 0.924(2)}In{sub 0.076(2)}){sub 8a}(In{sub 1.804(2)}Mn{sub 0.196(2)}){sub 16d}O{sub 4}, shows a slight degree of inversion, {lambda}=0.08 and a certain In deficiency. The presence of Mn ions, able to adopt mixed oxidation states, localize the charges that, otherwise, would be delocalized in the spinel conduction band; the presence of localized Mn{sup 2+} and Mn{sup 3+} ions provides the characteristic brown color. Highlights: Black-Right-Pointing-Pointer Accurate structural determination from NPD data: inversion degree (8%), and In deficiency. Black-Right-Pointing-Pointer Bond-valence indicates Mn{sup 2+}-Mn{sup 3+} ions; edge-sharing octahedra contain 90% In{sup 3+}+10% Mn{sup 3+} cations. Black-Right-Pointing-Pointer Conductivity several orders of magnitude lower than those of MgIn{sub 2}O

  17. One-pot synthesis of γ-MnS/reduced graphene oxide with enhanced performance for aqueous asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Zhang, Guanggao; Kong, Menglai; Yao, Yadong; Long, Lu; Yan, Minglei; Liao, Xiaoming; Yin, Guangfu; Huang, Zhongbing; Asiri, Abdullah M.; Sun, Xuping

    2017-02-01

    In this work, γ-MnS/reduced graphene oxide composites (γ-MnS/rGO) were prepared using a facile one-pot hydrothermal method. As an electrode material for supercapacitors, the γ-MnS/rGO-60 composite obtained under dosages of graphene oxide was 60 mg and exhibited an enhanced specific capacitance of 547.6 F g-1 at a current density of 1 A g-1, and outstanding rate capability (65% capacitance retention at 20 A g-1), with superior cycling stability and electrochemical reversibility. An asymmetric supercapacitor assembled from γ-MnS/rGO-60 composite and rGO (γ-MnS/rGO-60//rGO) showed a voltage window of 0-1.6 V and delivered a high energy density of 23.1 W h kg-1 at a power density of 798.8 W kg-1, and 15.9 W h kg-1 at 4.5 kW kg-1. Moreover, two such 1.0 × 1.0 cm2 devices connected together in series easily light up a group of LED lights, showing its potential practical application as an attractive energy storage device.

  18. Substituent effects on core structures and heterogeneous catalytic activities of Mn(III)(μ-O)2Mn(IV) dimers with 2,2':6',2″-terpyridine derivative ligands for water oxidation.

    PubMed

    Yamazaki, Hirosato; Igarashi, Satoshi; Nagata, Toshi; Yagi, Masayuki

    2012-02-06

    [(OH(2))(R-terpy)Mn(μ-O)(2)Mn(R-terpy)(OH(2)) ](3+) (R-terpy = 4'-substituted 2,2':6',2″-terpyridine, R = butoxy (BuO), propoxy (PrO), ethoxy (EtO), methoxy (MeO), methyl (Me), methylthio (MeS), chloro (Cl)) have been synthesized as a functional oxygen-evolving complex (OEC) model and characterized by UV-vis and IR spectroscopic, X-ray crystallographic, magnetometric, and electrochemical techniques. The UV-vis spectra of derivatives in water were hardly influenced by the 4'-substituent variation. X-ray crystallographic data showed that Mn centers in the Mn(III)(μ-O)(2)Mn(IV) cores for derivatives with R = H, MeS, Me, EtO, and BuO are crystallographically indistinguishable, whereas the derivatives with R = MeO and PrO gave the significantly distinguishable Mn centers in the cores. The indistinguishable Mn centers could be caused by rapid electron exchange between the Mn centers to result in the delocalized Mn(μ-O)(2)Mn core. The exchange integral values (J = -196 to -178 cm(-1)) for delocalized cores were lower than that (J = -163 to -161 cm(-1)) for localized cores, though the Mn···Mn distances are nearly the same (2.707-2.750 Å). The half wave potential (E(1/2)) of a Mn(III)-Mn(IV)/Mn(IV)-Mn(IV) pair of the derivatives decreased with an increase of the electron-donating ability of the substituted groups for the delocalized core, but it deviated from the correlation for the localized cores. The catalytic activities of the derivatives on mica for heterogeneous water oxidation were remarkably changed by the substituted groups. The second order rate constant (k(2)/mol(-1) s(-1)) for O(2) evolution was indicated to be correlated to E(1/2) of a Mn(III)-Mn(IV)/Mn(IV)-Mn(IV) pair; k(2) increased by a factor of 29 as E(1/2) increased by 28 mV.

  19. Response of lead-induced oxidative stress and alterations in biogenic amines in different rat brain regions to combined administration of DMSA and MiADMSA.

    PubMed

    Flora, S J S; Saxena, Geetu; Gautam, Pratibha; Kaur, Pushpinder; Gill, Kiran Dip

    2007-12-15

    The present study was planned to investigate if combined administration of meso-2,3-dimercaptosuccinic acid (DMSA) and monoisoamyl DMSA (MiADMSA) could achieve better recovery in the altered biochemical parameters suggestive of brain oxidative stress and depletion of lead from blood and brain following acute lead exposure. Male Wistar rats were exposed to lead nitrate (50 mg/kg, i.p., once daily for 5 days) followed by treatment with the above chelating agents using two different doses of 25 or 50 mg/kg (orally) either alone and in combination once daily for five consecutive days. Lead exposure resulted in the significant inhibition of delta-aminolevulinic acid dehydratase activity and depletion of glutathione (GSH) in blood. These changes were accompanied by significant reduction in blood hemoglobin, RBC levels and superoxide dismutase and catalase activities. Significant increase in blood reactive oxygen species (ROS) and thiobarbituric acid reactive substances (TBARS) levels were noted. We observed marked increase in brain ROS level while GSH/oxidized glutathione ratio showed significant decrease accompanied by a significant increase in blood and brain lead concentration. The levels of norepinephrine, dopamine and serotonin in different brain regions were also altered on lead exposure. Co-administration of DMSA and MiADMSA particularly at the lower dose was most effective in the recovery of lead-induced changes in the hematological variables and oxidative stress and resulted in more pronounced depletion of lead from blood and brain compared to monotherapy with these chelators. On the other hand, combined administration of MiADMSA (50 mg/kg) in combination with DMSA (25 mg/kg each) had additional beneficial effect over the individual effect of chelating agent in the recovery of altered levels of brain biogenic amines. The study suggests that administration of MiADMSA is generally a better lead chelator than DMSA while combined administration of DMSA and Mi

  20. 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.

  1. Modeling the inhibition of the bacteral reduction of U(VI) by beta-MnO2(s).

    PubMed

    Liu, Chongxuan; Zachara, John M; Fredrickson, James K; Kennedy, David W; Dohnalkova, Alice

    2002-04-01

    Pyrolusite (beta-MnO2(s)) was used to assess the influence of a competitive electron acceptor on the kinetics of reduction of aqueous uranyl carbonate by a dissimilatory metal-reducing bacterium (DMRB), Shewanella putrefaciens strain CN32. The enzymatic reduction of U(VI) and beta-MnO2(s) and the abiotic redox reaction between beta-MnO2(s) and biogenic uraninite (UO2(s)) were independently investigated to allow for interpretation of studies of U(VI) bioreduction in the presence of beta-MnO2(s). Uranyl bioreduction to UO2(s) by CN32 with H2 as the electron donor followed Monod kinetics, with a maximum specific reduction rate of 110 M/h/10(8) cells/mL and a half-saturation constant of 370 microM. The bioreduction rate of beta-MnO2(s) by CN32 was described by a pseudo-first-order model with respect to beta-MnO2(s) surface sites, with a rate constant of 7.92 x 10(-2) h(-1)/10(8) cells/mL. Uraninite that precipitated as a result of microbial U(VI) reduction was abiotically reoxidized to U(VI) by beta-MnO2(s), with concomitant reduction to Mn(II). The oxidation of biogenic UO2(s) coupled with beta-MnO2(s) reduction was well-described by an electrochemical model. However, a simple model that coupled the bacterial reduction of U(VI) and beta-MnO2(s) with an abiotic redox reaction between UO2(s) and beta-MnO2(s) failed to describe the mass loss of U(VI) in the presence of beta-MnO2(s). Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) revealed that the particle size and spatial distribution of the biogenic UO2(s) changed dynamically in systems with, as compared to without, beta-MnO2(s)). These observations suggested that the surface properties and localization of UO2(s) in relation to the cell and beta-MnO2(s) surfaces was an important factor controlling the abiotic oxidation of UO2(s) and, thus, the overall rate and extent of U(VI) bioreduction. The coupled model that was modified to account for the "effective" contact surface area between UO2

  2. Catalytic oxidation of toluene in contaminant emission control systems using Mn-Ce/gamma-Al2O3.

    PubMed

    Kim, H-J; Choi, S-W; Inyang, H I

    2008-05-01

    Toluene, the alkyl benzene, is a common constituent of contaminant streams emitted by hydrocarbon fuel combustion systems. The oxidation of toluene to less toxic compounds can be enhanced through catalysis. The capacity of Mn-Ce/gamma-Al2O3 to catalyze toluene oxidation was investigated using a fixed bed flow reactor, operating within a temperature range of 160-400 degrees C. Mono-metallic catalysts were prepared with the manganese and cerium contents of 1-21 wt% on gamma-Al2O3, support and bi-metallic catalysts were prepared with cerium (0.5-21 wt%/) on 18.2 wt% manganese. The results indicate that the 18.2 wt% Mn-10.0 wt% Ce catalyst combination had the best catalytic efficiency for toluene oxidation. Increase in cerium loading reduces the surface area of catalytic materials measured by BET, but increases catalytic activity. Data obtained through TGA (Thermogravimetric analysis), XRD (X-ray diffraction) and toluene-TPR (Temperature Programmed Reduction) measurements show that the reduction of the catalysts in the process of toluene oxidation is directly proportional to observed weight loss under hydrogen flow. From these results, it is concluded that cerium improves the catalytic role of manganese in toluene oxidation. Oxygen mobility is also promoted in a redox mechanism in which MnO2 serves as the active sites. These results are useful in the development of toluene emission control systems for hydrocarbon fuel combustion systems.

  3. Biogenic metals in advanced water treatment.

    PubMed

    Hennebel, Tom; De Gusseme, Bart; Boon, Nico; Verstraete, Willy

    2009-02-01

    Microorganisms can change the oxidation state of metals and concomitantly deposit metal oxides and zerovalent metals on or into their cells. The microbial mechanisms involved in these processes have been extensively studied in natural environments, and researchers have recently gained interest in the applications of microbe-metal interactions in biotechnology. Because of their specific characteristics, such as high specific surface areas and high catalytic reactivity, biogenic metals offer promising perspectives for the sorption and (bio)degradation of contaminants. In this review, the precipitation of biogenic manganese and iron species and the microbial reduction of precious metals, such as palladium, platinum, silver and gold, are discussed with specific attention to the application of these biogenic metals in innovative remediation technologies in advanced water treatment.

  4. Biogenic VOC and Climate

    NASA Astrophysics Data System (ADS)

    Guenther, A. B.

    2014-12-01

    Secondary organic aerosol (SOA) and ozone are short-lived contributors to radiative forcing that can drive relatively rapid changes in climate. They are not emitted into the atmosphere but are formed from precursors including biogenic volatile organic compounds (BVOC) that are emitted from terrestrial ecosystems. BVOC can also impact longer-lived climate-relevant compounds by acting as a sink for the oxidants that remove moderately reactive gases such as methane and by being a source of carbon dioxide. Emissions of BVOC are highly temperature sensitive, and some also respond to light, and so there is a potential feedback coupling between climate and BVOC emissions. Another potential feedback is associated with the water cycle since SOA can influence precipitation by serving as cloud condensation nuclei and because VOC emissions are sensitive to water availability. Anthropogenic air pollutants add to the complexity of this coupled system by enhancing the production of ozone and SOA from BVOC. The role of BVOC in the land-atmosphere-climate system and potential feedback couplings is conceptually clear but developing an accurate quantitative representation is challenging. Our current understanding of the role of BVOC in the climate system and potential feedback couplings will be presented and the major uncertainties will be discussed. Advances in observations for constraining models, including long-term measurements and recent multi-scale studies, will be presented and priorities for continued advances will be discussed.

  5. Synthesis and characterization of R{sub 2}MnTiO{sub 7} (R = Y and Er) pyrochlores oxides

    SciTech Connect

    Martínez-Coronado, R.; Alonso, J.A.; Fernández, M.T.

    2013-09-01

    Graphical abstract: - Abstract: New pyrochlore-like phases of composition R{sub 2}MnTiO{sub 7} (R = Er and Y) have been synthesized by a soft-chemistry procedure involving citrates of the different metal ions followed by thermal treatments at moderate temperatures (850 °C for 12 h in air). A characterization by X-ray diffraction and neutron powder diffraction (NPD) has been carried out in order to determine the crystal structure features: these phyrochlores are cubic, space group Fd-3m, defining an intrinsically frustrated three-dimensional system. The Rietveld-refinement from NPD data at room temperature evidences an antisite cation disorder (distribution of Mn between A and B positions) that is accompanied by an increment of the oxygen-vacancy concentration due to the reduction of Mn{sup 4+} at the B position to Mn{sup 2+} at the A position. Thermogravimetric analysis (TGA) was useful to evaluate the stability of these oxides in reducing conditions up to 500 °C. Magnetic susceptibility measurements indicate a ferromagnetic behavior, due to the random distribution of Mn{sup 4+} ions in the octahedral sublattice. At lower temperatures there is a polarization of the R{sup +3} magnetic moments, which also participate in the magnetic structure. Aiming to evaluate these materials as possible electrodes for solid oxide fuel cells (SOFC) we determined that the thermal expansion coefficients between 100 and 900 °C perfectly match with those of the usual electrolytes; however, these pyrochlore oxides display a semiconductor-like behavior with poor conductivity values, e.g. 6 × 10{sup −3} cm{sup −1} at 850 °C for Er, which would prevent its use as MIEC (mixed ionic-electronic conductors) oxides in SOFC devices.

  6. Protective effect of Mn(III)-desferrioxamine B upon oxidative stress caused by ozone and acid rain in the Brazilian soybean cultivar Glycine max "Sambaiba".

    PubMed

    Esposito, Jéssica Bordotti Nobre; Esposito, Breno Pannia; Azevedo, Ricardo Antunes; Cruz, Luciano Soares; da Silva, Luzimar Campos; de Souza, Silvia Ribeiro

    2015-04-01

    This study aimed to investigate the effects of the Mn complex (Mn(III)-desferrioxamine B (MnDFB)) on oxidative stress in the Brazilian soybean cultivar Glycine max "Sambaiba" following exposure to ozone and acid rain. We determined the suitable dose of MnDFB to apply to G. max seedlings using a dose-response curve. The highest superoxide dismutase (SOD) activity and Mn content in leaves were found upon the application of 8 μM MnDFB. Thus, G. max seedlings pretreated with 8 μM MnDFB were individually exposed to ozone and acid rain simulated. Pretreatment with MnDFB reduced lipid peroxidation upon ozone exposure and increased SOD activity in leaves; it did not alter the metal content in any part of the plant. Conversely, following acid rain exposure, neither the metal content in leaves nor SOD enzyme activity were directly affected by MnDFB, unlike pH. Our findings demonstrated that exogenous MnDFB application before ozone exposure may modulate the MnSOD, Cu/ZnSOD, and FeSOD activities to combat the ROS excess in the cell. Here, we demonstrated that the applied dose of MnDFB enhances antioxidative defenses in soybean following exposure to acid rain and especially to ozone.

  7. Influence of FeO and sulfur on solid state reaction between MnO-SiO2-FeO oxides and an Fe-Mn-Si solid alloy during heat treatment at 1473 K

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-song; Yang, Shu-feng; Kim, Kyung-ho; Li, Jing-she; Shibata, Hiroyuki; Kitamura, Shin-ya

    2015-08-01

    To clarify the influence of FeO and sulfur on solid state reaction between an Fe-Mn-Si alloy and MnO-SiO2-FeO oxides under the restricted oxygen diffusion flux, two diffusion couples with different sulfur contents in the oxides were produced and investigated after heat treatment at 1473 K. The experimental results were also compared with previous work in which the oxides contained higher FeO. It was found that although the FeO content in the oxides decreased from 3wt% to 1wt% which was lower than the content corresponding to the equilibrium with molten steel at 1873 K, excess oxygen still diffused from the oxides to solid steel during heat treatment at 1473 K and formed oxide particles. In addition, increasing the sulfur content in the oxides was observed to suppress the diffusion of oxygen between the alloy and the oxides.

  8. A2MnU3O11 (A = K, Rb) and Li3.2Mn1.8U6O22: Three New Alkali-Metal Manganese Uranium(VI) Oxides Related to Natrotantite.

    PubMed

    Read, Cory Michael; Morrison, Gregory; Yeon, Jeongho; Smith, Mark D; Zur Loye, Hans-Conrad

    2015-07-20

    Single crystals of three new alkali-metal manganese uranium oxides, K2MnU3O11, Rb2MnU3O11, and Li3.2Mn1.8U6O22, have been grown from molten chloride fluxes and structurally characterized by single-crystal X-ray diffraction. The first two compounds crystallize in the trigonal space group, R3̅c, in the three-dimensional (3D), natrotantite structure composed of α-U3O8-topological layers connected via MnO6 octahedra. The Li-containing compound crystallizes in the monoclinic space group, Cc, with a related 3D structure, composed of β-U3O8-topological sheets connected via irregular MnO7 polyhedra. All three compounds exhibit typical uranyl, UO2(2+), coordination environments consisting of either UO7 pentagonal bipyramids or UO6 flattened octahedra. The lattice parameters of the new oxides are K2MnU3O11, a = 6.8280(2) Å, c = 36.8354(17) Å; Rb2MnU3O11, a = 6.8407(2) Å, c = 37.5520(17) Å; and Li3.2Mn1.8U6O22, a = 11.8958(8) Å, b = 10.9639(7) Å, c = 13.3269(8) Å, and β = 91.442(4)°. The magnetic susceptibilities of the K and Rb phases are discussed.

  9. Significance of the Henri-Michaelis-Menten theory in abiotic catalysis: catechol oxidation by δ-MnO 2

    NASA Astrophysics Data System (ADS)

    Naidja, A.; Huang, P. M.

    2002-05-01

    The Henri-Michaelis-Menten theory, for more than eight decades, was only restricted to homogeneous enzymatic catalysis. A mimic of an enzymatic kinetics based on the Henri-Michaelis-Menten concept was experimentally observed in heterogeneous catalysis in the present study with δ-MnO 2 as an abiotic catalyst in the oxidation of catechol (1,2-dihydroxybenzene). Using the derived linear forms of Lineweaver-Burk or Hofstee, the data show that similar to the enzyme tyrosinase, the kinetics of the catechol oxidation catalyzed by δ-MnO 2 can be described by the Henri-Michaelis-Menten equation, V0= VmaxS/( Km+ S), where Vmax is the maximum velocity and Km the concentration of the substrate ( S) corresponding to an initial velocity ( V0) half of Vmax. By analogy to the enzymatic kinetics, the parameters Vmax and Km for an heterogeneous abiotic catalysis were derived for the first time. Further, based on the concentration of the active centers of the mineral oxide, the kinetic constants kcat and kcat/ Km, respectively, representing the turnover frequency and the efficiency of the mineral catalyst, were also determined from the derived general rate equation of Briggs and Haldane. As an abiotic catalyst, δ-MnO 2 has a paramount role in the oxidation of phenolic compounds in soil, sediment and water environments. Therefore, the present observation is of fundamental and practical significance in elucidating the affinity between an abiotic catalyst and a substrate based on the Henri-Michaelis-Menten theory.

  10. NMR-based metabonomic analysis of MnO-embedded iron oxide nanoparticles as potential dual-modal contrast agents

    NASA Astrophysics Data System (ADS)

    Li, Jinquan; Zhou, Zijian; Feng, Jianghua; Cai, Shuhui; Gao, Jinhao; Chen, Zhong

    2014-05-01

    MnO-embedded iron oxide nanoparticles (MnIO-NPs) can be treated as potential dual-modal contrast agents. However, their overall bio-effects and potential toxicity remain unknown. In this study, the metabolic effects of MnIO-NPs (dosed at 1 and 5 mg Fe/kg) on Sprague-Dawley rats were investigated using metabonomic analysis, histopathological examination, and conventional biochemical analysis. The histological changes included a focal inflammation in the liver at high-dose and a slightly enlarged area of splenic white pulp after 48 h post-dose. Blood biochemical analysis showed that albumin, globulins, aspartate aminotransferase, lactate dehydrogenase, blood urea nitrogen, and glucose changed distinctly compared to the control. The metabonomic analysis of body fluids (serum and urine) and tissues (liver, kidney, and spleen) indicated that MnIO-NPs induced metabolic perturbation in rats including energy, nucleotides, amino acids and phospholipid metabolisms. Besides, the variations of supportive nutrients: valine, leucine, isoleucine, nicotinamide adenine dinucleotide (phosphate), and nicotinamide, and the conjugation substrates: glycine, taurine, glutamine, glutathione, and methyl donors (formate, sarcosine, dimethylglycine, choline, and betaine) were involved in detoxification reaction of MnIO-NPs. The obtained information would provide identifiable ground for the candidate selection and optimization.

  11. 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.

  12. Oxygen atom transfer and oxidative water incorporation in cuboidal Mn3MO(n) complexes based on synthetic, isotopic labeling, and computational studies.

    PubMed

    Kanady, Jacob S; Mendoza-Cortes, Jose L; Tsui, Emily Y; Nielsen, Robert J; Goddard, William A; Agapie, Theodor

    2013-01-23

    The oxygen-evolving complex (OEC) of photosystem II contains a Mn(4)CaO(n) catalytic site, in which reactivity of bridging oxidos is fundamental to OEC function. We synthesized structurally relevant cuboidal Mn(3)MO(n) complexes (M = Mn, Ca, Sc; n = 3,4) to enable mechanistic studies of reactivity and incorporation of μ(3)-oxido moieties. We found that Mn(IV)(3)CaO(4) and Mn(IV)(3)ScO(4) were unreactive toward trimethylphosphine (PMe(3)). In contrast, our Mn(III)(2)Mn(IV)(2)O(4) cubane reacts with this phosphine within minutes to generate a novel Mn(III)(4)O(3) partial cubane plus Me(3)PO. We used quantum mechanics to investigate the reaction paths for oxygen atom transfer to phosphine from Mn(III)(2)Mn(IV)(2)O(4) and Mn(IV)(3)CaO(4). We found that the most favorable reaction path leads to partial detachment of the CH(3)COO(-) ligand, which is energetically feasible only when Mn(III) is present. Experimentally, the lability of metal-bound acetates is greatest for Mn(III)(2)Mn(IV)(2)O(4). These results indicate that even with a strong oxygen atom acceptor, such as PMe(3), the oxygen atom transfer chemistry from Mn(3)MO(4) cubanes is controlled by ligand lability, with the Mn(IV)(3)CaO(4) OEC model being unreactive. The oxidative oxide incorporation into the partial cubane, Mn(III)(4)O(3), was observed experimentally upon treatment with water, base, and oxidizing equivalents. (18)O-labeling experiments provided mechanistic insight into the position of incorporation in the partial cubane structure, consistent with mechanisms involving migration of oxide moieties within the cluster but not consistent with selective incorporation at the site available in the starting species. These results support recent proposals for the mechanism of the OEC, involving oxido migration between distinct positions within the cluster.

  13. FTIR Spectroscopic Study of Mn(II) Oxidizing Pseudomonas putida GB1 Biofilms on ZnSe, Ge, and CdTe Crystal Surfaces

    NASA Astrophysics Data System (ADS)

    Parikh, S. J.; Gilbert, H. L.; Conklin, M. H.; Chorover, J.

    2003-12-01

    Pseudomonas putida strain GB1 is an aerobic, gram-negative bacterium capable of gaining energy from the biological oxidation of Mn(II). The increased kinetics of Mn(II) oxidation resulting from this microbial catalysis is known to contribute to the formation of Mn(IV) oxides in natural waters. Environmental conditions, including aqueous and surface chemistry, greatly affect the macromolecular composition and surface adhesion behavior of bacteria. For example, the chemistry of GB1 biofilms forming on crystal surfaces is expected to vary with Mn(II) concentration in solution. We used Fourier transform infrared (FTIR) spectroscopy to probe the formation of GB1 biofilms on the surfaces of negatively-charged IR transparent ZnSe, Ge, and CdTe crystal windows. Bacterial adhesion experiments were carried out both in the presence and absence of Mn(II)(aq) with FTIR windows suspended in a bioreactor comprising GB1 cells in a mineral growth medium at pH 7.6 and 30° C. After 85 h, windows were removed from the reactor and IR spectra were collected. Oxidation of Mn(II) was confirmed via leucoberbelin blue (LBB) indicator and the appearance of Mn-O stretches in biofilm IR spectra. Transmission FTIR spectra do not reveal detectable effects of crystal type on biofilm composition, but do indicate changes in chemistry resulting from introduction of Mn(II). In the presence of Mn(II), spectra of biofilms show higher relative intensity in the carbohydrate region (specifically 1160, 1052 cm-1). A down frequency shift in the P=O absorbance was also observed (1240 to 1222 cm-1). These results indicate a modification of bacterial cell/biofilm composition resulting during biological oxidation of Mn(II). The CdTe transmission window permits measurements to low wavenumbers (<600 cm-1) and a peak at 588 cm-1 was observed when bacteria were surface-adhered in the presence of Mn(II). This peak, which has been attributed to Mn-O stretching vibrations, may provide an index of Mn oxide crystal

  14. 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.

  15. 3D Flower-like β-MnO2/Reduced Graphene Oxide Nanocomposites for Catalytic Ozonation of Dichloroacetic Acid

    PubMed Central

    Li, Gang; Li, Kezheng; Liu, Aijuan; Yang, Ping; Du, Yukou; Zhu, Mingshan

    2017-01-01

    Considering the potential use of manganese oxide based nanocomposite in catalytic ozonation of water contaminant, we report unique three-dimensional (3D) nanoarchitectures composed of β-MnO2 and reduced graphene oxide (RGO) for catalytic ozonation of dichloroacetic acid (DCAA) from drinking water. The catalytic results show that the 3D β-MnO2/RGO nanocomposites (FMOG) can be used as efficient and stable ozonation catalysts to eliminate DCAA from water. The probable mechanism of catalytic ozonation was also proposed by detecting intermediates using gas chromatography-mass spectrometry. This result likely paves a facile avenue and initiates new opportunities for the exploration of heterogeneous catalysts for the removal of disinfection by-products from drinking water.

  16. 3D Flower-like β-MnO2/Reduced Graphene Oxide Nanocomposites for Catalytic Ozonation of Dichloroacetic Acid

    NASA Astrophysics Data System (ADS)

    Li, Gang; Li, Kezheng; Liu, Aijuan; Yang, Ping; Du, Yukou; Zhu, Mingshan

    2017-03-01

    Considering the potential use of manganese oxide based nanocomposite in catalytic ozonation of water contaminant, we report unique three-dimensional (3D) nanoarchitectures composed of β-MnO2 and reduced graphene oxide (RGO) for catalytic ozonation of dichloroacetic acid (DCAA) from drinking water. The catalytic results show that the 3D β-MnO2/RGO nanocomposites (FMOG) can be used as efficient and stable ozonation catalysts to eliminate DCAA from water. The probable mechanism of catalytic ozonation was also proposed by detecting intermediates using gas chromatography-mass spectrometry. This result likely paves a facile avenue and initiates new opportunities for the exploration of heterogeneous catalysts for the removal of disinfection by-products from drinking water.

  17. Synthesis and study of the crystallographic and magnetic structure of DyFeMnO{sub 5}: A new ferrimagnetic oxide

    SciTech Connect

    Martinez-Lope, M.J.; Retuerto, M.; Alonso, J.A. Pomjakushin, V.

    2008-09-15

    The title oxide has been obtained by replacing Mn{sup 3+} by Fe{sup 3+} in the parent oxide DyMn{sub 2}O{sub 5}. The crystallographic and magnetic structures have been analysed from neutron powder diffraction (NPD) data, in complement with susceptibility and magnetic measurements. DyFeMnO{sub 5} is orthorhombic, belonging to the Pbam space group as the parent compound. The crystal structure contains infinite chains of edge-sharing Mn{sup 4+}O{sub 6} octahedra, interconnected by dimer units of Fe{sup 3+}O{sub 5} square pyramids. There is a certain antisite disorder in the crystal structure, with 8.0% of the Mn{sup 4+} sites occupied by Fe cations, and 8.2% of the Fe{sup 3+} positions occupied by Mn{sup 3+} cations. The magnetization measurements show that DyFeMnO{sub 5} presents magnetic order below T{sub C}{approx}178 K; a study of the magnetic structure from the low-temperature NPD patterns indicates an antiferromagnetic coupling of the Mn{sup 4+} and Fe{sup 3+} spins, with the polarization of the Dy{sup 3+} magnetic moments parallel to the those of the Fe sublattice. - Graphical abstract: DyFeMnO{sub 5} is orthorhombic (Pbam) as the parent DyMn{sub 2}O{sub 5} oxide. The crystal structure contains infinite chains of edge-sharing Mn{sup 4+}O{sub 6} octahedra, interconnected by dimer units of Fe{sup 3+}O{sub 5} square pyramids. It is ferrimagnetic below T{sub C}{approx}178 K; a NPD study indicated an antiferromagnetic coupling of the Mn{sup 4+} and Fe{sup 3+} spins, with Dy{sup 3+} magnetic moments parallel to those of Fe.

  18. Effects of plant polyphenols and a-tocopherol on lipid oxidation, microbiological characteristics, and biogenic amines formation in dry-cured bacons

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Effects of plant polyphenols (tea polyphenol, grape seed extract, and gingerol) and a-tocopherol on physicochemical parameters, microbiological counts, and biogenic amines were determined in dry-cured bacons at the end of ripening. Results showed that plant polyphenols and a-tocopherol significantly...

  19. Facile preparation of Ni(OH)2-MnO2 hybrid material and its application in the electrocatalytic oxidation of hydrazine.

    PubMed

    Anu Prathap, M U; Anuraj, V; Satpati, Biswarup; Srivastava, Rajendra

    2013-11-15

    A surfactant-free synthetic methodology is reported for the preparation of Ni(OH)2-MnO2 hybrid nanostructures. For comparative study, MnO2 and Ni(OH)2 were also synthesized. Materials were characterized by X-ray diffraction, nitrogen sorption, scanning electron microscopy, and transmission electron microscopy. Ni(OH)2-MnO2 modified electrode is fabricated for the determination of hydrazine. The electrochemical oxidation of hydrazine was investigated using cyclic, linear sweep voltammetries, and chronoamperometry methods. The Ni(OH)2-MnO2 modified electrode showed hydrazine oxidation with decrease in the over voltage and increase in the oxidation peak current, when compared to MnO2, Ni(OH)2, and bare GCE. pH was optimized to obtain the best peak potential and current sensitivity. Chronoamperometry was used to estimate the diffusion coefficient of hydrazine. The kinetic parameters such as overall number of electrons involved in the catalytic oxidation of hydrazine and the rate constant (k) for the oxidation of hydrazine at Ni(OH)2-MnO2 modified electrode were determined. The Ni(OH)2-MnO2 modified electrode exhibited good sensitivity, stability, and reproducibility in hydrazine sensing.

  20. Cyanobacterial Mn-catalase ‘KatB’: Molecular link between salinity and oxidative stress resistance

    PubMed Central

    Chakravarty, Dhiman; Banerjee, Manisha; Waghmare, Namrata; Ballal, Anand

    2016-01-01

    ABSTRACT Catalases are ubiquitous enzymes that detoxify H2O2 in virtually all organisms exposed to oxygen. The filamentous, nitrogen-fixing cyanobacterium, Anabaena PCC 7120, shows the presence of 2 genes (katA and katB) that encode Mn-catalases. We have recently shown that pre-treatment of Anabaena with NaCl causes substantial induction of the KatB protein, which consequently leads to increased oxidative stress resistance in that cyanobacterium. Interestingly, when compared to the wild-type, the katB mutant shows decreased growth and impaired photosynthetic activity in the presence of NaCl. Furthermore, the NaCl-treated katB mutant is extremely sensitive to H2O2. In this study, the ultrastructural changes occurring in the katB mutant and the wild-type Anabaena cells are analyzed to understand the cellular basis of the above-mentioned protective phenomena. Other data show that a wide variety of osmolytes induce katB expression in Anabaena, indicating that katB is a genuine osmo-inducible gene. These results have important biotechnological implications for the development of novel cyanobacterial biofertilzers and transgenic plants with improved resistance to salinity. PMID:27829979

  1. Morphological and magnetic study of CaMnO{sub 3-x} oxides obtained from different routes

    SciTech Connect

    Gil de Muro, Izaskun; Insausti, Maite; Lezama, Luis; Rojo, Teofilo . E-mail: qiproapt@lg.ehu.es

    2005-03-15

    The CaMnO{sub 3-x} (x=0 and 0.02) mixed oxide was synthesised from both thermal treatment of a metallo-organic precursor and ceramic method. The morphology of the different products is clearly different. The samples exhibit antiferromagnetic ordering with T{sub N} near to 120K and a weak ferromagnetic component above T{sub N}. This is slightly stronger in the phase prepared by the ceramic route.

  2. Stretchable Fiber Supercapacitors with High Volumetric Performance Based on Buckled MnO2 /Oxidized Carbon Nanotube Fiber Electrodes.

    PubMed

    Li, Mingyang; Zu, Mei; Yu, Jinshan; Cheng, Haifeng; Li, Qingwen

    2017-03-01

    A stretchable fiber supercapacitor (SC) based on buckled MnO2 /oxidized carbon nanotube (CNT) fiber electrode is fabricated by a simple prestraining-then-buckling method. The prepared stretchable fiber SC has a specific volumetric capacitance up to 409.4 F cm(-3) , which is 33 times that of the pristine CNT fiber based SC, and shows the outstanding stability and repeatability in performance as a stretchable SC.

  3. 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.

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

    SciTech Connect

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

    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 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%). Finally, 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.

  5. 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.

  6. Relative Reactivity of Biogenic and Chemogenic Uraninite and Biogenic Non Crystalline U(IV)

    PubMed Central

    Cerrato, José M.; Ashner, Matthew N.; Alessi, Daniel S.; Lezama-Pacheco, Juan S.; Bernier-Latmani, Rizlan; Bargar, John R.; Giammar, Daniel E.

    2013-01-01

    Aqueous chemical extractions and X-ray absorption spectroscopy (XAS) analyses were conducted to investigate the reactivity of chemogenic uraninite, nanoparticulate biogenic uraninite, and biogenic monomeric U(IV) species. The analyses were conducted in systems containing a total U concentration that ranged from 1.48 to 2.10 mM. Less than 0.02% of the total U was released to solution in extractions that targeted water soluble and ion exchangeable fractions. Less than 5% of the total U was solubilized via complexation with a 0.1 M solution of NaF. Greater than 90% of the total U was extracted from biogenic uraninite and monomeric U(IV) after 6 hours of reaction in an oxidizing solution of 50 mM K2S2O8. Additional oxidation experiments with lower concentrations (2 mM and 10 mM) of K2S2O8 and 8.2 mg L−1 dissolved oxygen suggested that monomeric U(IV) species are more labile than biogenic uraninite; chemogenic uraninite was much less susceptible to oxidation than either form of biogenic U(IV). These results suggest that non-crystalline forms of U(IV) may be more labile than uraninite in subsurface environments. This work helps fill critical gaps in our understanding of the behavior of solid-associated U(IV) species in bioremediated sites and natural uranium ore deposits. PMID:23906226

  7. Proteins involved in electron transfer to Fe(III) and Mn(IV) oxides by Geobacter sulfurreducens and Geobacter uraniireducens.

    PubMed

    Aklujkar, M; Coppi, M V; Leang, C; Kim, B C; Chavan, M A; Perpetua, L A; Giloteaux, L; Liu, A; Holmes, D E

    2013-03-01

    Whole-genome microarray analysis of Geobacter sulfurreducens grown on insoluble Fe(III) oxide or Mn(IV) oxide versus soluble Fe(III) citrate revealed significantly different expression patterns. The most upregulated genes, omcS and omcT, encode cell-surface c-type cytochromes, OmcS being required for Fe(III) and Mn(IV) oxide reduction. Other electron transport genes upregulated on both metal oxides included genes encoding putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc4 and Cbc5, periplasmic c-type cytochromes Dhc2 and PccF, outer membrane c-type cytochromes OmcC, OmcG and OmcV, multicopper oxidase OmpB, the structural components of electrically conductive pili, PilA-N and PilA-C, and enzymes that detoxify reactive oxygen/nitrogen species. Genes upregulated on Fe(III) oxide encode putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc3 and Cbc6, periplasmic c-type cytochromes, including PccG and PccJ, and outer membrane c-type cytochromes, including OmcA, OmcE, OmcH, OmcL, OmcN, OmcO and OmcP. Electron transport genes upregulated on Mn(IV) oxide encode periplasmic c-type cytochromes PccR, PgcA, PpcA and PpcD, outer membrane c-type cytochromes OmaB/OmaC, OmcB and OmcZ, multicopper oxidase OmpC and menaquinone-reducing enzymes. Genetic studies indicated that MacA, OmcB, OmcF, OmcG, OmcH, OmcI, OmcJ, OmcM, OmcV and PccH, the putative Cbc5 complex subunit CbcC and the putative Cbc3 complex subunit CbcV are important for reduction of Fe(III) oxide but not essential for Mn(IV) oxide reduction. Gene expression patterns for Geobacter uraniireducens were similar. These results demonstrate that the physiology of Fe(III)-reducing bacteria differs significantly during growth on different insoluble and soluble electron acceptors and emphasize the importance of c-type cytochromes for extracellular electron transfer in G. sulfurreducens.

  8. An aqueous method for the controlled manganese (Mn(2+)) substitution in superparamagnetic iron oxide nanoparticles for contrast enhancement in MRI.

    PubMed

    Ereath Beeran, Ansar; Nazeer, Shaiju S; Fernandez, Francis Boniface; Muvvala, Krishna Surendra; Wunderlich, Wilfried; Anil, Sukumaran; Vellappally, Sajith; Ramachandra Rao, M S; John, Annie; Jayasree, Ramapurath S; Varma, P R Harikrishna

    2015-02-14

    Despite the success in the use of superparamagnetic iron oxide nanoparticles (SPION) for various scientific applications, its potential in biomedical fields has not been exploited to its full potential. In this context, an in situ substitution of Mn(2+) was performed in SPION and a series of ferrite particles, MnxFe1-xFe2O4 with a varying molar ratio of Mn(2+) : Fe(2+) where 'x' varies from 0-0.75. The ferrite particles obtained were further studied in MRI contrast applications and showed appreciable enhancement in their MRI contrast properties. Manganese substituted ferrite nanocrystals (MnIOs) were synthesized using a novel, one-step aqueous co-precipitation method based on the use of a combination of sodium hydroxide and trisodium citrate (TSC). This approach yielded the formation of highly crystalline, superparamagnetic MnIOs with good control over their size and bivalent Mn ion crystal substitution. The presence of a TSC hydrophilic layer on the surface facilitated easy dispersion of the materials in an aqueous media. Primary characterizations such as structural, chemical and magnetic properties demonstrated the successful formation of manganese substituted ferrite. More significantly, the MRI relaxivity of the MnIOs improved fourfold when compared to SPION crystals imparting high potential for use as an MRI contrast agent. Further, the cytocompatibility and blood compatibility evaluations demonstrated excellent cell morphological integrity even at high concentrations of nanoparticles supporting the non-toxic nature of nanoparticles. These results open new horizons for the design of biocompatible water dispersible ferrite nanoparticles with good relaxivity properties via a versatile and easily scalable co-precipitation route.

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

    PubMed Central

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

    2015-01-01

    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. PMID:25765731

  10. 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.

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

    PubMed

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

    2015-03-13

    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.

  12. Reaction Between MnO-SiO2-FeO Solid Oxide and Solid Steel Deoxidized by Si and Mn During Heat Treatment at 1473 K (1200 °C)

    NASA Astrophysics Data System (ADS)

    Liu, Cheng-song; Kim, Kyung-Ho; Kim, Sun-Joong; Li, Jing-she; Ueda, Shigeru; Gao, Xu; Shibata, Hiroyuki; Kitamura, Shin-ya

    2015-08-01

    A new method using a confocal scanning laser microscope for melting oxide at 1673 K (1400 °C) to produce a diffusion couple, which consists of oxide and an iron-based alloy, has been developed for the investigation of a solid-state reaction between them. It is important to obtain good contact between the Fe-Mn-Si alloy and MnO-SiO2-FeO oxide before the diffusion experiment to observe diffusion of elements between them at 1473 K (1200 °C). In this system, the melting point of the oxides is higher than the temperature where the reaction would be observed. The pretreatment involving melting oxide at 1673 K (1400 °C) to obtain good contact with the alloy was carried out using a new method. The effect of the pretreatment at 1673 K (1400 °C) on the diffusion experiment at 1473 K (1200 °C) was minimized by this new method. The effect of diffusion of oxygen on the solid-state reaction between the Fe-Mn-Si alloy and MnO-SiO2-FeO oxide at 1473 K (1200 °C) was observed clearly and showed good agreement with Wagner's model of internal oxidation of metal.

  13. Ag{sub 2}CuMnO{sub 4}: A new silver copper oxide with delafossite structure

    SciTech Connect

    Munoz-Rojas, David; Subias, Gloria; Fraxedas, Jordi; Martinez, Benjamin; Casas-Cabanas, Montse; Canales-Vazquez, Jesus; Gonzalez-Calbet, Jose; Garcia-Gonzalez, Ester; Walton, Richard I.; Casan-Pastor, Nieves . E-mail: nieves@icmab.es

    2006-12-15

    The use of hydrothermal methods has allowed the synthesis of a new silver copper mixed oxide, Ag{sub 2}CuMnO{sub 4}, the first example of a quaternary oxide containing both elements. It crystallizes with the delafossite 3R structure, thus being the first delafossite to contain both Ag and Cu. Synthesis conditions affect the final particle size (30-500nm). Powder X-ray diffraction Rietveld refinement indicates a trigonal structure (R3-bar m) and cell parameters a=2.99991A and c=18.428A, where Cu and Mn are disordered within the octahedral B positions in the plane and linearly coordinated Ag occupies de A position between layers. X-ray absorption near edge spectroscopy (XANES) for copper and manganese, and XPS for silver evidence +2, +4, and +1 oxidation states. The microstructure consists of layered parts that may form large twins showing 5nm nanodomains. Finally, magnetic measurements reveal the existence of ferromagnetic coupling yielding in-plane moments that align antiferromagnetically at lower temperatures. The singularity of the new phase resides on the fact that is an example of a bidimensional arrangement of silver and copper in an oxide that also shows clear bidimensionality in its physical properties. That is of special relevance to the field of high T{sub c} superconducting oxides, while the ferromagnetic coupling in a bidimensional system deserves itself special attention.

  14. Molecular Recognition in Mn-Catalyzed C-H Oxidation. Reaction Mechanism and Origin of Selectivity from a DFT Perspective

    PubMed Central

    Balcells, David; Moles, Pamela; Blakemore, James; Raynaud, Christophe; Brudvig, Gary W.; Crabtree, Robert H.

    2010-01-01

    Experimental studies have shown that the C-H oxidation of ibuprofen and methylcyclohexane acetic acid can be carried out with high selectivies using [(terpy’)Mn(OH2)(μ-O)2Mn(OH2)(terpy’)]3+ as catalyst, where terpy’ is a terpyridine ligand functionalized with a phenylene linker and a Kemp’s triacid serving to recognize the reactant via H-bonding. Experiments, described here, suggest that the sulfate counter anion, present in stochiometric amounts, coordinates to manganese in place of water. DFT calculations have been carried out using [(terpy’)Mn(O)(μ-O)2Mn(SO4)(terpy’)]+ as model catalyst, to analyze the origin of selectivity and its relation to molecular recognition, as well as the mechanism of catalyst inhibition by tert-butyl benzoic acid. The calculations show that a number of spin states, all having radical oxygen character, are energetically accessible. All these spin states promote C-H oxidation via a rebound mechanism. The catalyst recognizes the substrate by a double H bond. This interaction orients the substrate inducing highly selective C-H oxidation. The double hydrogen bond stabilizes the reactant, the transition state and the product to the same extent. Consequently, the reaction occurs at lower energy than without molecular recognition. The association of the catalyst with tert-butyl benzoic acid is shown to shield the access of unbound substrate to the reactive oxo site, hence preventing non-selective hydroxylation. It is shown that the two recognition sites of the catalyst can be used in a cooperative manner to control the access to the reactive centre. PMID:19623399

  15. Where Water is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster from X-ray Spectroscopy

    SciTech Connect

    Yano, Junko; Yano, Junko; Yachandra, Vittal K.

    2007-10-24

    Light-driven oxidation of water to dioxygen in plants, algae and cyanobacteria iscatalyzed within photosystem II (PS II) by a Mn4Ca cluster. Although the cluster has been studied by many different methods, the structure and the mechanism have remained elusive. X-ray absorption and emission spectroscopy and EXAFS studies have been particularly useful in probing the electronic and geometric structure, and the mechanism of the water oxidation reaction. Recent progress, reviewed here, includes polarized X-ray absorption spectroscopy measurements of PS II single crystals. Analysis of those results has constrained the Mn4Ca cluster geometry to a setof three similar high-resolution structures. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 Angstrom-resolution X-ray structures or other previously proposed models. The differences between the models derived from X-rayspectroscopy and crystallography are predominantly because of damage to the Mn4Ca cluster by X-rays under the conditions used for structure determination by X-ray crystallography. X-ray spectroscopy studies are also used for studying the changes in the structure of the Mn4Ca catalytic center as it cycles through the five intermediate states known as the Si-states (i=0-4). The electronic structure of the Mn4Ca cluster has been studied more recently using resonant inelastic X-ray scattering spectroscopy (RIXS), in addition to the earlier X-ray absorption and emission spectroscopy methods. These studies are revealing that the assignment of formaloxidation states is overly simplistic. A more accurate description should consider the charge density on the Mn atoms that includes the covalency of the bonds and delocalization of the charge over the cluster. The geometric and electronic structure of the Mn4Ca cluster in the S-states derived from X-ray spectroscopy are leading to a detailed understanding of the mechanism of the O-O bond formation during the photosynthetic water

  16. RuO2 nanoparticle-modified (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide as an active anode for direct hydrocarbon type solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Shin, Tae Ho; Hagiwara, Hidehisa; Ida, Shintaro; Ishihara, Tatsumi

    2015-09-01

    Composite oxide anodes have recently attracted great attention as alternative materials for solid oxide fuel cell anodes because of their potential to overcome the serious performance deterioration associated with the traditional Ni-based cermet. In particular, oxide anodes show a greater tolerance to coke and reoxidation than existing Ni-based cermets. In this study, the anodic performance of a (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide modified with additional amounts of catalytically active RuO2 nanoparticles was investigated. Heat treatment resulted in highly dispersed RuO2 particles (ca. 10 nm). Anodes containing 10 wt% added RuO2 exhibited fairly high maximum power densities of 0.3 and 1.5 W cm-2 in H2 and C3H8, respectively, at 800 °C. The cells showed stable power density and negligible carbon formation even after 50 h of operation at 1 A cm-2. The increased power density was assigned to decreased anodic overpotential and internal resistance losses because RuO2 nanoparticles contribute to the increase in electrical conductivity.

  17. Role of Reactive Intermediates in Manganese Oxide Formation By Filamentous Ascomycete Fungi

    NASA Astrophysics Data System (ADS)

    Zeiner, C. A.; Anderton, C.; Wu, S.; Purvine, S.; Zink, E.; Paša-Tolić, L.; Santelli, C. M.; Hansel, C. M.

    2014-12-01

    Biogenic manganese (Mn) oxide minerals are ubiquitous in the environment, and their high reactivity can profoundly impact the fate of contaminants and cycling of carbon and nutrients. In contrast to bacteria, the pathways utilized by fungi to oxidize Mn(II) to Mn(III,IV) oxides remain largely unknown. Here, we explore the mechanisms of Mn(II) oxidation by a phylogenetically diverse group of filamentous Ascomycete fungi using a combination of chemical assays and bulk and spatially-resolved mass spectrometry. We show that the mechanisms of Mn(II) oxidation vary with fungal species, over time during secretome compositional changes, and in the presence of other fungi. Specifically, our work implicates a dynamic transition in Mn(II) oxidation pathways that varies between species. In particular, while reactive oxygen species (ROS) produced via transmembrane NADPH oxidases are involved in initial oxidation, over time, secreted enzymes become important Mn(II) oxidation mediators for some species. In addition, the overall secretome oxidation capacity varies with time and fungal species. Secretome analysis reveals a surprising absence of enzymes currently considered to be Mn(II)-oxidizing enzymes in these organisms, and instead highlights a wide variety of redox-active enzymes. Furthermore, we implicate fungal cell defense mechanisms in the formation of distinct Mn oxide patterns when fungi are grown in head-to-head competition. The identification and regulation of these secreted enzymes are under current investigation within the bulk secretome and within the interaction zone of structured fungal communities. Overall, our findings illustrate that Ascomycete Mn(II) oxidation mechanisms are highly variable and are dictated by complex environmental and ecological interactions. Future work will explore the connection between Ascomycete Mn(II) oxidation and the ability to degrade cellulose, a key carbon reservoir for biofuel production.

  18. 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.

  19. Stability of Li- and Mn-Rich Layered-Oxide Cathodes within the First-Charge Voltage Plateau

    SciTech Connect

    Iddir, Hakim; Bareño, Javier; Benedek, Roy

    2016-01-01

    Li and Mn rich layered oxides xLi2MnO3•(1-x)LiMO2 enable high capacity and energy density Li-ion batteries, but undergo structural transformations during the first charge that degrade their performance, and result in Voltage Fade upon cycling. First-principles density-functional-theory simulations reveal atomic transformations that occur in the bulk during the first charge. The simulations and experiment (particularly XRD) show that the O and Mn sublattices remain intact during the early part of the voltage plateau, and significant transformations occur only well into the voltage plateau, with perhaps close to half of the Li in the Li2MnO3 domains removed. That Voltage Fade is actually observed experimentally for a first charge with only minimal activation (extending only slightly beyond the onset of the voltage plateau) may be a consequence of surface and interface instabilities. Implications for the achievement of high energy-density, low-fade battery operation are discussed.

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

    PubMed

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

    2017-12-01

    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/cm(2)), the photocurrent density of DNA@ Mn3(PO4)2/GO electrodes reached 9 μA/cm(2) 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.

  1. Development and evaluation of Mn oxide-coated composite adsorbent for the removal and recovery of heavy metals from coal processing wastewater. Final report, December 1995

    SciTech Connect

    Fan, Huan Jung; Anderson, P.R.

    1995-12-31

    The overall objective of this research was to evaluate a Mn oxide-coated granular activated carbon (MnGAC) for the removal and recovery of metals from wastewaters. The composite adsorbent was prepared by coating M-n-oxide onto granular activated carbon. Three coating methods (adsorption, precipitation, and dry oxidation) were developed and studied in this research. The adsorbent (MnTOG) prepared by a dry oxidation method had the highest Cu(II) adsorption capacity of the three synthesis methods. In multiple adsorption/regeneration cycle tests, MnTOG had better Cu(II) removal relative to those adsorbents prepared by other methods. MnTOG had the ability to remove Cu(II) and Cd(II) to trace level (< 4 ug/L) in a column process at least through 3000 and 1400 BV, respectively. Cd(II) removal was hindered by the presence of Cu(II). However, Cu(II) removal was only slightly reduced by the presence of Cd(II). Cu(II) adsorption in batch and fixed-bed processes onto MnTOG was successfully modeled with a homogeneous surface diffusion model (HSDM). However, the HSDM could only successfully describe the adsorption of Cd(II) onto MnTOG in the batch process, but not the fixed-bed process. M-n oxide can be deposited on GAC to create a composite adsorbent with an increased Cu(II) or Cd(II) adsorption capacity. Composite adsorbent (MnGAC) has the potential to become an efficient way to remove metals from metal contaminated wastewater.

  2. 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

  3. Effects of plant polyphenols and α-tocopherol on lipid oxidation, microbiological characteristics, and biogenic amines formation in dry-cured bacons.

    PubMed

    Wang, Yongli; Li, Feng; Zhuang, Hong; Li, Lianghao; Chen, Xiao; Zhang, Jianhao

    2015-03-01

    Effects of plant polyphenols (tea polyphenol [TP], grape seed extract [GSE], and gingerol) and α-tocopherol on physicochemical parameters, microbiological counts, and biogenic amines were determined in dry-cured bacons at the end of ripening. Results showed that plant polyphenols and α-tocopherol significantly decreased pH, thiobarbituric acid reactive substances content, and total volatile basic nitrogen (TVBN) compared with the control (P < 0.05). Microbial counts and biogenic amine contents in dry-cured bacons were affected by plant polyphenols or α-tocopherol, with TP being the most effective (P < 0.05) in reducing aerobic plate counts, Enterobacteriaceae, Micrococcaceae, yeast, and molds, as well as in inhibiting formation of putrescine, cadaverine, tyramine, and spermine. Principal component analysis indicated that the first 2 principal components (PC) explained about 85.5% of the total variation. PC1 was related with physicochemical factors, parts of biogenic amines, and spoilage microorganisms, whereas PC2 grouped the TVBN, tyramine, 2-phenylethylamine, yeast, and molds. These findings suggest that plant polyphenols, especially TP, could be used to process dry-cured bacons to improve the quality and safety of finished products.

  4. Catalytic oxidation of elemental mercury over the modified catalyst Mn/alpha-Al2O3 at lower temperatures.

    PubMed

    Li, Jianfeng; Yan, Naiqiang; Qu, Zan; Qiao, Shaohua; Yang, Shijian; Guo, Yongfu; Liu, Ping; Jia, Jinping

    2010-01-01

    In order to facilitate the removal of elemental mercury (Hg(0)) from coal-fired flue gas, catalytic oxidation of Hg(0) with manganese oxides supported on inert alumina (alpha-Al2O3) was investigated at lower temperatures (373-473 K). To improve the catalytic activity and the sulfur-tolerance of the catalysts at lower temperatures, several metal elements were employed as dopants to modify the catalyst of Mn/alpha-Al2O3. The best performance among the tested elements was achieved with molybdenum (Mo) as the dopant in the catalysts. It can work even better than the noble metal catalyst Pd/alpha-Al2O3. Additionally, the Mo doped catalyst displayed excellent sulfur-tolerance performance at lower temperatures, and the catalytic oxidation efficiency for Mo(0.03)-Mn/alpha-Al2O3 was over 95% in the presence of 500 ppm SO2 versus only about 48% for the unmodified catalyst. The apparent catalytic reaction rate constant increased by approximately 5.5 times at 423 K. In addition, the possible mechanisms involved in Hg(0) oxidation and the reaction with the Mo modified catalyst have been discussed.

  5. Reconstructing deglacial Atlantic deep water circulation using the Nd isotopic composition of Fe-Mn oxide coatings from planktonic foraminfera

    NASA Astrophysics Data System (ADS)

    Piotrowski, A. M.; Galy, A.; Roberts, N. L.; Nicholl, J.; Yu, J.; Clegg, J.; Pomies, C.; Scrivner, A. E.

    2009-12-01

    During the last few decades, neodymium isotopes have been increasingly used as a paleoceanographic proxy, to reconstruct past changes in deep ocean circulation [1,2] and river outputs to the surface ocean [3]. The widespread use of the Nd isotope proxy depends on whether the Nd isotopic composition of past seawater can be reliably extracted from authigenic sediment phases. Here we show that the Fe-Mn oxide coatings which are removed from planktonic foraminifera during reductive cleaning can be used to reconstruct past deep water Nd isotopic composition. In effect, we are using the planktonic foraminiferal calcite as a low-Nd carrier phase to leach authigenic Fe-Mn oxides, which have higher Nd concentration and record the Nd isotopic composition of bottom water. Leaching experiments on northeastern North Atlantic core BOFS 8K (52N, 22W, 4045mbsl) show methodological artifacts during bulk sediment leaching, but that the Fe-Mn oxide coatings from the planktonic foraminifera have the same Nd isotopic composition as bottom water. Interestingly, the Nd isotopic composition of planktonic foraminifera which have not been cleaned of Fe-Mn oxide coatings, and planktonic foraminifera which have been reductively cleaned by the Boyle and Kiegwin (1987) [4] method are within error of each other throughout the deglacial records, suggesting incomplete removal or significant re-scavenging of Nd from Fe-Mn oxides to cleaned foraminiferal calcite during reductive cleaning. There is no indication that we are incorporating a significant surface-water Nd isotopic signal. Instead, these records and laboratory tests may suggest that some published “cleaned” planktonic foraminiferal records are preserving a deep water signal, rather than a surface ocean signal. The downcore BOFS 8K record of planktonic foraminferal Fe-Mn coating Nd isotopes shows a large deglacial change consistent with benthic carbon isotopes, supporting more southern-sourced water reaching the site during the last

  6. 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.

  7. Pathway for Mn-cluster oxidation by tyrosine-Z in the S2 state of photosystem II

    PubMed Central

    Narzi, Daniele; Bovi, Daniele; Guidoni, Leonardo

    2014-01-01

    Water oxidation in photosynthetic organisms occurs through the five intermediate steps S0–S4 of the Kok cycle in the oxygen evolving complex of photosystem II (PSII). Along the catalytic cycle, four electrons are subsequently removed from the Mn4CaO5 core by the nearby tyrosine Tyr-Z, which is in turn oxidized by the chlorophyll special pair P680, the photo-induced primary donor in PSII. Recently, two Mn4CaO5 conformations, consistent with the S2 state (namely, S2A and S2B models) were suggested to exist, perhaps playing a different role within the S2-to-S3 transition. Here we report multiscale ab initio density functional theory plus U simulations revealing that upon such oxidation the relative thermodynamic stability of the two previously proposed geometries is reversed, the S2B state becoming the leading conformation. In this latter state a proton coupled electron transfer is spontaneously observed at ∼100 fs at room temperature dynamics. Upon oxidation, the Mn cluster, which is tightly electronically coupled along dynamics to the Tyr-Z tyrosyl group, releases a proton from the nearby W1 water molecule to the close Asp-61 on the femtosecond timescale, thus undergoing a conformational transition increasing the available space for the subsequent coordination of an additional water molecule. The results can help to rationalize previous spectroscopic experiments and confirm, for the first time to our knowledge, that the water-splitting reaction has to proceed through the S2B conformation, providing the basis for a structural model of the S3 state. PMID:24889635

  8. Novel regenerable sorbent based on Zr-Mn binary metal oxides for flue gas mercury retention and recovery.

    PubMed

    Xie, Jiangkun; Qu, Zan; Yan, Naiqiang; Yang, Shijian; Chen, Wanmiao; Hu, Lingang; Huang, Wenjun; Liu, Ping

    2013-10-15

    To capture and recover mercury from coal-fired flue gas, a series of novel regenerable sorbents based on Zr-Mn binary metal oxides were prepared and employed at a relatively low temperature. PXRD, TEM, TPR, XPS, and N2-adsorption methods were employed to characterize the sorbents. The Hg(0) adsorption performance of the sorbents was tested, and the effects of the main operation parameters and the gas components on the adsorption were investigated. Zr significantly improved the sorbent's mercury capacity, which was nearly 5mg/g for Zr0.5Mn0.5Oy. Furthermore, the spent sorbent could be regenerated by heating to 350°C, and the highly concentrated elemental mercury released could be facilely recycled. Therefore, a much greener process for mercury capture and recovery could be anticipated based on this regenerable sorbent.

  9. Magneto-transport properties of oriented Mn{sub 2}CoAl films sputtered on thermally oxidized Si substrates

    SciTech Connect

    Xu, G. Z.; Du, Y.; Zhang, X. M.; Liu, E. K.; Wang, W. H. Wu, G. H.; Zhang, H. G.

    2014-06-16

    Spin gapless semiconductors are interesting family of materials by embracing both magnetism and semiconducting due to their unique band structure. Its potential application in future spintronics requires realization in thin film form. In this Letter, we report fabrication and transport properties of spin gapless Mn{sub 2}CoAl films prepared on thermally oxidized Si substrates by magnetron sputtering deposition. The films deposited at 673 K are well oriented to (001) direction and display a uniform-crystalline surface. Magnetotransport measurements on the oriented films reveal a semiconducting-like resistivity, small anomalous Hall conductivity, and linear magnetoresistance representative of the transport signatures of spin gapless semiconductors. The magnetic properties of the films have also been investigated and compared to that of bulk Mn{sub 2}CoAl, showing small discrepancy induced by the composition deviation.

  10. Naturally Occurring Cr and Ni in the Sacramento Valley: II. Mn Oxides and the Mobility of Cr(VI) and Ni

    NASA Astrophysics Data System (ADS)

    Mills, C. T.; Morrison, J. M.; Goldhaber, M. B.; Foster, A. L.; Wolf, R. E.; Wanty, R. B.

    2007-12-01

    Soil manganese oxides can strongly affect the mobility and redox state of several toxic trace metals. We are studying the biogeochemical origin of Mn oxides and their association with Cr and Ni in soils of the Sacramento Valley, California. Both Cr and Ni are likely derived from ultramafic rocks that underlie Coast Range drainages to the west of the study area. The impact of weathering and erosion of these rocks is evident in the high levels of total Cr (80 to 1420 μg g-1) and nickel (65 to 224 μg g-1) that occur broadly in western Sacramento Valley soils. Although much of the Cr is bound in refractory spinels as Cr(III), some mobilization of Cr is apparent in the coincidence of enriched soils with high contents of Cr(VI) in ground water. Data from the National Water Information System (NWIS) shows 7 of 12 sampled wells within a 600 km2 area in the Sacramento Valley having Cr(VI) concentrations between 60 and 100% of the CA maximum contaminant level for drinking water (50 μg l-1). A 3-meter depth soil profile collected within the lower Putah Creek watershed was examined to investigate processes contributing to the oxidation and mobilization of natural Cr(III). Hydroxylamine hydrochloride-reducible Mn was determined for 8 depth intervals as a measure of manganese oxide occurrence. Concentrations of reducible Mn varied between 360 and 690 μg g-1 with depth and peaked at 2.7 m below the surface. Concentrations of anion exchangeable Cr(VI) were as high as 6 ng g-1 and were positively correlated (r2=0.59; p=0.07) with reducible Mn. Scanning electron microscopy of soil minerals from the 2.9 to 3.0 m interval showed Cr-bearing spinel grains enclosed within Mn oxide micro concretions suggesting a potential mechanism for the oxidation of natural Cr(III) to mobile Cr(VI). Consistent with the known tendency of Ni to sorb on Mn oxides, substantial Ni (13 to 45 μg g-1) was released in the reducible Mn fraction and it strongly correlates (r2=0.76; p=0.005) with reducible Mn

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

    SciTech Connect

    She, Xiao; Zhang, Xinmin; Liu, Jingya; Li, Liang; Yu, Xianghua; Huang, Zhiliang; Shang, Songmin

    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 scanning 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.

  12. Determining the Role of Multicopper Oxidases in Manganese(II) Oxidation by Marine Bacillus Spores

    NASA Astrophysics Data System (ADS)

    Dick, G. J.; Tebo, B. M.

    2005-12-01

    Bacteria play an important role in the environmental cycling of Mn by oxidizing soluble Mn(II) and forming insoluble Mn(III/IV) oxides. These biogenic Mn oxides are renowned for their strong sorptive and oxidative properties, which control the speciation and availability of many metals and organic compounds. A wide variety of bacteria are known to catalyze the oxidation of Mn(II); one of the most frequently isolated types are Bacillus species that oxidize Mn(II) only as metabolically dormant spores. We are using genetic and biochemical methods to study the molecular mechanisms of this process in these organisms. mnxG, a gene related to the multicopper oxidase (MCO) family of enzymes, is required for Mn(II) oxidation in the model organism, Bacillus sp. strain SG-1. Mn(II)-oxidizing activity can be detected in crude protein extracts of the exosporium and as a discrete band in SDS-PAGE gels, however previous attempts to purify or identify this Mn(II)-oxidizing enzyme have failed. A direct link between the Mn(II)-oxidizing enzyme and the MCO gene suspected to encode it has never been made. We used genetic and biochemical methods to investigate the role of the MCO in the mechanism of Mn(II) oxidation. Comparative analysis of the mnx operon from several diverse Mn(II)-oxidizing Bacillus spores revealed that mnxG is the most highly conserved gene in the operon, and that copper binding sites are highly conserved. As with Mn(II) oxidases from other organisms, heterologous expression of the Bacillus mnxG in E. coli did not yield an active Mn(II) oxidase. Purifying sufficient quantities of the native Mn(II) oxidase from Bacillus species for biochemical characterization has proven difficult because the enzyme does not appear to be abundant, and it is highly insoluble. We were able to partially purify the Mn(II) oxidase, and to analyze the active band by in-gel trypsin digestion followed by tandem mass spectrometry (MS/MS). MS/MS spectra provided a conclusive match to mnx

  13. Free-standing reduced graphene oxide/MnO2-reduced graphene oxide-carbon nanotube nanocomposite flexible membrane as an anode for improving lithium-ion batteries.

    PubMed

    Li, Yong; Ye, Daixin; Shi, Bin; Liu, Wen; Guo, Rui; Pei, Haijuan; Xie, Jingying

    2017-03-15

    To solve the barriers of poor rate capability and inferior cycling stability for the MnO2 anode in lithium ion batteries, we present a highly flexible membrane anode employing two-dimensional (2D) reduced graphene oxide sheets (rGO) and a three-dimensional (3D) MnO2-reduced graphene oxide-carbon nanotube nanocomposite (MGC) by a vacuum filtration and thermal annealing approach. All the components in the 2D/3D thin film anode have a synergistic effect on the improved performance. The initial discharge specific capacity of the electrode with the MnO2 content of 56 wt% was 1656.8 mA h g(-1) and remains 1172.5 mA h g(-1) after 100 cycles at a density of 100 mA g(-1). On enhancing the density to 200 mA g(-1), the membrane-electrode still exhibits a large reversible discharging capacity of ∼948.9 mA h g(-1) after 300 cycles. Moreover, the flexible Li-ion battery with a large area also shows excellent electrochemical performance in different bending positions, which provides the potential for wearable energy storage devices.

  14. Could hypoxia acclimation cause morphological changes and protect against Mn-induced oxidative injuries in silver catfish (Rhamdia quelen) even after reoxygenation?

    PubMed

    Dolci, G S; Rosa, H Z; Vey, L T; Pase, C S; Barcelos, R C S; Dias, V T; Loebens, L; Dalla Vecchia, P; Bizzi, C A; Baldisserotto, B; Burger, M E

    2017-05-01

    Exposure to hypoxia has shown beneficial adjustments in different species, including silver catfish (Rhamdia quelen), especially in situations of aquatic contamination with pollutants such as manganese (Mn). Considering that hypoxia is seasonal in the natural aquatic environment, we decided to assess whether these adaptive mechanisms could be maintained when reoxygenation is established. Silver catfish acclimated to moderate hypoxia (∼3 mg L(-1), 41% O2 saturation) for 10 days and subsequently exposed to Mn (∼8.1 mg L(-1)) for additional 10 days displayed lower (47%) Mn accumulation in the gills, and it was maintained (62.6%) after reoxygenation, in comparison to normoxia. Oxidative status in the gills allowed us to observe increased reactive species (RS) generation and protein carbonyl (PC) level together with decreased mitochondrial viability induced by Mn under normoxia. Inversely, while hypoxia per se was beneficial on RS generation and PC level, this acclimation was able to minimize Mn toxicity, as observed by the minor increase of RS generation and the minor reduction of mitochondrial viability, together with decreased PC level. Interestingly, after reoxygenation, part of the protective influences observed during hypoxia against Mn toxicity were maintained, as observed through a lower level of PC and higher mitochondrial viability in relation to the group exposed to Mn under normoxia. Only groups exposed to Mn under hypoxia showed increased activity of both catalase (CAT) and Na(+)/K(+)-ATPase in the gills, but, while CAT activity remained increased after reoxygenation, Na(+)/K(+)-ATPase activity was decreased by Mn, regardless of the oxygen level. Based on these outcomes, it is possible to propose that environment events of moderate hypoxia are able to generate rearrangements in the gills of silver catfish exposed to Mn, whose influence persists after water reoxygenation. These responses may be related to the adaptive development, reducing Mn

  15. 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.

  16. Carbon-wrapped MnO nanodendrites interspersed on reduced graphene oxide sheets as anode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Liu, Boli; Li, Dan; Liu, Zhengjiao; Gu, Lili; Xie, Wenhe; Li, Qun; Guo, Pengqian; Liu, Dequan; He, Deyan

    2017-02-01

    Carbon-wrapped MnO nanodendrites interspersed on reduced graphene oxide sheets (C-MnO/rGO) were prepared on nickel foam by a facile vacuum filtration and a subsequent thermal treatment. As a binder-free anode of lithium-ion battery, the nanodendritic structure of C-MnO accommodates the huge volume expansion and shortens the diffusion length for lithium ion and electron, rGO sheets prevent C-MnO nanodendites from aggregation and offer a good electronic conduction. As a result, the electrode with such a novel architecture delivers superior electrochemical properties including high reversible capacity, excellent rate capability and cycle stability. Moreover, MnO nanodendrites change to nanoparticles wrapped in graphene sheets during the lithiation/delithiation process, which is a more beneficial microstructure to further increase the specific capacity and cycle life of the electrode.

  17. Combined experimental and theoretical investigation of the CO 2 adsorption on LaMnO 3+y perovskite oxide

    NASA Astrophysics Data System (ADS)

    Hammami, Ramzi; Batis, Habib; Minot, Christian

    2009-10-01

    The surface interaction of CO 2 with the perovskite-type oxide LaMnO 3+y has been investigated by means of density functional theory calculations and experimental measurements of adsorption isotherms in the temperature range 298-473 K. A (1 0 0) oriented slab of the cubic structure was used for modeling CO 2 adsorption. The reference unit cell contains alternating LaO + layers and MnO2- layers; one slab is LaO +-terminated and the opposite surface is MnO2- terminated. A Freundlich isotherm fitted the experimental data satisfactorily. Analysis of the isosteric heat revealed an energetically heterogeneous character for the lanthanum manganite oxide surface, mainly due to the degree of heterogeneity of the adsorption center and due to the adsorbate-adsorbate lateral interactions. Considering theoretical calculations and thermodynamical approaches, two types of active sites were found to be responsible for irreversible and reversible adsorption of CO 2 as a function of surface coverage and O 2 treatment. Strong adsorption takes place on the surface containing La cations. The strongest adsorption is associated with surface oxygen vacancies, Fs° center. The next strongest adsorption, a flat adaptation of CO 2 molecules with respect to the surface sites, with a strong binding to a surface oxygen, leads to chemisorbed carbonate species. These adsorption modes are chiefly indicative of a high basic character of the lanthanum manganite oxide surface. Several cationic sites formed by lanthanum and manganese cations are able to weakly adsorb CO 2 molecules in perpendicular or bridged forms. The latter adsorption modes suggest a weak acidic character of the manganite adsorbent.

  18. Synthesis and Study of Optical properties of MgO based TM oxide (TM=Cu, Mn and Zn) nanocomposites

    NASA Astrophysics Data System (ADS)

    Tamizh Selvi, K.; Alamelumangai, K.; Priya, M.; Rathnakumari, M.; Kumar, P. Suresh; Sagadevan, Suresh

    2016-11-01

    A nanocomposite of MgO based transition metal (TM) oxide (TM=Zn, Mn, and Cu) was synthesized using sol-gel method. The powder x-ray diffraction confirmed the phase purity and particle size. The surface morphology and elemental composition were examined by High resolution scanning electron microscopy and energy-dispersive x-ray spectroscopy. The change in optical band gap of the synthesized nanocomposites, by increasing the Mg content was determined using UV-vis spectra and the luminescent properties were analyzed using photoluminescence spectra.

  19. Ultralow Loading of Silver Nanoparticles on Mn2O3 Nanowires Derived with Molten Salts: A High-Efficiency Catalyst for the Oxidative Removal of Toluene.

    PubMed

    Deng, Jiguang; He, Shengnan; Xie, Shaohua; Yang, Huanggen; Liu, Yuxi; Guo, Guangsheng; Dai, Hongxing

    2015-09-15

    Using a mixture of NaNO3 and NaF as molten salt and MnSO4 and AgNO3 as metal precursors, 0.13 wt % Ag/Mn2O3 nanowires (0.13Ag/Mn2O3-ms) were fabricated after calcination at 420 °C for 2 h. Compared to the counterparts derived via the impregnation and poly(vinyl alcohol)-protected reduction routes as well as the bulk Mn2O3-supported silver catalyst, 0.13Ag/Mn2O3-ms exhibited a much higher catalytic activity for toluene oxidation. At a toluene/oxygen molar ratio of 1/400 and a space velocity of 40,000 mL/(g h), toluene could be completely oxidized into CO2 and H2O at 220 °C over the 0.13Ag/Mn2O3-ms catalyst. Furthermore, the toluene consumption rate per gram of noble metal over 0.13Ag/Mn2O3-ms was dozens of times as high as that over the supported Au or AuPd alloy catalysts reported in our previous works. It is concluded that the excellent catalytic activity of 0.13Ag/Mn2O3-ms was associated with its high dispersion of silver nanoparticles on the surface of Mn2O3 nanowires and good low-temperature reducibility. Due to high efficiency, good stability, low cost, and convenient preparation, 0.13Ag/Mn2O3-ms is a promising catalyst for the practical removal of volatile organic compounds.

  20. Self-recovery of Pd nanoparticles that were dispersed over La(Sr)Fe(Mn)O3 for intelligent oxide anodes of solid-oxide fuel cells.

    PubMed

    Shin, Tae Ho; Okamoto, Yohei; Ida, Shintaro; Ishihara, Tatsumi

    2012-09-10

    Self-recovery is one of the most-desirable properties for functional materials. Recently, oxide anodes have attracted significant attention as alternative anode materials for solid-oxide fuel cells (SOFCs) that can overcome reoxidation, deactivation, and coke-deposition. However, the electrical conductivity and surface activity of the most-widely used oxide anodes remain unsatisfactory. Herein, we report the synthesis of an "intelligent oxide anode" that exhibits self-recovery from power-density degradation in the redox cycle by using a Pd-doped La(Sr)Fe-(Mn)O(3) cell as an oxide anode for the SOFCs. We investigated the anodic performance and oxidation-tolerance of the cell by using Pd-doped perovskite as an anode and fairly high maximum power densities of 0.5 and 0.1 W cm(-2) were achieved at 1073 and 873 K, respectively, despite using a 0.3 mm-thick electrolyte. Long-term stability was also examined and the power density was recovered upon exposure of the anode to air. This recovery of the power density can be explained by the formation of Pd nanoparticles, which were self-recovered through reoxidation and reduction. In addition, the self-recovery of the anode by oxidation was confirmed by XRD and SEM and this process was effective for improving the durability of SOFC systems when they were exposed to severe operating conditions.

  1. Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries.

    PubMed

    Wang, Xuanpeng; Xu, Xiaoming; Niu, Chaojiang; Meng, Jiashen; Huang, Meng; Liu, Xiong; Liu, Ziang; Mai, Liqiang

    2017-01-11

    K-ion battery (KIB) is a new-type energy storage device that possesses potential advantages of low-cost and abundant resource of K precursor materials. However, the main challenge lies on the lack of stable materials to accommodate the intercalation of large-size K-ions. Here we designed and constructed a novel earth abundant Fe/Mn-based layered oxide interconnected nanowires as a cathode in KIBs for the first time, which exhibits both high capacity and good cycling stability. On the basis of advanced in situ X-ray diffraction analysis and electrochemical characterization, we confirm that interconnected K0.7Fe0.5Mn0.5O2 nanowires can provide stable framework structure, fast K-ion diffusion channels, and three-dimensional electron transport network during the depotassiation/potassiation processes. As a result, a considerable initial discharge capacity of 178 mAh g(-1) is achieved when measured for KIBs. Besides, K-ion full batteries based on interconnected K0.7Fe0.5Mn0.5O2 nanowires/soft carbon are assembled, manifesting over 250 cycles with a capacity retention of ∼76%. This work may open up the investigation of high-performance K-ion intercalated earth abundant layered cathodes and will push the development of energy storage systems.

  2. Bi-Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    NASA Astrophysics Data System (ADS)

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-05-01

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn-Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi2O(1,3,5-BTC)2]n (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi4O2(COO)12 clusters which are further connected to Mn(COO)6 fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of {413.62}{413.68}{416.65}{418.610}{422.614}{43} corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones.

  3. Implication of (Mn)superoxide dismutase of Enterococcus faecalis in oxidative stress responses and survival inside macrophages.

    PubMed

    Verneuil, Nicolas; Mazé, Alain; Sanguinetti, Maurizio; Laplace, Jean-Marie; Benachour, Abdellah; Auffray, Yanick; Giard, Jean-Christophe; Hartke, Axel

    2006-09-01

    The gene encoding the manganese-containing superoxide dismutase (MnSOD) of Enterococcus faecalis was characterized. It is transcribed monocistronically from an upstream promoter identified by rapid amplification of cDNA ends (RACE)-PCR. A sodA mutant was constructed and characterized. Growth of the mutant strain was not significantly different from that of its wild-type counterpart in standing and aerated cultures. However, the mutant was more sensitive towards menadione and hydroperoxide stresses. The response to H(2)O(2) stress was analysed in more detail, and the mode of killing of this oxidant was different under anaerobic and aerobic conditions. Cultures grown and challenged under anaerobic conditions were highly sensitive to treatment with 35 mM H(2)O(2). They were largely protected by the iron chelator deferoxamine, which suggested that killing was mainly due to an enhanced Fenton reaction. In contrast, neither strain was protected by the iron chelators deferoxamine and diethylenetriaminepentaacteic acid when grown and challenged under aerobic conditions, which suggested that inactivation of the cells by H(2)O(2) was due to another killing mode. The sodA mutant was more sensitive under these conditions, showing that MnSOD is also important for protecting the cells from damage under aerobic conditions. Finally, the MnSOD of Ent. faecalis may be considered to be a virulence factor, since survival of the corresponding mutant strain was highly affected inside mouse peritoneal macrophages.

  4. Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

    PubMed

    Hong, Yong Seok; Kinney, Kerry A; Reible, Danny D

    2011-03-01

    Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase.

  5. Towards models of the oxygen-evolving complex (OEC) of photosystem II: a Mn4Ca cluster of relevance to low oxidation states of the OEC.

    PubMed

    Koumousi, Evangelia S; Mukherjee, Shreya; Beavers, Christine M; Teat, Simon J; Christou, George; Stamatatos, Theocharis C

    2011-10-21

    Synthetic access has been achieved into high oxidation state Mn/Ca chemistry with the 4 : 1 Mn : Ca stoichiometry of the oxygen-evolving complex (OEC) of plants and cyanobacteria; the anion of (Et(3)NH)(2)[Mn(III)(4)Ca(O(2)CPh)(4)(shi)(4)] has a square pyramidal metal topology and an S = 0 ground state.

  6. Sulfate radicals induced from peroxymonosulfate by cobalt manganese oxides (Co(x)Mn(3-x)O4) for Fenton-Like reaction in water.

    PubMed

    Yao, Yunjin; Cai, Yunmu; Wu, Guodong; Wei, Fengyu; Li, Xingya; Chen, Hao; Wang, Shaobin

    2015-10-15

    A series of CoxMn3-xO4 particles as Fenton-like solid catalysts were synthesized, and their catalytic performance in oxidative degradation of organic dye compounds in water was investigated. The surface morphology and structure of the CoxMn3-xO4 catalysts were characterized by field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that, as an oxide composite of Co and Mn elements, CoMn2O4 showed much stronger catalytic activity in peroxymonosulfate (PMS) oxidation than Co3O4, Mn2O3, and their physical mixture. Typically, the uses of 0.02 g/dm(3) CoMn2O4 and 0.2 g/dm(3) PMS yielded a nearly complete removal of Rhodamine B (0.03 g/dm(3)) in 80 min at 25 °C. The efficiency of Rhodamine B decomposition increased with increasing temperature (15-55 °C), but decreased with the increase of fulvic acid concentration (0-0.08 g/dm(3)). Furthermore, CoMn2O4 could maintain its catalytic activity in the repeated batch experiments. Moreover, HO· and SO4(·-) radicals participating in the process were evidenced using quenching experiments, and a rational mechanism was proposed. PMS oxidation with CoMn2O4 is an efficient technique for remediation of organic contaminants in wastewater.

  7. Biogenic UO2 - Characterization and Surface Reactivity

    SciTech Connect

    Singer, David M.; Farges, Francois; Brown, Gordon E. Jr.

    2007-02-02

    Nano-scale biogenic UO2 is easier to oxidize and more reactive to aqueous metal ions than bulk UO2. In an attempt to understand these differences in properties, we have used a suite of bulk and surface characterization techniques to examine differences in the reactivity of biogenic UO2 versus bulk UO2 with respect to aqueous Zn(II). Precipitation of biogenic UO2 was mediated by Shewanella putrefaciens CN32, and the precipitates were washed using two protocols: (1) 5% NaOH, followed by 4 mM KHCO3/KCl (NA-wash; 'NAUO2', to remove surface organic matter), and (2) 4 mM KHCO3-KCl (BI-wash; 'BIUO2', to remove soluble uranyl species). BET surface areas of biogenic-UO2 prepared using the two protocols are 128.63 m2g-1 and 92.56 m2g-1, respectively; particle sizes range from 2-10 nm as determined by FEG-SEM. Surface composition was probed using XPS, which showed a strong carbon 1s signal for the BI-washed samples; surface uranium is > 90% U(IV) for both washing protocols. U LIII-edge XANES spectra also indicate that U(IV) is the dominant oxidation state in the biogenic UO2 samples. Fits of the EXAFS spectra of these samples yielded half the number of uranium second-shell neighbors relative to bulk UO2, and no detectable oxygen neighbors beyond the first shell. At pH 7, the sorption of Zn(II) onto both biogenic and bulk UO2 is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. Fits of Zn K-edge EXAFS spectra for biogenic UO2 indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations are observed for the NA-washed samples, but not for the BI-washed ones, suggesting that Zn(II) sorbs directly to the UO2 surface in the first case, and possibly to organic matter in the latter. Further work is required to elucidate the binding mechanism of Zn(II) to bulk UO2.

  8. Composition Optimization of Al-DOPING Lithium Manganese Oxide from Al2O3-Li2CO3-MnO2 Ternary System

    NASA Astrophysics Data System (ADS)

    He, Gang; Sun, Xinyan; Hong, Jianhe; He, Mingzhong

    2013-07-01

    In order to synthesize eutectic compound of Al doping lithium manganese oxide which can be used as cathode material in lithium battery, using γ-Al2O3, Li2CO3 and MnO2 as starting raw materials, the composition optimization research work has been done by the solid state synthesis method. A limited composition range was found in Al2O3-Li2CO3-MnO2 ternary system, in which the synthesized Al doping lithium manganese oxides have single spinel structure and good electrochemical performance. The results showed that the LiAl0.04Mn1.96O4 material presented better charge-discharge cycling behavior than pure LiMn2O4, and showed the best electrochemistry property among the compounds in the Al2O3-Li2O-Mn2O3 ternary system. LiAl0.04Mn1.96O4 still kept perfect cubic structure, but LiMn2O4 kept the coexistence of the cubic and tetragonal phases after 50 charge-discharge cycles.

  9. 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 CO2, 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 Mn4CaO5 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 S1 to S2 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)2Mn(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.

  10. Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure

    NASA Astrophysics Data System (ADS)

    Hong, Fang; Yue, Binbin; Hirao, Naohisa; Liu, Zhenxian; Chen, Bin

    2017-03-01

    Highly efficient energy storage is in high demand for next-generation clean energy applications. As a promising energy storage material, the application of Mn2O3 is limited due to its poor electrical conductivity. Here, high-pressure techniques enhanced the electrical conductivity of Mn2O3 significantly. In situ synchrotron micro X-Ray diffraction, Raman spectroscopy and resistivity measurement revealed that resistivity decreased with pressure and dramatically dropped near the phase transition. At the highest pressure, resistivity reduced by five orders of magnitude and the sample showed metal-like behavior. More importantly, resistivity remained much lower than its original value, even when the pressure was fully released. This work provides a new method to enhance the electronic properties of Mn2O3 using high-pressure treatment, benefiting its applications in energy-related fields.

  11. Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure

    PubMed Central

    Hong, Fang; Yue, Binbin; Hirao, Naohisa; Liu, Zhenxian; Chen, Bin

    2017-01-01

    Highly efficient energy storage is in high demand for next-generation clean energy applications. As a promising energy storage material, the application of Mn2O3 is limited due to its poor electrical conductivity. Here, high-pressure techniques enhanced the electrical conductivity of Mn2O3 significantly. In situ synchrotron micro X-Ray diffraction, Raman spectroscopy and resistivity measurement revealed that resistivity decreased with pressure and dramatically dropped near the phase transition. At the highest pressure, resistivity reduced by five orders of magnitude and the sample showed metal-like behavior. More importantly, resistivity remained much lower than its original value, even when the pressure was fully released. This work provides a new method to enhance the electronic properties of Mn2O3 using high-pressure treatment, benefiting its applications in energy-related fields. PMID:28276479

  12. Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure.

    PubMed

    Hong, Fang; Yue, Binbin; Hirao, Naohisa; Liu, Zhenxian; Chen, Bin

    2017-03-09

    Highly efficient energy storage is in high demand for next-generation clean energy applications. As a promising energy storage material, the application of Mn2O3 is limited due to its poor electrical conductivity. Here, high-pressure techniques enhanced the electrical conductivity of Mn2O3 significantly. In situ synchrotron micro X-Ray diffraction, Raman spectroscopy and resistivity measurement revealed that resistivity decreased with pressure and dramatically dropped near the phase transition. At the highest pressure, resistivity reduced by five orders of magnitude and the sample showed metal-like behavior. More importantly, resistivity remained much lower than its original value, even when the pressure was fully released. This work provides a new method to enhance the electronic properties of Mn2O3 using high-pressure treatment, benefiting its applications in energy-related fields.

  13. Mn (III) tetrakis (4-benzoic acid) porphyrin scavenges reactive species, reduces oxidative stress, and improves functional recovery after experimental spinal cord injury in rats: comparison with methylprednisolone

    PubMed Central

    2013-01-01

    Background Substantial experimental evidence supports that reactive species mediate secondary damage after traumatic spinal cord injury (SCI) by inducing oxidative stress. Removal of reactive species may reduce secondary damage following SCI. This study explored the effectiveness of a catalytic antioxidant - Mn (III) tetrakis (4-benzoic acid) porphyrin (MnTBAP) - in removing reactive oxygen species (ROS), reducing oxidative stress, and improving functional recovery in vivo in a rat impact SCI model. The efficiency of MnTBAP was also compared with that of methylprednisolone – the only drug used clinically in treating acute SCI. Results In vivo measurements of time courses of ROS production by microdialysis and microcannula sampling in MnTBAP, methylprednisolone, and saline (as vehicle control)-treated SCI rats showed that both agents significantly reduced the production of hydrogen peroxide, but only MnTBAP significantly reduced superoxide elevation after SCI. In vitro experiments further demonstrated that MnTBAP scavenged both of the preceding ROS, whereas methylprednisolone had no effect on either. By counting the immuno-positive neurons in the spinal cord sections immunohistochemically stained with anti-nitrotyrosine and anti-4-hydroxy-nonenal antibodies as the markers of protein nitration and membrane lipid peroxidation, we demonstrated that MnTBAP significantly reduced the numbers of 4-hydroxy-nonenal-positive and nitrotyrosine-positive neurons in the sections at 1.55 to 2.55 mm and 1.1 to 3.1 mm, respectively, rostral to the injury epicenter compared to the vehicle-treated animals. By behavioral tests (open field and inclined plane tests), we demonstrated that at 4 hours post-SCI treatment with MnTBAP and the standard methylprednisolone regimen both significantly increased test scores compared to those produced by vehicle treatment. However, the outcomes for MnTBAP-treated rats were significantly better than those for methylprednisolone-treated animals

  14. Comparative study of supported CuOx and MnOx catalysts for the catalytic wet air oxidation of β-naphthol

    NASA Astrophysics Data System (ADS)

    Liu, Jie; Yu, Chaoying; Zhao, Peiqing; Chen, Gexin

    2012-09-01

    MnOx/nano-TiO2, MnOx/Al2O3-TiO2 (Al-Ti), CuOx/nano-TiO2 and CuOx/Al-Ti were prepared and their application in catalytic wet air oxidation (CWAO) of β-naphthol were investigated. The catalysts had been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) measurements. Phases of CuO, Cu2O, CuAl2O4, MnO2 and Mn2O3 could be found on the surface of the aforementioned catalysts. Significant differences in activities were observed among the prepared catalysts. Compared to CuOx/nano-TiO2, the combined action of highly dispersed CuO as well as CuAl2O4 of CuOx/Al-Ti helped to achieve higher activity for the CWAO of β-naphthol, while the Cu2O component lead to lower efficiency of CuOx/nano-TiO2. On the surface of MnOx/nano-TiO2, both the larger amount of highly dispersed MnO2 and the stronger electron transfer between MnO2 and Mn2O3 were helpful to promote the activity for the degradation of β-naphthol. However, the higher amount of bulk MnO2 and the weaker electron transfer for MnOx/Al-Ti were unfavorable to increase its efficiency. Among the four catalysts as-prepared, MnOx/nano-TiO2 was identified the highest activity with 93.7% COD removal.

  15. MnO/reduced graphene oxide sheet hybrid as an anode for Li-ion batteries with enhanced lithium storage performance

    NASA Astrophysics Data System (ADS)

    Mai, Y. J.; Zhang, D.; Qiao, Y. Q.; Gu, C. D.; Wang, X. L.; Tu, J. P.

    2012-10-01

    Relatively small hysteresis in voltage, appropriate electromotive force and low average delithiation voltage make MnO, among many transition metal oxides. MnO/reduced graphene oxide sheet (MnO/RGOS) hybrid is synthesized by a two-step electrode design consisting of liquid phase deposition of MnCO3 nanoparticles on the surface of graphene oxide sheets followed by heat treatment in flowing nitrogen. As an anode for Li-ion batteries, the MnO/RGOS hybrid electrode shows a reversible capacity of 665.5 mA h g-1 after 50 cycles at a current density of 100 mA g-1 and delivers 454.2 mA h g-1 at a rate of 400 mA g-1, which is obviously better than that of bare MnO electrode. Those reasons for such enhanced electrochemical properties are investigated by galvanostatic intermittent titration technique (GITT) as well as electrochemical impedance spectroscopy (EIS). The probable origins, in the term of thermodynamic and kinetic factors, for the marked hysteresis in voltage observed between charge and discharge are also discussed.

  16. Extracellular Dopamine Potentiates Mn-Induced Oxidative Stress, Lifespan Reduction, and Dopaminergic Neurodegeneration in a BLI-3–Dependent Manner in Caenorhabditis elegans

    PubMed Central

    Benedetto, Alexandre; Au, Catherine; Avila, Daiana Silva; Milatovic, Dejan; Aschner, Michael

    2010-01-01

    Parkinson's disease (PD)-mimicking drugs and pesticides, and more recently PD-associated gene mutations, have been studied in cell cultures and mammalian models to decipher the molecular basis of PD. Thus far, a dozen of genes have been identified that are responsible for inherited PD. However they only account for about 8% of PD cases, most of the cases likely involving environmental contributions. Environmental manganese (Mn) exposure represents an established risk factor for PD occurrence, and both PD and Mn-intoxicated patients display a characteristic extrapyramidal syndrome primarily involving dopaminergic (DAergic) neurodegeneration with shared common molecular mechanisms. To better understand the specificity of DAergic neurodegeneration, we studied Mn toxicity in vivo in Caenorhabditis elegans. Combining genetics and biochemical assays, we established that extracellular, and not intracellular, dopamine (DA) is responsible for Mn-induced DAergic neurodegeneration and that this process (1) requires functional DA-reuptake transporter (DAT-1) and (2) is associated with oxidative stress and lifespan reduction. Overexpression of the anti-oxidant transcription factor, SKN-1, affords protection against Mn toxicity, while the DA-dependency of Mn toxicity requires the NADPH dual-oxidase BLI-3. These results suggest that in vivo BLI-3 activity promotes the conversion of extracellular DA into toxic reactive species, which, in turn, can be taken up by DAT-1 in DAergic neurons, thus leading to oxidative stress and cell degeneration. PMID:20865164

  17. Quantification of both the presence, and oxidation state, of Mn in Bacillus atrophaeus spores and its imparting of magnetic susceptibility to the spores.

    PubMed

    Sun, Jianxin; Zborowski, Maciej; Chalmers, Jeffrey J

    2011-05-01

    Bacillus atrophaeus spores were previously reported to have significant magnetic susceptibility in a magnetic field due to the presence of Mn. However, relatively little is known about the total amount and distribution of the oxidation state of Mn associated with this specific strain's spores. Using the instrument, cell tracking velocimetry (CTV) both magnetically induced velocity and settling velocity was quantitatively measured. Visual observations, and calculated diameter using previously reported densities, indicate that the spores are present in the form of clusters of approximately 3-6 µm. Treatment of these clusters with EDTA or pH of 2.0 or below resulted in not only the disruption of the spore clusters, but also a significant decrease in magnetic susceptibility, in some cases by almost two orders of magnitude. Since the magnetic susceptibility of Mn varies significantly between the three typically reported valance states of Mn, Mn(II), Mn(III), and Mn(IV); X-Ray Photoelectron Spectroscopy, XPS, was used to determined the valance states of Mn in the spores. This XPS analysis, which penetrates up to 10 nm into the spore, returned the following fractions: 0.41, 0.38, and 0.21 for the valance states: Mn(II), Mn(III), and Mn(IV), respectively. The total mass of Mn associated with each spore cluster was determined by ICP-MS. A second, completely independent estimate of Mn mass associated with each spore cluster was made, by mathematically solving for the amount of Mn per spore cluster using the experimentally measured magnetophoretic mobility and the magnetic susceptibility of each of the three valence states from the XPS analysis. IPC-MS returned a value of 3.28 × 10(-11) g of Mn per spore cluster while the calculated estimation from mobility and XPS analysis retuned a value of 1.16 × 10(-11) g, which given the complexity of the two techniques, is a reasonable agreement. Finally, a discussion of potential applications of the magnetic properties

  18. Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes

    DOE PAGES

    Mohanty, Debasish; Sefat, Athena S.; Payzant, E. Andrew; ...

    2015-02-19

    Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (~250 mAh/g) lithium–manganese-rich (LMR) layered composite oxides. In spite of the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a ‘permanent’ spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalationmore » (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of ‘unfilled’ lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. Finally, these situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.« less

  19. Fast Optimization of LiMgMnOx/La2O3 Catalysts for the Oxidative Coupling of Methane.

    PubMed

    Li, Zhinian; He, Lei; Wang, Shenliang; Yi, Wuzhong; Zou, Shihui; Xiao, Liping; Fan, Jie

    2017-01-09

    The development of efficient catalyst for oxidative coupling of methane (OCM) reaction represents a grand challenge in direct conversion of methane into other useful products. Here, we reported that a newly developed combinatorial approach can be used for ultrafast optimization of La2O3-based multicomponent metal oxide catalysts in OCM reaction. This new approach integrated inkjet printing assisted synthesis (IJP-A) with multidimensional group testing strategy (m-GT) tactfully takes the place of conventionally high-throughput synthesis-and-screen experiment. Just within a week, 2048 formulated LiMgMnOx-La2O3 catalysts in a 64·8·8·8·8 = 262 144 compositional space were fabricated by IJP-A in a four-round synthesis-and-screen process, and an optimized formulation has been successfully identified through only 4·8 = 32 times of tests via m-GT screening strategy. The screening process identifies the most promising ternary composition region is Li0-0.48Mg0-6.54Mn0-0.62-La100Ox with an external C2 yield of 10.87% at 700 °C. The yield of C2 is two times as high as the pure nano-La2O3. The good performance of the optimized catalyst formulation has been validated by the manual preparation, which further prove the effectiveness of the new combinatorial methodology in fast discovery of heterogeneous catalyst.

  20. Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes

    SciTech Connect

    Mohanty, Debasish; Sefat, Athena S.; Payzant, E. Andrew; Li, Jianlin; Wood, David L.; Daniel, Claus

    2015-02-19

    Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (~250 mAh/g) lithium–manganese-rich (LMR) layered composite oxides. In spite of the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a ‘permanent’ spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of ‘unfilled’ lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. Finally, these situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.

  1. Unconventional irreversible structural changes in a high-voltage Li-Mn-rich oxide for lithium-ion battery cathodes

    NASA Astrophysics Data System (ADS)

    Mohanty, Debasish; Sefat, Athena S.; Payzant, E. Andrew; Li, Jianlin; Wood, David L.; Daniel, Claus

    2015-06-01

    Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li+), high capacity (∼250 mAh/g) lithium-manganese-rich (LMR) layered composite oxides. Despite the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a 'permanent' spin-glass type magnetically frustrated phase indicating a dominant AB2O4 (A = Li, B = Mn) type spinel after a short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of 'unfilled' lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. These situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.

  2. Crystal structure of BaMnB2O5 containing structurally isolated manganese oxide sheets

    PubMed Central

    Maschmeyer, Elizabeth M.; Sanjeewa, Liurukara D.; Ranmohotti, Kulugammana G. S.

    2016-01-01

    In an attempt to search for mixed alkaline-earth and transition metal pyroborates, the title compound, barium manganese(II) pyroborate, has been synthesized by employing a flux method. The structure of BaMnB2O5 is composed of MnO5 square pyramids that form Mn2O8 dimers by edge-sharing and of pyroborate units ([B2O5]4−) that are composed of two corner-sharing trigonal–planar BO3 units. These building blocks share corners to form ∞ 2[MnB2O5]2− layers extending parallel to (100). The Ba2+ cations reside in the gap between two manganese pyroborate slabs with a coordination number of nine. The title compound forms an inter­esting spiral framework propagating along the 21 screw axis. The structure is characterized by two alternating layers, which is relatively rare among known transition-metal-based pyroborate compounds. PMID:27920925

  3. Oxidative Stress Induced by MnSOD-p53 Interaction: Pro- or Anti-Tumorigenic?

    PubMed Central

    Robbins, Delira; Zhao, Yunfeng

    2012-01-01

    The formation of reactive oxygen species (ROS) is a result of incomplete reduction of molecular oxygen during cellular metabolism. Although ROS has been shown to act as signaling molecules, it is known that these reactive molecules can act as prooxidants causing damage to DNA, proteins, and lipids, which over time can lead to disease propagation and ultimately cell death. Thus, restoring the protective antioxidant capacity of the cell has become an important target in therapeutic intervention. In addition, a clearer understanding of the disease stage and molecular events that contribute to ROS generation during tumor promotion can lead to novel approaches to enhance target specificity in cancer progression. This paper will focus on not only the traditional routes of ROS generation, but also on new mechanisms via the tumor suppressor p53 and the interaction between p53 and MnSOD, the primary antioxidant enzyme in mitochondria. In addition, the potential consequences of the p53-MnSOD interaction have also been discussed. Lastly, we have highlighted clinical implications of targeting the p53-MnSOD interaction and discussed recent therapeutic mechanisms utilized to modulate both p53 and MnSOD as a method of tumor suppression. PMID:22007296

  4. The impact of electrostatics in redox modulation of oxidative stress by Mn porphyrins: Protection of SOD-deficient E. coli via alternative mechanism where Mn porphyrin acts as a Mn-carrier

    PubMed Central

    Rebouças, Júlio S.; DeFreitas-Silva, Gilson; Spasojević, Ivan; Idemori, Ynara M.; Benov, Ludmil; Batinić-Haberle, Ines

    2008-01-01

    Understanding the factors that determine the ability of Mn porphyrins to scavenge reactive species is essential for tuning their in vivo efficacy. We present herein the revised structure-activity relationships accounting for the critical importance of electrostatics in the Mn porphyrin-based redox modulation systems and show that the design of effective SOD mimics (per se) based on anionic porphyrins is greatly hindered by inappropriate electrostatics. A new strategy for the β-octabromination of the prototypical anionic Mn porphyrins Mn(III) meso-tetrakis(p-carboxylatophenyl)porphyrin ([MnIIITCPP]3− or MnTBAP3−) and Mn(III) meso-tetrakis(p-sulfonatophenyl)porphyrin ([MnIIITSPP]3−), to yield the corresponding anionic analogues [MnIIIBr8TCPP]3− and [MnIIIBr8TSPP]3−, respectively, is described along with characterization data, stability studies, and their ability to substitute for SOD in SOD-deficient E. coli. Despite the MnIII/MnII reduction potential of [MnIIIBr8TCPP]3− and [MnIIIBr8TSPP]3− being close to the SOD-enzyme optimum and nearly identical to that of the cationic Mn(III) meso-tetrakis(N-methylpyridinium-2-yl)porphyrin (MnIIITM-2-PyP5+), the SOD activity of both anionic brominated porphyrins ([MnIIIBr8TCPP]3−, E½ = +213 mV vs NHE, log kcat = 5.07; [MnIIIBr8TSPP]3−, E½ = +209 mV, log kcat = 5.56) is considerably lower than that of MnIIITM-2-PyP5+ (E½ = +220 mV, log kcat = 7.79). This illustrates the impact of electrostatic guidance of O2•− toward the metal center of the mimic. With low kcat, the [MnIIITCPP]3−, [MnIIITSPP]3−, and [MnIIIBr8TCPP]3− did not rescue SOD-deficient E. coli. The striking ability of [MnIIIBr8TSPP]3− to substitute for the SOD enzymes in the E. coli model does not correlate with its log kcat. In fact, the protectiveness of [MnIIIBr8TSPP]3− is comparable to or better than that of the potent SOD mimic MnIIITM-2-PyP5+, even though the dismutation rate constant of anionic complex is 170-fold smaller

  5. Nitrate storage behavior of Ba/MnOx-CeO2 catalyst and its activity for soot oxidation with heat transfer limitations.

    PubMed

    Wu, Xiaodong; Liu, Shuang; Lin, Fan; Weng, Duan

    2010-09-15

    A BaMnCe ternary catalyst was prepared by impregnating barium acetate on MnO(x)-CeO(2) mixed oxides, with the monoxide supported catalysts and the solid solution support as references. The activities of the catalysts for soot oxidation were evaluated in the presence of NO under an energy transference controlled regime. BaMnCe presented the lowest maximal soot oxidation rate temperature at 393 degrees C among the catalysts investigated. Although BaMnCe experienced a loss in the specific surface area and low-temperature redox property due to blocking of the support pores by barium carbonate, its superior soot oxidation activity highlighted the importance of relatively stable bidentate/monodentate nitrates coordinated to Mn(x+) and Ce(x+) sites and more stable ionic barium nitrate. About half of the nitrates stored on this catalyst decomposed within the temperature interval of 350-450 degrees C, and the ignition temperature of soot decreased significantly with involvement of the nitrates or NO(2) released.

  6. Three-Dimensional Reduced Graphene Oxide Coupled with Mn3O4 for Highly Efficient Removal of Sb(III) and Sb(V) from Water.

    PubMed

    Zou, Jian-Ping; Liu, Hui-Long; Luo, Jinming; Xing, Qiu-Ju; Du, Hong-Mei; Jiang, Xun-Heng; Luo, Xu-Biao; Luo, Sheng-Lian; Suib, Steven L

    2016-07-20

    Highly porous, three-dimensional (3D) nanostructured composite adsorbents of reduced graphene oxides/Mn3O4 (RGO/Mn3O4) were fabricated by a facile method of a combination of reflux condensation and solvothermal reactions and systemically characterized. The as-prepared RGO/Mn3O4 possesses a mesoporous 3D structure, in which Mn3O4 nanoparticles are uniformly deposited on the surface of the reduced graphene oxide. The adsorption properties of RGO/Mn3O4 to antimonite (Sb(III)) and antimonate (Sb(V)) were investigated using batch experiments of adsorption isotherms and kinetics. Experimental results show that the RGO/Mn3O4 composite has fast liquid transport and superior adsorption capacity toward antimony (Sb) species in comparison to six recent adsorbents reported in the literature and summarized in a table in this paper. Theoretical maximum adsorption capacities of RGO/Mn3O4 toward Sb(III) and Sb(V) are 151.84 and 105.50 mg/g, respectively, modeled by Langmuir isotherms. The application of RGO/Mn3O4 was demonstrated by using drinking water spiked with Sb (320 μg/L). Fixed-bed column adsorption experiments indicate that the effective breakthrough volumes were 859 and 633 mL bed volumes (BVs) for the Sb(III) and Sb(V), respectively, until the maximum contaminant level of 5 ppb was reached, which is below the maximum limits allowed in drinking water according to the most stringent regulations. The advantages of being nontoxic, highly stable, and resistant to acid and alkali and having high adsorption capacity toward Sb(III) and Sb(V) confirm the great potential application of RGO/Mn3O4 in Sb-spiked water treatment.